Chemistry and Technology of The Cosmetics and Toiletries Industry (PDFDrive)

Chemistry and Technology
of the
Cosmetics and Toiletries Industry
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Chemistry and Technology
of the
Cosmetics and Toiletries Industry
Second edition
Edited by
D.F. WILLIAMS
Environment and Quality Assurance Manager
Givaudan-Roure UK
Surrey
UK
and
W.H. SCHMITT
Vice President, R&D
Chesebro ugh Ponds, Inc
Connecticut
USA
BLACKIE ACADEMIC &. PROFESSIONAL

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First edition 1992

Second edition 1996
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001: 10.1 007/978-94-009-1555-8
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Contents
List of Contributors xiii

Preface xv
Preface to the first edition xvii
1 Raw materials 1
E. SPIESS
1.1 Introduction 1
1.2 Basic surfactants 1
1.2.1 Alkyl ether sulfates I
1.2.2 Alkyl sulfates 4
1.2.3 a-Olefin sulfonates 5
1.2.4 Other basic surfactants 6
1.3 Mild anionic surfactants 6
1.3.1 Sulfosuccina tes 6
1.3.2 Cocoyl isethionates 7
1.3.3 Acyl amides 8
1.3.4 Alkyl ether carboxylates 8
1.3.5 Magnesium surfactants 9
1.3.6 Alkyl phosphates 9
1.4 Amphoteric surfactants 10
1.4.1 Alkyl betaines 10
1.4.2 Alkylamido betaines 11
1.4.3 Acylamphoglycinates and acylamphopropionates 11
1.4.4 Amine oxides 12
1.5 Non-ionic surfactants 13
1.5.1 Ethoxylated products 13
1.5.2 Alkyl polyglycosides 15
1.6 Cationic surfactants 15
1.6.1 Monoalkyl quaternaries 16
1.6.2 Dialkyl quaternaries 16
1.6.3 Trialkyl quaternaries 17
1.6.4 Benzyl quaternaries 18
1.6.5 Ester quaternaries 18
1.6.6 Ethoxylated quaternaries 18
1.7 Shampoo and bath additives 19
1.7.1 Thickeners 19
1.7.2 Foam stabilizers 20
1.7.3 Pearle scent agents 21
1.7.4 Conditioning agents 21
1.7.5 Emollients 21
1.7.6 Sequestering agents 22
1.8 Oil components 22
1.8.1 Mineral oil 22
1.8.2 Natural oils 23
1.8.3 Synthetic oils 24
vi CONTENTS
1.9 Waxes 26
1.9.1 Natural waxes 26
1.9.2 Synthetic waxes 27
1.10 Silicone oils 27
1.11 Cream bases 28
1.11.1 Fatty alcohols 28
1.11.2 Polyol esters 28
1.11.3 Fatty acids 29
1.12 Oil-in-water (O/W) emulsifiers 29
1.12.1 Anionic O/W emulsifiers 29
1.12.2 Cationic O/W emulsifiers 30
1.12.3 Non-ionic O/W emulsifiers 30
1.12.4 O/W stabilizers 30
1.13 Water-in-oil (W/O) emulsifiers 31
1.13.1 Single W / 0 emulsifiers 31
1.13.2 Lanolin derivatives 32
1.13.3 Absorption bases 32
1.13.4 W / 0 stabilizers 32
1.14 Humectants 33
1.15 Aerosol propellants 33
1.15.1 Hydrocarbons 33
1.15.2 Dimethyl ether 33
References 34
2 Hair-care products 36
J.J. SHIPP
2.1 Introduction 36
2.2 Hair: structure and chemistry 37
2.2.1 Structure of hair keratin 38
2.3 Shampoos 39
2.3.1 Detergents 40
2.3.2 Thickeners and foam stabilisers 45
2.3.3 Perfumes 49
2.3.4 Preservatives 49
2.3.5 Opacifiers and pearlisers 50
2.3.6 Conditioning agents 52
2.3.7 Colours and colour fading 55
2.3.8 Other additives 56
2.4 Conditioners 58
2.4.1 Cationic surfactants 60
2.4.2 Cationic polymers and other active ingredients 63
2.4.3 Bodying agents 66
2.4.4 Auxiliary emulsifiers 66
2.4.5 Oil components 66
2.4.6 Thickeners 67
2.4.7 Perfumes 67
2.4.8 Preservatives 68
2.4.9 Colours 68
2.4.10 Manufacture 68
2.4.11 Clear conditioners 68
2.4.12 Hair thickeners 69
2.4.13 Leave-on conditioners 69
2.4.14 'Hot oils', tonics and other conditioners 70
2.5 Styling aids 72
2.5.1 Hairsprays 72
2.6 Setting lotions 77
CONTENTS Vll
2.7 Other styling aids in spray form 78

2.8 Hair gels 79
2.9 Styling creams and glazes 82
2.10 Hair oils/brilliantines/pomades/styling waxes 83
2.11 Hair creams 83
2.12 Permanent waving 84
2.12.1 Neutralisation 88
2.13 Bleaches 89
2.14 Hair dyes 91
2.14.1 Temporary dyes 91
2.14.2 Semi-permanent colourants 92
2.14.3 Permanent hair dyes 93
2.14.4 Other hair dyes 97
2.14.5 Dye removers 97
2.15 Product evaluation and testing 98
2.15.1 Stability testing 98
2.15.2 Claims justification 99
2.15.3 Product safety 99
2.16 Summary 99
References 100
3 Skin-care products 104

W.H. SCHMITT
3.1 Introduction 104
3.2 Anatomy and physiology of the skin 104
3.2.1 Epidermis 106
3.2.2 Dermis 106
3.2.3 Skin color 108
3.3 Test methods 108
3.3.1 Efficacy testing 109
3.4 Formulation 112
3.4.1 Formula information 112
3.4.2 Consumer testing 113
3.4.3 Stability testing 114
3.4.4 Microbiological testing 115
3.4.5 Manufacturing trials 115
3.4.6 Safety testing 116
3.4.7 Regulatory and environmental requirements 116
3.5 Skin cleansers 117
3.5.1 Anhydrous oily cleansers 118
3.5.2 Water-in-oil emulsions: cold creams 118
3.5.3 Oil-in-water emulsions: cleansing milks 119
3.5.4 Fatted mild syndet foaming bars and cleansers 120
3.5.5 Super fatted bar soaps 121
3.5.6 Astringents I toners 121
3.5.7 Bar soaps 122
3.5.8 Particulate scrubs 122
3.6 Moisturizers 123
3.6.1 All-purpose creams 124
3.6.2 Hand and body lotions 125
3.6.3 Hand and body creams 126
3.6.4 Facial moisturizer lotions 126
3.6.5 Facial moisturizer creams: night creams 127
3.7 Anti-ageing products 128
3.8 Sunscreen products 130
3.8.1 Solar radiation 130
viii CONTENTS
3.8.2 Sunscreen chemicals 133

3.8.3 Testing 133
3.8.4 Sunscreen formulations 136
3.9 Acne 141
3.9.1 Sebaceous gland 141
3.9.2 Acne nomenclature 142
3.9.3 Acne grades 142
3.9.4 Treatment 143
3.10 Liposomes 144
References 145
4 Color cosmetics 149

J. CUNNINGHAM

4.2 Lip color 149
4.2.1 Lipsticks 149
4.2.2 Lip glosses 156
4.2.3 Lip liners 157
4.3 Nail polish 159
4.3.1 Consumer expectations 159
4.3.2 Formulation 159
4.4 Face make-up 162
4.4.1 Consumer expectations 162
4.4.2 Face powders 163
4.4.3 Liquid foundations 168
4.4.4 Blushers 170
4.5 Eye make-up 171
4.5.1 Eyeshadow 171
4.5.2 Mascara 174
4.5.3 Eyeliners 177
4.6 Preservation 179
4.7 Color coating 180
4.8 General considerations 181
References 181
Further reading 181
5 Baby care 183

J.L. KNOWLTON
5.2 Specific basic requirements for baby products 183
5.3 Product types and their presentation 184
5.3.1 Baby powders 184
5.3.2 Lotions and creams 186
5.3.3 Soaps 188
5.3.4 Hair products 188
5.3.5 Bath products 190
5.3.6 Moussed products 191
5.3.7 Wipes and tissues 192
5.3.8 Oils 192
5.3.9 Perfumes and colognes 193
5.4 Raw materials for baby products 194
CONTENTS IX
5.5 Developmental pathways 195

5.5.1 Formulation development 195
5.5.2 Practical requirements 195
5.6 Product evaluation 195
5.6.1 Laboratory evaluation 195
5.6.2 Mother and baby panels 196
5.6.3 Consumer research 196
5.7 Product safety requirement 197
5.8 Product preservation 198
5.9 Product stability 198
5.10 Manufacture and quality control 199
5.10.2 Quality control 200
References 200
Further reading 200
6 Afro products 201

J.F.L. CHESTER
6.2 Hair structures 201
6.3 Skin characteristics 202
6.4 Hair products 203
6.4.1 Relaxing and restyling products 203
6.4.2 Hair pomades and grooming aids 216
6.5 Skin products 218
6.5.1 Raw material selection-factors for consideration 218
6.5.2 Emulsification systems 219
6.6 General practical considerations 224
Further reading 224
7 Dental products 225

M. PADER

7.2 The human dentition and its environment 226
7.2.1 Teeth and associated oral structures 226
7.2.2 Saliva and crevicular fluid 226
7.3 Oral accretions and conditions 228
7.3.1 Dental pellicle 228
7.3.2 Dental plaque 228
7.3.3 Dental calculus (tartar) 231
7.3.4 Periodontal diseases 232
7.3.5 Dental stain 233
7.3.6 Dental hypersensitivity 234
7.3.7 Oral malodor 234
7.4 Oral-care products 235
7.4.1 Product categories 235
7.4.2 Toothpaste 235
7.4.3 Tooth powder 236
7.4.4 The toothbrush 236
7.4.5 Oral rinses 237
7.4.6 Mechanical devices 237
7.5 Consumer practices 237
X CONTENTS
7.6 Oral-care product marketing 239

7.6.1 Targeting consumer groups 239
7.6.2 Regulation of the industry 240
7.6.3 Product evaluation; support of marketing claims 242
7.7 Principles of product formulation 244
7.7.1 The toothbrush and other mechanical aids 244
7.7.2 Toothpaste formulation practice 246
7.7.3 Basic dentifrice ingredients 250
7.7.4 Type I versus Type II toothpastes 260
7.7.5 Dentifrice manufacture 261
7.7.6 Dentifrice packaging 262
7.8 Oral rinses 263
7.8.1 Function 263
7.8.2 Dosage forms and formulations 264
7.8.3 Pre-brushing dental rinse 265
7.8.4 Manufacture and packaging 265
7.9 Active agents 266
7.9.1 Anti-caries agents 266
7.9.2 Reduction in tooth hypersensitivity 266
7.9.3 Reduction of plaque and calculus and improvement in gingival
health 267
7.10 Specialty products 268
7.10.1 Tooth whiteners 268
7.10.2 Products for the edentulous 269
References 269
8 Perfumery 272
A. DALLIMORE
8.2 Fragrance--a definition 272
8.3 Role of fragrance 272
8.4 Perfumery raw materials 273
8.4.1 Natural perfumery raw materials 273
8.4.2 Synthetic perfumery raw materials (aroma chemicals) 274
8.5 Development of a fragrance 276
8.5.1 The brief 276
8.5.2 The creative process 278
8.5.3 Evaluation and marketing of the new creation 281
8.6 The current market in fine fragrance 281
8.6.1 The trickle-down effect 282
8.7 Odour types 282
8.8 Technical performance of perfumes 283
8.9 Stability testing 285
8.10 Compounding 286
8.11 Quality control 286
8.12 Special additives 287
8.13 Glossary of odour descriptors 288
Further reading 289
9 Personal hygiene products 290

M.J. WILLCOX
9.2 Soap and other solid bathing products 290
CONTENTS Xl
9.2.1 Toilet soaps 290

9.2.2 Shaving soaps 295
9.2.3 Transparent/translucent soaps 295
9.2.4 Synthetic detergent/combination bars 299
9.2.5 Bath salts/bath crystals/bath cubes 299
9.3 Liquid bathing and showering products 301
9.3.1 FoaJ,Il baths 301
9.3.2 Bat4 oils 305
9.3.3 Shower gels 308
9.3.4 After-bath and after-shower conditioners 309
10 Antiperspirants and deodorants 310

R. GIOVANNIELLO
10.2 Regulations 312
10.3 Mechanism of sweating 314
10.4 Antiperspirant active properties 315
10.4.1 Basic aluminum chloride 315
10.4.2 Aluminum zirconium complexes 321
10.5 Clinical assessment 324
10.6 Formulary considerations 326
10.6.1 Performance 326
10.6.2 Cost 327
10.6.3 Esthetics 328
10.7 Formulations 329
10.7.1 Roll-on products 329
10.7.2 Stick products 332
10.7.3 Spray products 335
10.8 Deodorants 338
10.8.1 Odor control 338
10.8.2 Clinical assessment 339
10.8.3 Formulations 340
References 342
Miscellaneous patent literature 343
11 Regulation of cosmetic products 344

E.G. MURPHY and P.l. WILSON
11.1 Historical development 344
11.2 Self-regulation 345
11.3 Regulation in the United States 346
11.3.1 Federal regulation of cosmetics 346
11.3.2 Cosmetic composition 347
11.3.3 Cosmetic labeling 348
11.3.4 The relationship of cosmetic products to drugs 350
11.3.5 Regulation of cosmetics by other federal agencies 353
11.3.6 Cosmetics and the Consumer Product Safety Commission 355
11.3.7 Regulation of cosmetics by the states 355
11.3.8 Conclusion 355
11.4 Regulation in Europe 356
11.5 Regulation in Japan 357
11.6 Regulation in other countries 357
11.7 General considerations 358
11.7.1 Environmental impact 35R
xu CONTENTS
11. 7.2 Animal protection and rights 358

11. 7.3 Drug or cosmetic? Borderline products 358
11.7.4 Product liability 359
References 359
12 Quality 362
W.E. DUPUY
12.1 Introduction to quality 362
12.2 Definition of quality 362
12.3 Inspection 363
12.4 Prevention 364
12.5 Total quality 365
12.5.1 Product design 367
12.5.2 Quality assurance 369
12.5.3 Manufacturing processes and technology 369
12.5.4 Cost of quality 370
12.5.5 Human and organisational aspects 370
12.6 The new thinking 373
12.7 Quality standards and guides 373
12.7.1 Links between ISO 9000 and total quality 374
References 377
Further reading 377
13 Environmental issues 378

D.F. WILLIAMS
13.2 Raw materials 379
13.3 Energy 379
13.4 Water 380
13.5 Waste 380
13.6 Packaging waste 380
13.7 Eco labelling 381
13.8 Volatile organic compounds 381
13.9 Environmental management systems 382
13.10 Sources of information 382
13.10.1 European Community 383
13.10.2 USA 384
13.10.3 UK 384
Appendices 385
Appendix I List of suppliers 385
Appendix II Useful addresses 387
Index 389
Contributors
Mr J.F.L. Chester Conform Associates, 80 Broadacres, Carlton, Goole,

East Yorkshire DN14 9NF, UK
Mr J. Cunningham Vice-President Technical Services, Cosmo1ab, 1100
Garrett Road, Lewisberg, Tennessee 37091, USA
Mr A. Dallimore Perfumery Director, Phoenix Fragrances Ltd, Unit 6,
Fleming Close, Park Farm Industrial Estate, Welling-
borough, Northants NN8 6UF, UK
Dr W.E. Dupuy Personnel and Total Quality Director, Rimme1 Inter-
national, Carlton Road, Ashford, Kent, UK
Mr R. Giovanniello Vice President-Technical Director, Westwood Chem-
ical Corporation, 46 Tower Drive, Middletown, NY
10940, USA
Mr. J.L. Knowlton Vice President, Research and Development, Justin-
Avon, 326 Fifth Street, Wynberg, Johannesburg,
Republic of South Africa
E.G. Murphy Esq. Bryan Cave LLP, 700 Thirteenth Street, N.W.
Washington, DC 20005-3960, USA
Dr M. Pader President, Consumer Products Development
Resources Inc., 1358 Sussex Road, Teaneck 07666,
New Jersey, USA
Mr W.H. Schmitt Senior Vice President, Research and Development,
Chesebrough Ponds USA Co., Trumbull Corporate
Park, Merritt Boulevard, Trumbull, Connecticut
06611, USA
Mr J.J. Shipp Technical Director, Chester Laboratories Ltd, Unit
11, First Avenue, Deeside Industrial Park, C1wyd
CH52NU, UK
Mr E. Spiess Sales Manager, Akzo Nobel Chemicals GmbH, Post-
fach 100132, D-52301, Duren, Germany
Mr M.J. Willcox Technical Director, The Standard Soap Co. Ltd,
Ashby de 1a Zouch, Leicestershire LE6 2HG, UK
xiv CONTRIBUTORS
Mr D.F. Williams Environment and Quality Assurance Manager, Givau-

dan-Roure UK, Godstone Road, Whyteleafe, Surrey,
UK
Dr P.J. Wilson Adams, Wilson & Associates Ltd, 8 Queens Park
Road, Chester CH4 7AD, UK
Preface
This second edition has been designed to monitor the progress in develop-
ment over the past few years and to build on the information given in the first
edition.
It has been extensively revised and updated. My thanks go to all who have
contributed to this work.
D.F.W. May 1996

Preface to the first edition
This book is the result of a group of development scientists feeling that there
was an urgent need for a reference work that would assist chemists in
understanding the science involved in the development of new products. The
approach is to inform in a way that allows and encourages the reader to
develop his or her own creativity in working with marketing colleagues on
the introduction of new products.
Organised on a product category basis, emphasis is placed on formulation,
selection of raw materials, and the technology of producing the products
discussed. Performance considerations, safety, product liability and all aspects
of quality are covered. Regulations governing the production and sale of
cosmetic products internationally are described, and sources for updated
information provided.
Throughout the book, reference is made to consumer pressure and
environmental issues-concerns which the development scientist and his or
her marketing counterpart ignore at their own, and their employer's peril. In
recent years, many cosmetic fragrances and toiletry products have been
converted from aerosols to mechanically press uri sed products or sprays, and
these are described along with foam products such as hair conditioning
mousses.
The information set out in the following pages has been acquired by the
hard work and enthusiasm of a number of international authors who hold
senior positions within the industry and it has been my privilege to work
with William H. Schmitt in bringing together their accumulated knowledge.
Information presented is given in good faith and the greatest possible care
has been taken to ensure that it is correct. No warranty can, however, be
given on fitness for a particular use or freedom from patent infringement. All
the information given is for consideration, study and verification. It is hoped
that the book will inspire newcomers to progress within, and advance, the
industry that has provided me with a livelihood and much enjoyment over
many years.
D.F.W.1992
1 Raw materials
E. SPIESS
1.1 Introduction
A wide range of chemical and natural materials is used in the formulation

of cosmetic and toiletry preparations. It is outside the scope of this book
to give a complete overview, therefore only those materials of primary
importance will be stressed. This chapter deals with the basic raw materials
for the production of hair-, skin- and oral-care products. It does not include
special additives such as herbal extracts, nor raw materials, such as pigments,
for decorative cosmetics. An overview of herbal extracts is given by Nowak [1].
The materials described are listed by application rather than by chemical
classification, which is difficult to follow. This means that some products are
described twice, for example the alkyl sulfates as basic surfactants and as
oil-in-water emulsifiers, but makes it easier to provide an overview of a
specific field and allows the direct comparison of possible ingredients. For
each material, the chemical pathway of production and special precautions
regarding stability and compatibility with other ingredients are also described.
1.2 Basic surfactants
The purpose of a shampoo or shower bath is to clean the skin and hair.
Customers also expect a dense and luxurious lather, although this effect is
not essential for the cleansing. To fulfil these requirements, the so-called basic
or primary surfactants, which are the backbone of the cleansing products,
are necessary.
1.2.1 Alkyl ether sulfates
(OCHzCHz)xS04M
Alkyl ether sulfates are the most widely used surfactants for cosmetics and
toiletries due to their well-balanced properties. They are excellent foamers,
= alkyl C chain = R
2 COSMETICS AND TOILETRIES INDUSTRY
although the foam structure is relatively coarse. Foaming is not affected by

hard water and this, together with their low critical micelle concentration,
makes alkyl ether sulphates ideal for use in foam-bath preparations, shampoos
and shower baths. Therefore Gohlke and Berghausen called it an 'ideal
Tensid' [2].
The alkyl moiety usually consists of a mixture of C 12 -C 16 chains. The
degree of ethoxylation is between 1 and 4 (x = 1-4). M is either sodium,
ammonium or magnesium.
In former times, chlorosulfonic acid was used in a batch process. Today,
however, the most common process for the production of alkyl ether sulfates is
the continuous S03-sulfonation of ethoxylated fatty alcohols in a thin-film
reactor, followed by a neutralization step. The typical products, called lauryl
ether sulfates or sodium laureth sulfate (CTFA-Cosmetic Toiletry and
Fragrance Association -nomenclature), are based on alcohol mixtures. Well-
accepted and approved for use in cosmetics and toiletries are the products
based on 'natural' alcohols derived from the coconut palm (C 12 approx. 70%;
C 14 approx. 25%; C 16 approx. 5%), the 'semi-natural' alcohols from the
Ziegler process (CdC 14 approx. 50/50%) and the partly branched SHOp@
alcohols (C12:C13:C14:C15 approx. 20:30:30:20)[3].
The properties of alkyl ether sulfates are largely determined by the number
of ethylene glycol units in the starting ethoxylated alcohols. Figure 1.1 shows
the influence of the degree of ethoxylation on skin compatibility as measured
by the Zein number (an in vitro measurement of the irritancy of surfactants).
The presence of 2 to 3 ethylene glycol units leads to ideal behavior regarding
foam and detergency. Such alkyl ether sulphates are easily thickened with
salts and show good water solubility, even at low temperatures. The skin
and eye compatibility is acceptable for most applications but is usually
700
600
... 500
1l
E 400
::J
C
c 300
'0:;
N
200
100
oL-______
o 2 4
-=======~~
6 8 10 12
Moles of ethylene oxide
Figure 1.1 Zein number as a function of the POE-chain (moles of ethylene oxide) in laureth-
x-sulfates, sodium and magnesium forms [4].
RAW MATERIALS 3
improved by combination with mild secondary surfactants. Higher degrees
of ethoxylation, up to 8 or 12, can significantly reduce irritation. Combina-
tions of these highly ethoxylated ether sulfates, especially the magnesium
form with normal ether sulfates, are recommended for baby shampoos.
Alkyl ether sulfates have been found to be a source of relative high levels of
l,4-dioxane. Up to 600 ppm of this impurity has been found in shampoos.
The impurity at this level presents little or no health risk, but improvements
in the sulfonation process have resulted in lowering of the dioxane level below
20 ppm (calculated on active matter). This level of dioxane is now standard
for ether sulfates.
Water-based and salt-free alkyl ether sulfates are commercially available
in two forms: (i) low concentrate (27-30% active matter), a low viscosity clear
solution; and (ii) high concentrate (70% active matter), a translucent paste
with pseudoplastic flowing behavior. In low concentrations the ether sulfates
form spherical micelles which are transformed into rod-like micelles when the
concentration increases (Figure 1.2, phase I). At around 50% active matter
these rods are tightly packed and form a hexagonal structure, a stiff gel
(Figure 1.2, phase II). At 70% active matter a sandwich-like structure, the
liquid crystalline lamellar phase, appears. The layers can glide on each other
and the product is easily pumpable (Figure 1.2, phase III). Advantages of the
70% form are: (i) reduced transport costs, (ii) increased storage capacity; and
(iii) microbiological safety without the need for preserving agents. The
concentrate must be stored above 20°C and needs special equipment for dilu-
tion because the gel phase between 30 and 65% must be passed through. Tech-
1000000
100000
en 10000
co
a..
.s 1000
~
'00
0
u
(/)
100
:>
10
o 10 20 30 40 50 60 70
Concentration (%)
Figure 1.2 The different liquid crystalline phases of ether sulfates. I : L-phase, spherical to rod-
like micelles. II: M1-phase, hexagonal structure. III: G-phase, lamellar (sandwich) structure.
nology is available for both batch and continuous dilution. The principle is
always the same: to increase the speed of dilution a large surface has to be
formed using colloid mills or a spray process [5].
1.2.2 Alkyl sulfates
Alkyl sulfates were the first synthetic surfactant to be used in large quantities
in cosmetics and toiletries and, in some countries including the USA, they are
still the most popular. The alkyl sulfates used for cleansing products are
usually lauryl derivatives (alkyl = C l2 to C 16). As in the case of the ether
sulfates, the starting alcohols are seldom pure. Sodium, ammonium, mono-
and triethanolamine, magnesium and other salt forms are present in concen-
trations of 30-40% active product diluted in water.
Alkyl sulfates are excellent foamers, producing a rich and creamy foam,
but are unstable in hard water. This is not a problem for shampoo or shower
applications, but means that they cannot be used as the main component in
foam baths. Instead, they must be combined with surfactants such as olefin
sulfonates or sulfosuccinates, which are stable in hard water. The sodium
forms of fatty alcohol sulfates are not very soluble at low temperatures, and
formulations with high amounts of sodium lauryl sulfate often cloud up at
temperatures below 5°C. Triethanolamine (TEA) salts show much better
cold-temperature stability but relatively higher amounts must be used since
TEA represents nearly one third of the molecular weight and does not contri-
bute greatly to foaming and cleansing properties of the surfactant. The TEA
is a type of solvent. With respect to solubility, the ammonium form is some-
what better than the sodium form but the formulation must have a pH of
5-6.5 since, at alkaline pH, ammonia will be liberated.
A negative point of the alkyl sulfates is their high irritation value although
an exception is magnesium lauryl sulfate, which combines the mildness of a
secondary surfactant with the good cleansing and foaming properties of the
primary surfactants. Figure 1.3 gives an overview of the irritation index of
several surfactants, as determined by the Zein method. This laboratory test
correlates well with in vivo test results [6]. The high irritancy of the sodium
alkyl sulfates is one reason why alkyl ether sulfates are often preferred in
liquid formulations, while sodium cocoyl isethionates are preferred in the
field of syndet (synthetic detergent) bars.
A very important application of alkyl sulfates is their use in toothpastes.
Sodium lauryl sulfate is available in very pure form with low amounts of
un sulfated matter. This results in a very neutral taste compared to the bitter
taste of other surfactants.
Chemically, both alkyl sulfates and alkyl ether sulfates are esters of sulfuric
RAW MATERIALS 5
mo r- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - .
LS, TEA LE2S, Na LE3SC, Na PFAC, K

AOS, Na LE3S, Na LS, Mg AE3SC, Na
Figure 1.3 Zein number of various surfactants. LS = lauryl sulfate; LExS = laureth sulphate
(x = 2, 3, 8); AOS = olefin sulfonate; PFAC = protein fatty acid condensate; LE3SC = laureth-3
sulfosuccinate; AE3SC = lauramido PEG 3 sulfosuccinate.
acid and are therefore unstable at acidic pH values. In this case, the hydrolysis
is an autocatalytic process where the velocity of hydrolysis increases with
decreasing pH. This is mainly a problem regarding storage at elevated
temperatures, but should also be taken into account during the development
of formulations with low pH values [3]. .
1.2.3 a-Olefin sulfonates
CH=CH~S04Na
a-Olefin sulfonates are a mixture of alkene sulfonates and hydroxy alkane

sulfonates prepared by sulfonation of a-olefins followed by alkaline hydrolysis
[7]. Contrary to most other surfactants, where the C 12 alkyl chains show the
highest surface activity, olefin sulfonates show maximum activity when C 14
and C 16 olefins are used. In the first step of production, which is the sulfonation
in a thin-film reactor, alkene sulfonic acid and sultones are formed. These
sultones are then hydrolysed into alkene sulfonates and hydroxy alkane
sulfonates. The mixture usually contains approx. 60-65% of alkene sulfonates,
35-40% of hydroxy alkane sulfonates and up to 10% of disulfonates. The
olefin sulfonates are commercially available as solutions with approx. 40o~
active matter.
From Figure 1.3 it can be seen that a-olefin sulfonates are milder than
alkyl sulfates and of similar irritation to the alkyl ether sulfates. An in vivo
test did not differentiate between olefin sulfonates and ether sulfates. Olefin
sulfonates also produce an excellent flash foam when used in cold water and
are therefore particularly recommended for liquid hand soaps. They are
stable in hard water and show hydrotropic properties. This results in low
cloud points on cooling, and high solubilizing power for superfatting agents.
The difficulty of thickening can be overcome by combination with other
surfactants. For example, a mixture of 60% olefin sulfonate and 40% sulfo-
succinate, which are individually very difficult to thicken, shows a thickening
behavior comparable to alkyl ether sulfates. Contrary to the alkyl sulfates
and the alkyl ether sulfates, olefin sulfonates are stable at both acidic and
alkaline pH values.
Olefin sulfonate is a well-established basic surfactant particularly in the
US and Japan. Regarding toxicology it is one of the best known anionic
surfactants besides alkyl sulfate [8]. Today's technology allows the
production oflight colored sulfonates without bleaching.
1.2.4 Other basic surJactants

Linear alkyl benzene sulfonate and alkane sulfonate are very powerful
surfactants with good detergency and foaming properties. However, due to
their strong defatting action, they leave a harsh and dry feel on skin and
hair. For very cheap formulations, small amounts can be used to reduce the
costs of raw materials. Their main use is in dish-washing liquids and all-
purpose cleaners.
1.3 Mild anionic surfactants
Compared to the basic surfactants, a much wider group of mild anionic

surfactants is used in cosmetics and toiletries. The purpose of mild or secondary
surfactants is to improve skin and eye compatibility of the formulation. On
the other hand, mild surfactants usually show reduced foaming and cleansing
compared with basic surfactants. Fortunately there are many synergisms for
combinations of surfactants which are known to compensate or partially
compensate for this behavior.
1.3.1 Sulfosuccinates
ROOC-CH-CH2-COONa
I
S03 Na
R = e.g. lauryl, laureth, lauramido PEG-3, oleamido MEA
RAW MATERIALS 7
Sulfosuccinates represent a diverse group of derivatives of sulfosuccinic acid.

Both mono- and diesters are known. The diesters, particularly the sodium
diethylhexyl sulfosuccinate, are very effective wetting agents for industrial
use, while the monoesters are mild surfactants with good foaming properties,
and are widely used in cosmetics and toiletries. Sulfosuccinates are prepared
in a two-step process. The first step is the esterification of maleic anhydride
with an alcohol. This can be, for example, a fatty alcohol, an ethoxylated
fatty alcohol, a fatty acid monoethanolamide or an ethoxylated monoethanol-
amide. The second step is the sulfonation of the resulting half-ester with
sodium sulfite.
The most popular derivative used in Europe is dis odium laureth sulfo-
succinate, where laureth refers to an ethoxylated lauryl/myristyl alcohol with
approx. 2-3 moles ethylene oxide. In the USA, sulfosuccinates based on
amides, particularly the dis odium oleamido sulfosuccinate, are more
important.
The sulfosuccinates have good skin compatibilities compared with the
basic surfactan ts (Figure 1.3). In general, the amide-based sulfosuccina tes are
better than the alcohol-based types. Sulfosuccinates are good foamers and
are relatively cheap. A disadvantage is their instability at both low and high
pH values. The highest stability is obtained at pH values between 6 and 6.5.
The ethoxylated forms are stable in hard water and are useful lime soap
dispersants. They are mainly used in liquid formulations. The non-ethoxylated
forms are good co-surfactants for syndet bars. Sulfosuccinates are relatively
poor solubilizers for perfumes.
1.3.2 Cocoyl isethionates
alkyl = cocos
The cocoyl isethionates can be prepared in two ways: (i) by the direct esterifi-
cation of sodium 2-hydroxyethansulfonate with coconut fatty acid; and (ii) by
condensation with fatty acid chloride, which leaves small amounts of sodium
chloride in the product.
Cocoyl isethionate is mainly used as a surfactant in syndet bars. In normal
soaps it improves skin compatibility and acts as a lime soap dispersant. The
extraordinary mildness of this surfactant has been proven by more than 30
years experience [9-11]. For syndet bar production, plasticizers such as
stearic acids, fatty alcohols or waxes are used. Cocoyl isethionate is relatively
insoluble in these plasticizers, but has to be dispersed. Consequently, cocoyl
isethionates are usually offered as extremely fine powders with a particle size
below 40 .urn. Ready-made premixes in noodle-form, which are combinations
ofplaticizers with cocoyl isethionate and other surfactants, are also available
to the cosmetic formulator.
At room temperature cocoyl isethionate shows only limited solubility in

water. This permits its use in syndet bars but can lead to crystallization in
liquid preparations that are not properly formulated. Due to its excellent
skin compatibility and emolliency properties, the use of sodium cocoyl
isethionate in baby products and in facial-wash formulations has been reported.
Since it is an ester, cocoyl isethionate shows maximum stability in the pH
range 5-7.
1.3.3 Acyl amides
CO-N-CH2COONa
I
CH 3
Sodium acyl sarcosinate
CO-(NH-CH-CO) n -OK
X
I
Potassium acyl hydrolysed animal protein
The two most important acyl amides used in cosmetics and toiletries are the
sarcosinates and the protein fatty acid condensates. They are prepared by
reaction of fatty acid chloride with N-methylglycine or with oligopeptides.
The acyl amides can be considered as modified soaps with good water
solubility. Due to their enlarged polar ends, they are stable in hard water.
The fact that they are amides means that they are more stable than esters.
Their high price and specific odor is the reason for their limited use.
The acyl peptides, in particular, have been recognised for many years as
very mild surfactants, which, when combined with other anionic surfactants,
can synergistically reduce irritancy [12]. Since there is usually a relatively
high amount ofunreacted fatty acid in the products, the potassium and TEA
salts are most commonly used.
1.3.4 Alkyl ether carboxylates
(OCH2 -CH2)-x-OCH2 -COOM
M = H or alkali
Alkyl ether carboxylates are prepared by reaction of chloroacetic acid with

fatty alcohol ethoxylates. R typically represents C 12 / 14 alkyl groups. The
structure is similar to the fatty alcohol ether sulfates, but the acidity of the
RAW MATERIALS 9
carboxyl group is lower than that of the sulfate group. Consequently, ether
carboxylates are milder surfactants. However, they also show reduced foaming
and cleansing. In principle, the influence of the degree of ethoxylation on
skin compatibility is similar to that for alkyl ether sulfates as shown in
Figure 1.1.
Unlike alkyl ether sulfates, alkyl ether carboxylates have no ester linkages
and are stable at low pH-values. They are available as 100% active material
in the acidic form, or as neutralized solutions [13].
1.3.5 Magnesium surJactants
It is often stated in literature that magnesium surfactants have significantly

better skin compatibility than sodium, ammonium or amine neutralized
anionic surfactants. Figure 1.3 shows that there is indeed a large difference,
especially in the fatty alcohol sulfates which can be considered as ether sulfates
with zero EO groups. In vivo tests have also proven this effect. In a flex wash
test on ten volunteers, nine strong and one weak reactions were found in
the case of the sodium lauryl sulfate, while just one weak reaction was found
in the case of a magnesium lauryl sulfate.
The advantage of the magnesium surfactants compared with other mild
surfactants is that their applicational properties are practically unchanged
compared with the sodium forms. From this point of view they belong
to the group of basic surfactants showing high foaming and excellent clean-
sing properties [4, 11]. In case of the ether sulfate, easy thickening with electro-
lytes is still possible. The solubility for oils and perfumes is much
greater when magnesium surfactants, rather than sodium surfactants are
used.
The preservation of formulations based on magnesium surfactants is
somewhat problematic, since divalent ions such as magnesium increase
the resistance of microbes [14, 15]. Consequently, where magnesium
surfactants are used in formulations, the preservation system should be
carefully checked.
1.3.6 Alkyl phosphates
While di- and trialkyl phosphates are known as emulsifiers, the pure mono-
alkyl phosphates are good surfactants that show high foaming combined
with mildness to the skin [16]. Due to the fact that dialkyl phosphates are
defoamers, a high amount of monoalkyl phosphate is necessary. In Japan,
particularly, this product group is used for mild shampoos and shower-bath
preparations. Both the alkyl phosphates based on fatty alcohols, and the
alkyl phosphates based on low ethoxylated fatty alcohols are described in
the Japanese Comprehensive Licensing Standards of Cosmetics.
1.4 Amphoteric surfactants
Amphoteric surfactants are surfactants where the charge changes as a function

of the pH value of the formulation in which they are used. They are generally
regarded as mild surfactants but this is not a simple matter and may not
always be true. Amphoteric surfactants build complexes in combination with
anionic surfactants and these complexes are milder than the individual
surfactants. This is shown in Figure 1.4 for the combination of lauryl sulfate
and cocamidopropyl betaine [17].
1.4.1 Alkyl betaines
CH 3
1+
N-CH2-COO
-
1
CH 3
This product group derives its name from the betaine, trimethylglycine, which
is found in sugar beets. The betaines are zwitterionic, with positive and
negative charges on the molecules.
55
50
45
c 40
0
~
~ 35
30
25
20
0:10 2:8 4:6 6:4 8:2 10:0
Relation NaLS : CAPB
Figure 1.4 Irritation of mixtures of sodium lauryl sulfate and cocamidopropyl betaine [17].
RAW MATERIALS 11
Alkyl betaines are prepared by condensation of an alkyl dimethyl amine
with sodium chloroacetate. Commercial betaines are usually 30% active
products containing approx. 6% sodium chloride, which is a by-product of
the reaction. Depending on the pH, the alkyl betaines can be cationic or
anionic surfactants. At pH values between 5 and 7, which are typical for
shampoos or shower baths, they form ionic complexes in combination with
anionic surfactants such as ether sulfates or fatty alcohol sulfates. These
complexes are poorly soluble in water but the presence of excess anionic
surfactant or betaine aids solubilization. The improvement of the skin com-
patibility of an anionic formulation due to the addition of betaine is partly
based on a reduction in the overall activity. A side-effect is the increase in
the size of the micelles and, consequently, an increase in the viscosity. This
principle is often used for thickening of a formulation, especially in case of
formulas based on non-ether sulfates.
Betaines can improve the foaming of a formulation, particularly the structure
of the foam, which becomes finer and more creamy. On the other hand, a
1: 1 complex of anionic surfactant and betaine shows poor foaming and poor
solubility in water. In conditioning shampoos, betaines support the effect of
polymeric quaternaries, which impart good manageability and body to the
hair.
1.4.2 Alkylamido betaines
Alkylamido betaines are prepared by condensation of fatty acids with di-

methylamino propyl amine (DMAPA), followed by reaction with sodium
chloroacetate. The amido betaines are considered to be milder than the alkyl
betaines. This, together with their lower price, is the main reason why amido
betaines are much more often used in cosmetic formulations. Today, efforts
are being made to improve the quality and to reduce the level of by-products
such as free amine and free chloroacetic acid. The application properties of
alkylamido betaines are generally similar to those of the alkyl betaines. The
coco-type is by far the most important.
1.4.3 Acylamphoglycinates and acylamphopropionates

RCO-NH-CH 2CH2-N-CH 2COONa
I
CH 2CH 20H Acylamphoglycinate
RCO-NH-CH2CH2-~-CH2COONa
CH 2CH 20CH 2COONa Acylamphocarboxyglycinate

RCO-NH-CH 2CH2-N-CH 2 CH 2COONa

I
CHzCHzOH Acylamphopropionate
RCO-NH-CH 2CH2-N-CH 2CH 2COONa

I
CH 2CH 20CH 2CH 2COONa Acylamphocarboxypropionate
The most important products of this group are the cocoderivatives-coco-

amphoglycinate, cocoamphocarboxyglycinate, cocoamphopropionate and
cocoamphocarboxypropionate. In former times these were called imidazoline
derivatives but chemical studies have shown that the imidazoline structure
hydrolyses completely during the production process. In the first production
step, aminoethyl ethanolamine (AEEA) is reacted with fatty acid to produce
an amide. During this stage the imidazoline ring is formed. The next step is
reaction with sodium chloroacetate. This leads to the production of glycinate
or, in case of reaction of two moles sodium chi oro acetate, the carboxy-
glycinate [18]. As in the case of the betaines, salt (NaCl) is a by-product of
the reaction. When acrylic acid is used in the second step, salt-free products,
which are the propionates, can be obtained.
The glycinates and propionates have good skin compatibilities and show
some conditioning properties in shampoo application. They are excellent
foamers but the foam is not very stable in hard water. When combined with
anionics, they synergistically reduce the irritancy [19]. In the US the glycinates
and propionates are widely used, while in Europe the betaines are more often
selected. The glycinates and propionates are generally regarded as milder
than the betaines.
1.4.4 Amine oxides
Alkyl dimethyl
aminoxide
Unlike betaines, amine oxides are never anionic. However, they do show
cationic or non-ionic behavior depending on the pH, and therefore behave
quite similarly [20]. Amine oxides are produced by oxidation of tertiary alkyl
amines (e.g. dimethyl or ethoxylated amines) with hydrogen peroxide. They
are colorless liquids and free from salt (NaCl). As such, they are excellent
foamers. In combination with anionics, small amounts can act as foam
boosters and can improve the foam structure. Like betaines, they are good
thickeners for anionic surfactants. In addition, amine oxides are good con-
ditioning agents in hair rinses. They are commercially available as 30-50%
aqueous solutions.
RAW MATERIALS 13
1.5 Non-ionic surfactants
1.5.1 Ethoxylated products
Fatty alcohol ethoxylate
CO-(OCH2CH2)xOH
Fatty acid ethoxylate
CO-NH-(OCH 2CH 2\H

Fatty amide ethoxylate
CO-CH2
I
I
CH-(OCH 2CH 2) OH
x
CH-(OCH 2CH2) pH
Monoglyceride ethoxylate
on(OCH2CH2l pH
Sorbitan ester ethoxylate
(OCH2CH2lyOH
I
CH-(OCH 2 CH 2 l OH
Z
CH2-OOC
Due to their poor foaming properties, non-ionic surfactants are rarely used
as shampoo surfactants, although they are often added as solubilizers for
perfumes. An exception is polysorbate 20, an ester oflauric acid and sorbitan,
ethoxylated with approx. 20 moles of ethylene oxide. Due to its extraordinary
mildness, this is used as the main surfactant in 'non-sting' baby-shampoo
formulations [21]. For this application a relatively low foaming is acceptable.
Ethoxylation allows the production of a wide range of products. Variables
are the hydrophobic part of the molecule, and the number of ethylene oxide
units added. Pure ethers are obtained when fatty alcohols are used as starting
molecules. The ethoxylation is carried out using ethylene oxide under pressure
and heat. Alkalis are usually added as catalysts. The resulting product contains
a broad range of ethoxylated alcohols differing in the polyoxyethylene (POE)
chain length. The nominal degree of ethoxylation represents an average.
Ethoxylated alcohols do not follow the Poisson distribution. Typically
they contain a relatively high amount of unreacted fatty alcohol because the
16
14
12
10
~ 8
~
o
6
2 4 6 8 10
Degree of Ethoxylation
Figure 1.5 Distribution of homo logs in a commerciallaureth-3.
extension of the POE chain is preferred to the starting reaction, which is the
addition of ethylene oxide at the hydroxyl group of the alcohol. Figure 1.5
shows a typical ethylene oxide (EO) distribution of a C 12 / 14 alcohol reacted
with nominal three moles EO. There is approx. 13% of unreacted fatty alcohol
in the product (degree of ethoxylation = 0). During the following sulfatation
step, the free alcohol forms fatty alcohol sulfate. As a result the sodium
laureth sulfate contains a substantial amount of fatty alcohol sulfate.
D sing a new generation of ethoxylation catalysts, 'peaked' ethoxylates can be
obtained with a narrower distribution of homo logs [22].
The degree of ethoxylation allows the tailoring of the molecules for specific
requirements. The properties of the products can be estimated by the HLB
(hydrophilic lipophilic balance) value. The HLB ranges from 0 to 20 and is
calculated from the following expression:
%wt/wt ethylene oxide
HLB=-
5
Table 1.1 outlines the main properties and applications of ethoxylates as a
function of the HLB value.
Table 1.1 Properties and applications of ethoxylates as a
function of the HLB value [23]
HLB value Solubility in water Application
0-2 Insoluble Anti-foam additives

3-6 Poorly dispersable WIO-emulsifiers
7-9 Dispersable Wetting agents
8-18 Dispersable o IW -em ulsifiers
13-15 Soluble Surfactants, detergents
15-18 Soluble Solubilizers
RAW MATERIALS 15
Other non-ionic surfactants are ethoxylated glycerol esters, ethoxylated
castor oil derivatives, ethoxylated fatty amides, and ethoxylated fatty acids.
Nonylphenol ethoxylates are also very effective emulsifiers and solubilizers
but, due to ecological reasons, are now rarely used in Europe [22].
1.5.2 Alkyl polyglycosides
WM/WvINNM- 0 R=octylldecylor
R
H lauryl/myristyl
OH x =1-5
A relatively new range of commercially available surfactants is the alkyl

polyglycosides (APG). First described by Emil Fischer approx. 100 years
ago they have been produced on a large scale since 1992. Based on carbohy-
drates, APGs are mixtures of different isomers, (i) stereoisomers, (ii) binding
isomers and (iii) ring isomers. This together with the C-chain distribution of
the alkyl group and the variation in the degree of glucosidation makes them
of extremely complex composition [24].
Surface active APGs are prepared by the glycosylation of starch or
monomer glucose with fatty alcohols. This can be done directly or by trans-
glycosylation using butylpolyglucosides as intermediates in a two-step
process. These processes are proton catalysed and carried out at 120-140°C
under pressure and with excess fatty alcohol. In a separate step the excess
fatty alcohol is removed by vacuum distillation and recycled [25].
The optimum surface activity is obtained with an alkyl chain C S-C 16 and a
mean value degree of polymerization between 1.1 and 3. Although not as
good as anionic surfactants these show surprisingly good foaming properties
compared with ethoxylates [26]. This combined with their excellent skin
compatibility makes them useful secondary surfactants. Since the raw
materials used are from renewable sources and they are considered neutral
with regard to the Earth's CO 2 balance these surfactants can be expected to
play an important role in the future.
1.6 Cationic surfactants

R
I
R-N+ -R x-
I
R
Unlike the anionic or amphoteric surfactants, cationics are seldom used for
cleansing applications [27]. Due to their conditioning properties, cationic
surfactants show a high substantivity to surfaces such as skin and hair. They
can act as emollients for the skin, or as conditioning agents on the hair. The
main effects are to stop 'tangling', to improve wet- and dry-combing and, as a
result of antistatic properties, to prevent fly-away of the hair.
A quaternary ammonium salt can generally be considered as ammonium
chloride (NH 4 CI) where the four hydrogen atoms are substituted by alkyl
groups. At least one of them is a hydrophobic entity with a carbon-chain
length between 12 and 22. The other alkyl groups are typically methyl. The
most widely used counter-ion is chloride, but bromide or methyl sulfates can
also be found. The methyl sulfates are particularly useful in systems such as
aerosols, where metal corrosion may be a concern. Quaternary ammonium
compounds are usually obtained by reaction of methyl chloride, dimethyl
sulfate or, in special cases benzyl chloride, with tertiary amines.
1.6.1 M onoalkyl quaternaries
R = cetyl
The mono alkyl quaternaries are still of major importance in conditioning.

The most important is cetyl trimethyl ammonium chloride (CTMAC) which
shows a light to moderate conditioning intensity combined with excellent
water solubility. The substantivity and conditioning properties are improved
as the length of the carbon chain increases. Behenyl quaternaries are now
offered as products with good conditioning properties, but are more difficult
to incorporate compared with CTMAC.
1.6.2 Dialkyl quaternaries

CH 3
I
R-N+ -CH Quaternium-18
I 3
R R = cetyljstearyl
CH 3
I Hydrogenated tallow octyl
R-N+ -CH3
I dim onium chloride
CH 1 CHCH 1 CH 1 CH 2 CH 3 R = cetyljstearyl
I
CH 2 CH 3
The dialkyl quaternaries are well known as relatively strong conditioning
agents. The most important product is the so-called Quaternium-18 (CTF A
nomenclature). This is a dialkyl dimethyl quaternary based on hydrogenated
tallow (DHTDMAC). In addition to its use in cosmetic formulations, it has
also become the most widely used quaternary for fabric softeners. It exhibits
strong conditioning properties, good detangling and combing, and adds
RAW MATERIALS 17
manageability to unruly or 'damaged hair. Quaternium-18 is not soluble in
water but forms stable dispersions. It is usually offered in form of a paste
(75% active in water/isopropanol), or as powder or granular forms.
Quaternium-18 represents a mixture of dicetyl-, distearyl- and cetyljstearyl
dimethyl quaternaries in a statistical distribution. A relatively new quaternary
available to the cosmetic industry is the so-called hydrogenated tallow octyl
dim onium chloride (CTF A adopted name). This new quaternary has strong
conditioning properties, close to Quaternium-18, but is clearly soluble in
water. In addition, it forms stable dispersions in mineral oil and isopropyl
myristate. This is untypical for quaternaries [28].
1.6.3 Trialkyl quaternaries

R
I Tricetylmonium chloride
R-N+ -CH3 R = cetyl/stearyl
I
R
An increase in the number of alkyl chains leads to considerable improvement
in properties (Figure 1.6). A relatively new product is tricetyl methyl ammonium
chloride (TCMAC), which shows superior detangling, static control, and
excellent combing properties on both wet and dry hair. It is a suitable product
when really intensive conditioning is required, for example in split-end fluids
and in hair cures.
It is interesting to note that the TCMAC forms stable dispersions in
solutions of anionic surfactants. In this case, the two-phase titration for the
determination of active matter using anionic surfactants as titrating agents
Detangling Wet combing Dry combing Static control

Itft~;t}t:l Monocetyl . . Dicetyl _ Tricetyl
Figure 1.6 Conditioning properties of a cetyltrimonium chloride, dicetyldimonium chloride

and a tricetylmonium chloride in a hair-rinse formulation [28].
is not possible. The reason could be steric hindrance, which prevents the
complexation.
1.6.4 Benzyl quaternaries

Benzyl quaternaries are obtained by reaction of alkyl dimethyl amines with
benzyl chloride. Based on short-chain amines, quaternaries with good anti-
microbial properties are obtained. Products with a carbon-chain length
between 12 and 14 are particularly effective. As the length of the carbon
chain increases, the microbial activity is reduced. Stearyl benzyl ammonium
chloride (stearyl alkonium chloride in the CTF A nomenclature) is a very
effective conditioner. It was the first to be used in cosmetics and is still widely
used, particularly in the USA.
1.6.5 Ester quaternaries
Fabric softeners provide by far the biggest market for cationic surfactants.
Under pressure of the environmental authorities the European detergent
industry gave up the use of the DHTD MAC which was for years the standard
quaternary for this application (see section 1.6.2) [22]. It has been replaced by
so-called 'ester quats' which have at least one ester group between the alkyl
functions and the cationic nitrogen. Due to this 'breaking point' the
molecules show improved biodegradation and meet current requirements
regarding ecotoxicity. Examples are N-methyl-dihydrogenated tallowyl-
triethanolammonium chloride and the similar dimethyl-dihydrogenated
tallowylethanolammonium chloride. It can be expected that they will find
use in the cosmetics industry in the near future. The conditioning properties
are excellent. Chemical stability seems to be somewhat problematic for
cosmetic applications as rather low pH values are necessary to prevent
hydrolysis [29].
1.6.6 Ethoxylated quaternaries
Ethoxylated quaternaries (ethoquats) are obtained by reaction of methyl

RAW MATERIALS 19
chlorides with ethoxylated amines. They are more hydrophilic than normal
quaternaries, but show relatively good conditioning properties regarding
both wet-combing and, particularly, static control. As in the case of betaines
and aminoxides, the ethoquats are compatible with anionic surfactants. Due
to the presence of hydrophilic groups, complexes of ethoquats and anionic
surfactants are quite soluble in anionic surfactants. These combinations
are ideal bases for conditioning shampoos, especially if combined with poly-
meric quaternaries.
1.7 Shampoo and bath additives
1.7.1 Thickeners
PEG-6000 distearate
Talloweth - 60 myristyl glycol
A high viscosity is often very important both for product stability and for
handling of a cosmetic product. For shampoos, shower and foam bath
products, viscosities between 400 and 4000 mPa s are typical. Pearlescent
products should have a minimum viscosity of 2000 mPa s to avoid pre-
cipitation. In the case of ether sulphate as the main surfactant, the thickening
can easily be achieved by addition of electrolytes (chlorides of sodium,
ammonium or magnesium, for example) to the formulation. The mechanism
is by an increase in the size of the micelles. The thickening effect of alkanol
amides is similar and will be described in more detail in section 1.7.2. Due to
possible contamination with nitrosamines, low ethoxylated fatty alcohols
such as the laureth-3 are recommended as replacements. These products are
also good thickeners but, unlike the alkano1 amides, they increase the cloud
point of the formulations.
A different principle of thickening is obtained by the use of special, high
molecular weight thickeners such as PEG-6000 distearate, talloweth-60
myristyl glycol or PEG-120 methyl glucose dioleate. The structure of
talloweth-60 myristyl glycol with its hydrophobic ends is very similar to that
of PEG-6000 distearate. An advantage is that it is an ether product which
remains stable against hydrolysis at higher temperatures or extreme pH
values.
A side-effect of all these thickeners is that they modify the flow properties,
leading to increased Newtonian flow. This contrasts with salt- or polymer-
thickened systems, which show typically pseudoplastic flow behavior.
Polymer thickeners like natural gums, cellulose derivatives (carboxy-
methyl cellulose, hydroxyethyl cellulose) and carbomers (CTFA name)
are used more often in emulsions than surfactant-based formulations. An
excellent review of polymers and thickeners is given by Lockhead and Fron
[30].
Another type of rheological modifier is the inorganic bentonites, which can
be used to obtain a yield point. This gives stability to shampoos carrying
particles in suspension, e.g. pearle scent formulations or formulations
containing zinc pyrithione, preventing sedimentation and separation. The
systems are often thixotropic and will flow on shaking. In the absence of
shear stress, such systems behave as solids.
1.7.2 Foam stabilizers
Acyl monoethanolamide
Acyl diethanolamide
In the presence of oily soils such as sebum, the stability of shampoo foam
can be drastically reduced. The so-called foam boosters act as stabilizers and
also modify the foam structure to give a richer, dense foam with small bubbles.
The alkanol amides are well known for this behavior. The most important
types are the monoethanolamides, which are obtained by amidation of fatty
acids with monoethanolamine. Diethanolamides are usually obtained by
amidation of fatty acid methylester, or triglycerides such as coconut oil, with
diethanolamine. The latter are liquid products with a typical glycerol content.
The monoethanolamides are the most effective foam boosters but are
difficult to incorporate due to their high melting points (approx. 80°C). The
diethanolamide based on coconut oil is the most popular one, although the
thickening effect is reduced, due to the glycerol. The price is relatively low
and the product is easy to handle compared with pure amides based on
methyl ester. Today, the diethanolamides are under discussion due to possible
formation of carcinogenic nitrosamines. Consequently, EC regulations allow
only alkanolamides with free diethanolamine below 4%.
Other well-known foam boosters are the amine oxides and betaines
described previously. Protein hydrolysates and cellulose derivatives such as
CMCs are recommended as foam stabilizers.
RAW MATERIALS 21
1.7.3 Pearlescent agents
CO-OCH 2CH 2 - O H
Glycol monostearate
CO-OCH2CH2 O--OC
Glycol distearate
Ethylene glycol mono- and distearates (EGMS, EGDS) are most often used
as pearlescent agents in surfactant formulations. They have to be incorporated
at high temperatures (approx. 70-75°C), therefore ready-made liquid pearle-
scent bases are now very popular. A wide range of bases with different appear-
ances, from turbid to real peariescent, is offered on the market. Very effective
opacity without peariescent effect can be achieved with polystyrol dispersions.
These are already highly effective at very low concentrations. Direct contact
with perfume oils can result in coagulation of the polys tyrol, and must be
avoided.
1.7.4 Conditioning agents

Shampooing with pure anionic surfactants can leave hair difficult to comb
while wet, and prone to 'fly-away' when combed after drying. Improvement
of the wet-combability, and reduction of static charge build-up can be achieved
by addition of conditioning agents. These are especially effective if the
formulation also contains amphoteric surfactants such as betaines or amine
oxides. Cationic surfactants used in hair rinses are normally incompatible
with anionic surfactants and cannot be used in shampoo formulations. This
problem can be overcome by the use of quaternized polymers. An example
is Polyquaternium 10, a quaternized hydroxyethyl cellulose, which is compatible
with most of the anionic surfactants and can therefore also be used in clear
formulations. It shows excellent conditioning properties and imparts manage-
ability and body to hair. Due to its very high substantivity to hair, very low
concentrations (below 0.5%) are sufficient. Use of high concentrations may
lead to over-conditioning and build-up on the hair. Used in shower- or
foam-bath formulations, polyquaternium 10 can improve skin-feel after use.
Other important polyquats are Polyquaternium 7, Polyquaternium 23, Poly-
quaternium 8, and Polyquaternium 11 (CTFA nomenclature) [30].
Small amounts offatty components such as fatty alcohols or monoglycerides
can support the conditioning effect of shampoos. Silicones can be very effective
conditioners but are difficult to incorporate and may act as antifoaming
agents.
1. 7.5 Emollients
To overcome possible harsh effects of shower and foam baths on the skin,
special refatting agents (emollients) are often added. Real lipids like
isopropyl myristate (see section 1.8.3.1) are difficult to incorporate due to
their limited solubility in water-based formulations. Water-soluble lipids,
which still have a certain lipophilic character can be obtained by ethoxylation
to an HLB of approx. 6 to 8. Examples are PEG-7 glyceryl cocoate, PEG-6
caprylic/ capric glycerides and ethoxylated lanolin. They do not interfere
with the foaming of the surfactants.
1.7.6 Sequestering agents

Sequestering agents like ethylenediamine tetraacetate (EDTA) are used to
prevent the formation and deposition of Ca and Mg soaps and to clarify
formulations when hard water is used for the production of shampoo and
bath preparations. As a positive side-effect they can also give support to the
preservation system as shown in Table 1.2.
Table 1.2 Influence of sequestering agents on the performance of preservatives in a solution of

lauryl ether sulfate
No additive 0.05%EDTA
pHB-Me pHB-Me DBDCB pHB-Me pHB-Me DBDCB

0.4% 0.2% 0.05% 0.4% 0.2% 0.05%
Start +++ +++ +++ +++ +++ +++
1 day ++ ++ +++ ++ ++
3 day ++ ++ +++ +
7 day ++
Scaling: +++, strong contamination to -, no bacteria (semi-quantitative determination). pHB-
Me = pHB methyl ester; DBDCB = dibromo-2,4-dicyanobutane.
The outer membrane of Gram-negative organisms like Pseudomonas is

very complex and is stabilized by Ca and Mg ions [14]. Strong chelating
agents will destabilize this membrane making it more permeable for the
preserving agents [15].
1.8 Oil components
1.8.1 Mineral oil

Mineral oils for cosmetic use are high-boiling fractions obtained from crude
oil distribution that are purified and refined by treatment with sulfuric acid.
Two types are of importance: (i) liquid paraffin (viscosity 110 to 230mPas);
and (ii) light liquid paraffin (viscosity 25 to 80mPas). Mineral oils are colorless,
clear and odorless liquids, insoluble in alcohol or water. They are excellent
cosmetic emollients because they are inert and do not penetrate into the
RAW MATERIALS 23
skin. They therefore have excellent skin compatibility and little or no comedo-
genic potential. Since they are not considered 'natural', mineral oils have
been attacked repeatedly but are still the most widely used oil component
in skin-care formulations. Nevertheless, 3.7% of the humanstrateum corneum
lipids are n-alkanes [31].
Due to their fatty character, mineral oils form a film on the skin which
increases hydration by blocking the normal evaporation of water. Combi-
nations with synthetic esters such as isopropyl stearate are recommended in
order to open the film, and to guarantee the right balance for water evaporation.
1.8.2 Natural oils
1.8.2.1 Triglycerides
CH2-0-0C
I
CH-O-OC
CH2-O-OC
alkyl =c 7 to C 21
Natural oils from vegetable sources are mainly glycerol esters based on
mixtures of C S/22 fatty acids. The most important are the saturated lauric
(Cd, myristic (C I4 ), palmitic (C I6 ) and stearic (CIS) acids and the unsaturated
oleic (CIS) and linoleic (CIS) acids. These fatty acids are derived from natural
sources and typically have even numbers of carbon atoms in their chains.
Important characteristic values for triglycerides are the saponification
number and the iodine number. The latter indicates the amount of unsaturated
fatty acids present. Although, due to the natural source, better skin com-
patibility compared with synthetic materials is expected, triglycerides are
relatively problematic to use in cosmetic emulsions. In addition to the difficulty
of emulsification, the products can become rancid due to the presence of
unsaturated fatty acids. Consequently, antioxidizing agents usually have to
be added.
It is important to use only high-quality triglycerides. Polycyclic aromatic
hydrocarbons (PAHs) can be a problem, particularly in the case of coconut
oil. This is due to contamination from flue gases when the copra, from which
the coconut oil is derived, is dried. Treatment with activated carbon can
remove these impurities.
Triglycerides are relatively fatty and spread very little on the skin. They
generally show moderate comedogenicity, exceptions being sunflower oil and
safflower oil where no comedogenic effects have been found [32]. Other
examples of natural triglycerides are peanut oil, soy oil, olive oil, wheat germ
oil and avocado oil.
A special triglyceride is castor oil, which is obtained from the seed of Ricinus
communis. This oil is based on ricinoleic acid, an unsaturated CiS hydroxy
fatty acid. Contrary to other triglycerides, it is easily soluble in alcohol. Castor
oil is used in lipsticks and also in alcoholic preparations.
1.8.2.2 Jojoba oil Unlike the oils described in the previous section, jojoba
oil is not a triglyceride. It is a liquid, unsaturated wax from the esters of
long carbon-chain fatty acids (C 20 to C 22 ) and long carbon-chain unsaturated
alcohols (C 20 , C Z2 )' Its source is the jojoba plant, which grows in California
and Mexico. Jojoba oil has a very fatty character and shows excellent cosmetic
properties.
1.8.3 Synthetic oils

Synthetic oils are esters, usually obtained by direct reaction of fatty acids
with alcohols. Common fatty acids are caprylic, caprinic, lauric, myristic,
palmitic, stearic, oleic, linoleic and behenic acid, and also adipic acid, a
dicarboxylic acid Alcohols can be, for example, isopropyl, butyl, ethylhexyl,
myristyl or oleyl alcohol, as well as polyvalent alcohols such as ethylene
glycol, propylene glycol and glycerol. A wide range of combinations to
produce different synthetic esters is possible, and the list of synthetic oils
available to the cosmetic industry is long.
In addition to products obtained via normal esterification using chemical
catalysts, esters obtained by enzymatic catalysis are now also available [33].
Possibly advantages can be found in the case of oleic acid derivatives, because
esterification can be obtained under milder conditions. Consequently, a light
color and weak odor can be expected.
1.8.3.1 I sopropyl esters
RCO = myristic, palmitic, stearic
The most important synthetic ester for cosmetics is isopropyl myristate. It

has a very dry character and shows good spreading on the skin. It can open
films of mineral oil or other fatty oils in order to let water evaporate, and
it is an excellent solvent for perfumes, ultraviolet filters, etc.
A disadvantage of isopropyl myristate is its high comedogenicity [32].
Nowadays therefore, isopropyl palmitate and isopropyl stearate, which show
similar properties but reduced comedogenic effects, are increasingly used.
RAW MATERIALS 25
Due to their good solvent properties, the isopropyl esters can cause
difficulties when used in formulations that are filled into polystyrene or poly-
ethylene containers.
1.8.3.2 Ethylhexyl esters
Other alternatives to isopropyl myristate are the ethylhexyl esters of

palmitic acid or stearic acid. These have become important products for the
cosmetic industry. Compared with isopropyl esters, the molecular weight is
higher, but spreading properties are similar.
1.8.3.3 Oleic acid esters
~CH=CH~CO_O _ _ ~
Decyl oleate
~CH=CH~CO-O ~CH=CH~
Oleyl oleate
The two most important oleates are decyl oleate and oleyl oleate. The
character of these esters is relatively fatty and, as with unsaturated esters,
they can become rancid. The advantage of the oleates is that, even at high
molecular weight, the esters are liquid.
Interesting alternatives to the oleates are the isostearates. Esters of
branched isostearic acid are also liquid and present no oxidation problem.
The limiting factor for use is the price, which is much higher than that of
the oleates.
1.8.3.4 Caprylic/capric acid esters The most important caprylic/capric

esters are the triglyceride and the propylene glycol diester. The glycerol ester
is mainly used as a replacement for natural triglycerides, with the advantage
that it is stable against oxidation. Like the natural triglycerides, the products
are relatively difficult to emulsify. Due to the typical odor of short chain
fatty acids, caprylic/capric esters must be produced in very pure form.
Following long-term storage, hydrolysis, which leads to changes in the odor
of cosmetic products, can take place.
1.8.3.5 N-butyl stearate N -butyl stearate is an excellent skin-compatible

ester with very good emollience. The character is not very fatty compared
with the isopropyl esters.
1.8.3.6 I socetyl stearate Isocetyl stearate is a saturated liquid ester of high

molecular weight and good emollience. Water can evaporate easily through
the ester and even small amounts can perforate a hydrophobic film of mineral
oil.
1.8.3.7 Octyldodecanol Octyldodecanol is not an ester but may be used

as a cosmetic oil component. It is a guerbet alcohol made by condensation
of two molecules of decyl alcohol. It combines a fatty character with good
spreading properties.
1.8.3.8 Diisopropyl adipate
(CH3)2CHO-OqCHz)4CO-OCH(CH3)2
Diisopropyl adipate is an ester of a dicarbonic acid. Contrary to most other

oils, it is soluble in alcohol and is therefore used, for example, as a refatting
agent in aftershave formulations.
1.8.3.9 Pentaerythritol tetraisostearate
CH 2 -OOCR
I
RCOO-CH 2-C-CH z-OOCR
I
CH 2 -OOCR RCOO = isostearic acid
Pentaerythritol tetraisostearate is a high molecular weight, highly branched

ester of pentaerythritol and isostearic acid. It has a very fatty character and
shows no comedogenic effects. Consequently, it is an ideal ester for skin-
protection formulations such as baby products and, due to its water-repellent
properties, water-resistant suntan preparations. The liquid pentaerythritol
tetraisostearate has a melting point well below o°e.
1.9 Waxes
The word wax has two different meanings. From a chemical point of view
it means an ester of a fatty acid and a fatty alcohol. Jojoba oil is therefore
a liquid wax. In this section, however, the word wax is considered from a
physical point of view, and means compounds having a high melting point
(approx. 50-100°C).
1.9.1 Natural waxes

The most important wax, and a classical component for creams, is beeswax,
which is the construction material of honeycombs [34]. Chemically, it consists
of mixed esters oflong-chain alcohols (C 26-d plus fatty acids and hydroxy
RAW MATERIALS 27
fatty acids of chain length of 16-26. At room temperature the beeswax is
very hard. The melting point is around 61 to 66°C. Untreated beeswax is
dark-yellow and is usually treated to improve the color.
Beeswax is a very good consistency regulator in creams and ointments
and is also used in stick formulations. The addition of approx. 6 per cent of
borax, calculated on the beeswax, results in partial saponification and
provides the beeswax with some emulsifying properties. This principle was
used in the classic cold-cream formulations. Nowadays, European law restricts
the use of borax in cosmetic products.
Two other natural waxes that are harder and therefore mainly used in
stick formulations are carnauba wax (melting point approx. 85°C) and
candelilla wax (melting point approx. 70°C). Both are extracted from South
American plants.
1.9.2 Synthetic waxes

Due to the varying qualities of the natural products, especially yearly and
source variations of beeswax, synthetic substitutes are of interest. These are
often mixtures of very different chemicals, and result from empirical research.
An example of a beeswax replacement is the mixture of glyceryl hydroxy stearate
(and) cetyl palmitate (and) microcrystalline wax (and) trihydroxy stearine. A
single defined product with a structure close to beeswax is hydroxyoctacosanyl
hydroxystearate, an ester of a C 26 -f3-hydroxyalcohol and hydroxystearic acid.
This product, which shows very similar behavior compared with beeswax,
is easy to emulsify and can be used as a general consistency regulator for
cosmetic emulsions [35].
Another synthetic wax is synthetic spermaceti. The natural type is no
longer available because it is obtained from whales, but was formerly an
excellent wax compound for emulsions. Replacements are cetyl palmitate,
which is the main component of the natural spermaceti, or special mixtures
like the cetyl esters wax NF, which comes very close to the natural product.
1.10 Silicone oils
R
I
[Si-O]n
I
R R = methyl or phenyl
The high molecular weight organo polysiloxanes (dimethicone) are hydrophobic

oils with good skin protection and non-sticky skin-feel. They show very high
spreading and are used in small amounts in stearate creams to avoid the
soap-up effect. To prevent eye-sting, non-volatile oils should not be used in
products that are applied to the eye area. Due to their water-repellent
properties, silicone oils are important for waterproof sun products. They are
usually classified by viscosity.
Cyclic methyl polysiloxanes (cyclomethicone) are particularly volatile.
They are used in hair-care products to improve the gloss of the hair and the
compatibility of the product.
1.11 Cream bases
1.11.1 Fatty alcohols
OH
Fatty alcohols are important raw materials for surfactants, emollients and
emulsifiers. Pure fatty alcohols, mainly cetyl alcohol and stearyl alcohol, are
also used per se as consistency regulators and co-emulsifiers in, for example,
creams, lotions and hair rinses. The so-called natural fatty alcohols are
obtained by hydration of fatty acid methyl esters. Similar, linear primary
alcohols can be obtained from the Ziegler process. The branched types
obtained from oxo-synthesis are important as raw material feedstock, but
are not used as alcohols per se.
Mixtures of cetyl and stearyl alcohols combined with hydrophilic emulsifiers
are known as the 'emulsifying waxes' of the British Pharmacopoeia. In such
combinations the fatty alcohols are self-emulsifying. Common combinations
are:
(i) cetearyl alcohol plus sodium cetearyl sulfate
(ii) cetearyl alcohol plus PEG-lOOO monocetyl ether
(iii) cetearyl alcohol plus alkyl trimethyl ammonium bromide
as examples for (i) anionic; (ii) non-ionic; and (iii) cationic cream bases. Type
(iii) combinations are mainly used in hair-rinse formulations. The fatty alcohol
gives texture and body to the formulation and acts as consistency regulator.
1.11.2 Polyol esters

The most important polyol ester is the so-called glycerol monostearate
(GMS). Generally, it is not a pure product but a mixture of mono- and
diesters of stearic and palmitic acids. The main distinguishing feature is the
content of monoester. Products with approx. 40% monoester are obtained
by direct esterification of stearic acid and glycerol. Products with approx.
60% monoester are produced by glycerolysis of triglycerides with glycerol.
The 90% material can be obtained by molecular distillation but is seldom
RAW MATERIALS 29
used in cosmetic formulations because the mono/diesters provide the best
applicational properties.
GMS is poorly soluble in water. However, as with the fatty alcohols, when
combined with more hydrophilic emulsifiers, it is an excellent co-emulsifier
and becomes self-emulsifying. Typical combinations are:
• GMS plus potassium stearate (,GMS self-emulsifying')
• GMS plus sodium lauryl sulfate
• GMS plus ethoxylated fatty alcohols (,GMS self-emulsifying, acid
stable')
Other polyol esters used as co-emulsifiers are the sorbitan esters, especially
the monostearate. These are obtained by dehydration of sorbitol to sorbitan
followed by esterification with fatty acid. Such products are typically offered
as pure products, and function as water-in-oil (W /0) emulsifiers. In oil-in-
water formulations they are most often combined with ethoxylated products
of the same family.
1.11.3 Fatty acids

Fatty acids, like the fatty alcohols, are important raw materials for cosmetic
ingredients such as surfactants, emulsifiers and emollients. Fatty acids are
obtained by saponification of naturally-derived triglycerides. As such, they
are seldom used in emulsions. They act as consistency regulators but tend
to crystallize in the formulation.
Fatty acids especially stearic acids, are mainly used in the form of soaps.
As the pH increases, they become truly anionic and act as oil-in-water (O/W)
emulsifiers, forming a group of so-called stearate creams.
Commercially available stearic acids are often mixtures of C 16 and C 1S
fatty acids, mainly 1: 1. The preferred cosmetic quality with low odor is a
triple-pressed stearine with an iodine value below 2. A special application of
the fatty acids is their use in alcohol stick formulations, where stearic acid
is dissolved in ethanol and then neutralized with sodium hydroxide. These
hard sticks are used as deodorant bases.
1.12 Oil-in-water (O/W) emulsifiers
1.12.1 Anionic O/Wemulsifiers

Anionic O/W emulsifiers can be used to obtain very stable emulsions because
they can build an electrical double layer around the droplets, which prevents
the droplets from coalescing. On the other hand, anionic emulsifiers are
sensitive to low pH and electrolytes.
The most important anionic O/W emulsifier is soap, which forms the
stearate creams. Neutralized with potassium hydroxide, the stearate is

alkaline. The use of triethanolamine as a neutralizing agent is more common.
A disadvantage of stearic acid is the typical 'soap-up' effect, a type of foaming
that occurs when the cream is rubbed into the skin. To prevent this, silicon
oil is frequently added to the formulations.
Other very effective anionic emulsifiers are alkyl sulfates, particularly
sodium cetearyl sulfate. In principle, all anionic surfactants can be used.
However, due to the fact that the soaps are relatively alkaline and fatty
alcohol sulfates are irritant to the skin, the mild surfactants are of more
interest. These include sodium cocoyl isethionate as an extremely mild
emulsifier, and phosphoric acid esters, like potassium cetyl phosphate which
are very effective at low concentrations.
1.12.2 Cationic D/Wemulsifiers

Cationic emulsifiers have generally been avoided in skin-care products
because they are often more irritant compared with anionic emulsifiers. They
are important in hair-care formulations, where they act as conditioners and
anti-static agents. Their advantage, particularly distearylammonium
chloride, is that they produce emulsified products with excellent cushion feel
on skin and mitigate the heavy feel imparted by glycerin.
1.12.3 Non-ionic D/Wemulsifiers

A wealth of non-ionic O/W emulsifiers is available. These are mainly PEG
derivatives such as ethoxylates or PEG esters. Typical O/W emulsifiers are:
• ethoxylated fatty alcohol
• PEG esters of fatty acids
• ethoxylated sorbitan esters
• ethoxylated mono glycerides
• ethoxylated castor-oil derivatives.
The degree of ethoxylation determines the primary properties of that part
of the molecule that results in the HLB classification. Good O/W emulsifiers
can be found in the HLB range between 8 and 18. However, the type of
hydrophobic moiety is also very important for the stability of the emulsions.
Contrary to anionic emulsifiers, the non-ionics are unaffected by changes in
pH and, in the case of pure ethers, they can also be used at extreme pH values.
Following the trend towards more 'natural' cosmetics, trials have been
made in order to replace the EO chain by polyglycerol or sugars [36] but up
till now it has not been possible to reach high HLB values.
1.12.4 D/W stabilizers

Very efficient and widely used stabilizers for O/W emulsions are polymers,
RAW MATERIALS 31
especially the carbomers (CTFA-name) [30]. These are polyacrylate resins
which have to be neutralized in order to form gels, usually by the use of
triethanolamine (TEA). Amounts up to 0.5% are recommended for cosmetic
emulsions. Too much can leave an unpleasant feel on the skin. The principle
of stabilization is the thickening of the outer phase. The use of preneutralized
copolymers, e.g. acrylamidel sodium acrylate copolymer can make incor-
poration and handling easier.
1.13 Water-in-oil (W10) emulsifiers
From the dermatological point of view, W 10 emulsions are preferable to

0/W emulsions. The natural lipid film on the skin is also a W/O emulsion.
W/0 emulsions can improve the hydration of the skin and are an ideal base for
lipid-soluble active ingredients. A problematic point is that they usually leave
a 'fatty-feeling' on the skin, and this is not particularly appreciated by customers.
Another problem can be 'oiling-off' or separation of the oil phase on
storage. Viscosity and stability are extremely process sensitive.
1.13.1 Single H10 emulsifiers
(_(H s~"... mooool""

o (---\OH
CH-OH
bHz-OOC~CH=CH
~
R-CHCH20CHCH20CHCHz-(OCH2CH2)220CH3
I I
OH R Methoxy PEG-22 dodecyl
copolymer (R = C 10 H 21 )
A limited number of W/0 emulsifiers are available. This is because ionic

emulsifiers will not work in the case of W/O emulsions and, since very low
HLB is required, variations using ethylene oxide are not possible. W /0
emulsifiers have HLB values between 3 and 6. However, the type of the alkyl
chain is also important. In practice, oleyl derivatives have shown good effects.
The most widely used W/O emulsifiers are sorbitan mono oleate, sorbitan
sequioleate and glycerol monooleate, and with increasing importance, poly-
glycerol esters.
In addition to oleate, ricinoleates and isostearates have also found use.
The methoxy PEG-22 dodecyl glycol copolymer is a high molecular weight

W/O emulsifier, which is especially effective in formulations containing
mineral oils [35]. It is a saturated ether and is therefore stable against
oxidation and hydrolysis.
1.13.2 Lanolin derivatives

Lanolin or wool wax obtained from sheep wool is a mixture of different
esters from higher alcohols, mainly cholesterol, with higher fatty acids. The
alcohol fraction contains linear and iSO-C 16 _ 30 alcohols, while the fatty acids
are mainly linear and hydroxy fatty acids with carbon-chain lengths between
10 and 29. Lanolin can bind 200-300% of water in the form ofa W/O emulsion.
Since lanolin can cause allergies, lanolin alcohols extracted after saponification
of the wool wax are now mainly used. Due to the high amount of cholesterol,
they are better emulsifiers than lanolin itself.
1.13.3 Absorption bases

Since it is relatively difficult to obtain stable W10 systems, pre-mixtures,
which are able to bind high amounts of water are available. Relatively simple
absorption bases are, for example, mineral oil (and) lanolin alcohol or
petrolatum (and) lanolin alcohol. Very complex systems are also offered and
include petrolatum (and) decyl oleate (and) sorbitan sesquioleate (and)
beeswax (and) mineral oil (and) ceresin (and) aluminum stearate, or mineral
oil (and) petrolatum (and) ozokerite (and) glycerol oleate (and) lanolin alcohol.
Using these premixtures it is relatively simple to obtain stable emulsions,
although the resulting emulsion often behaves more like an ointment than a
cosmetic product.
1.13.4 W;'O stabilizers

A relatively simple way of obtaining highly stable W/O emulsions is to use
block copolymers such as PEG-45 dodecyl glycol copolymer [35]. These
products, with molecular weights of 2000 to 4000, can improve the stability
of W/O emulsions by protection of the droplets from coalescence. The
hydrophilic middle part is responsible for a good anchorage in the water
phase, while the highly branched ends give a steric hindering effect. The high
molecular weight imparts excellent skin compatibility. Contrary to other
stabilizers, for example metal soaps, which increase the viscosity of the outer
emulsion phase, these copolymers typically reduce the viscosity. It is possible
to obtain light, highly stable W/O lotions that are good bases for sun
preparations and which give a skin-feel very close to emulsions.
RAW MATERIALS 33
1.14 Humectants
Humectants protect emulsions or toothpaste from 'drying-up'. The most

important humectants are glycerol, obtained from saponification of trigly-
cerides, and sorbitol [C 6H 8 (OH)6], a hexa-alcohol. Sorbitol is a hygroscopic
powder but is most often used in the form of a 70% aqueous solution. Glycerol
is typically used at 99% with a density of 1.26 or at 85% with a density of
1.22. Both are non-toxic and have a sweet taste, which makes them ideal for
the use in toothpastes.
Other humectants for emulsions are lactates, 1,3-butylene glycol and
1,2-propylene glycol. The latter should be of high quality as it has occasion-
ally been implied as a skin irritant [23]. A positive side-effect of humectants is
a reduction of the freezing point. Humectants are also important in
moisturizing products.
1.15 Aerosol propellants
A few years ago only one group of aerosol propellants, the fluorocarbons,
was used. Due to the well-founded suspicion that these chemicals damage
the ozone layer, they are now virtually obsolete. The gap has been filled by
the increased use of pump systems, and by hydrocarbons and dimethyl ether.
1.15.1 Hydrocarbons
The hydrocarbon propellants are propane (freezing point - 42.1), n-butane
(freezing point - 0.5) and isobutane (freezing point - 11.7). Commercial
butane is always a mixture of n-butane and isobutane. Mixtures with propane
in different ratios are usually used to adjust the pressure. Hydrocarbons are
cheap, stable and of low toxicity, but are highly flammable.
1.15.2 Dimethyl ether
Dimethyl ether (DME) has been known as a propellant for over 50 years. It
is a gas (freezing point - 24.8) with a vapor pressure of 4.2 bar at 20°C.
It shows very low toxicity [37] and does not damage the ozone layer. Like
hydrocarbons it is inflammable, but unlike hydrocarbons it is miscible with
water. This can reduce or prevent the risk of flammability of DME aerosol
sprays, since 6% water can be solved in DME, or 34% DME can be solved
in water. Alcohol/DME mixtures are good solvents for PVP/PV A resins for
hair sprays, whereas hydrocarbon propellants are difficult to use in this field.
References
1. Nowak, G.A. (1985) Cosmetic Preparations Volume 1, Process Technology of Cosmetics,

Microbiology-GMP-Preservation, Data on Skin, Special Active Agents and Adjuvants.
Verlag fUr chem Industrie H. Zidkowsky KG, Augsburg.
2. Gohlke, F.J. and Bergerhausen, H. (1967) Alkylethersulfat, ein ideales Tensid. Seifen-Ole-
Fette-Wachse 93521-526.
3. Adam, W.E. and Neumann, K. (1978) Alkylethersulfate-ein Uberblick aus anwendung-
stechnischer Sicht. Fette Seifen Anstrichmittel80 392-40 I.
4. Seibert, K. and Boltersdorf, D. (1988) Magnesium surfactants. Second World Surfactant
Congress, Paris, CESIO.
5. Dilution of concentrated ether sulfates. Technical Information, Verhoeven N.V., Braam-
straat 229, B-2120 Schoten, 1992.
6. Giitte, E. (1964) Chemistry and physics of surface active substances. Proceedings of the
Fourth International Congress on Surface Active Substances. Volume 3, p. 83.
7. Mori, A. and Okumura, O. (1985) AOS. Happi(1) 51-52.
8. Ter Haar, G. (1978) AOS-The safety of alpha olefin sulfonates. Happi (3) 38-39.
9. Markland, W.R. (1976) The acyl isethionate surfactants. Norda Briefs no. 476.
10. Liebert, A.N. (1993) Final report on the safety assessment of sodium cocoyl isethionate. 1.
Am. College Toxicol. 12459.
11. Plate, H. (1995) Magnesium surfactants-Cleansing at its best and mildest. Parfumerie und
Kosmetik 7628-32.
12. Schuster, G. and Modde, H. (1965) Anwendungstechnisches Verhalten der Kombination
von Alkylarylsulfonat und Laurylathersulfat mit EiBfettsaurekondensaten. Fette Seifen
Anstrichmittel 67347-350.
13. Paassen, N.A.I. van (1984) Alkylethercarboxylate: Hautfreundliche Rohstoffe fUr
kosmetische Anwendungen. Kosmetik-lahrbuch 1994. Volume 8. Verlag H. Ziolkowsky,
Augsburg p. 121.
14. Cowen, R.A. (1974) Relative merits of in use and laboratory methods for the evaluation of
antimicrobial products. 1. Soc. Cosmet. Chern. 25307-323.
15. Schmitt, H.G. (1987) Uber die Wirkung antimikrobieller Substanzen. Parfumerie und
Kosmetik 69 5.
16. Imokawa, G. (1980) Comparative study on the mechanism of irritation by sulfate and
phosphate types of anionic surfactants. 1. Soc. Cosmet. Chern. 31 45-46.
17. Zeidler, U. and Reese, G. (1983) In-vitro-Test zur Hautvertraglichkeit von Tensiden.
Arztliche Kosmetologie 13 39--45.
18. Ellis, P.R., Derian, P.-J. and Vokov, R. (1994) Amphoteric surfactants-The next
generation. Euro Cosmetics 2 (July) 14-16.
19. Hodgson, J.E., Martin, e.G. and Nicholson, S.H. (1992) The use ofCocoampho(di)acetates
as an aid in the in-vitro safety assessment of mild surfactants. Parfumerie und Kosmetik 73
248.
20. Roerig, H. and Stephan, R. (1991) Amine oxides and their applications. La rivista Italiana
delle sostanze grasse 68317-321.
21. Markland, W.R. (1977) Low eye irritation shampoo systems. N orda Briefs no. 479.
22. Ruback, W. (1994) Surfactant trends in Europe. Chimicaoggi/chemistry today (5/6) 16-18.
23. Schrader, K.H. (1989) Grundlagen und Rezepturen der Kosmetika. 2nd edn. Hiithig Buch
Verlag, Heidelberg, 241 pp.
24. Balzer, D. (1991) Alkylpolyglucosides, their physico-chemical properties and their uses.
Tenside Surf Detergents 28419--427.
25. Biermann, M., Schmid, K. and Schulz, P. (1993) Alkylpolyglucoside-Technologie und
Eigenschaften. Starch/Starke 45281.
26. Busch, P., Hensen, H. and Tesmann, H. (1993) Alkylpolyglucoside-eine neue
Tensidgeneration fiir die Kosmetik. Tenside Surf Detergents 30116-121.
27. Wilkinson, J.B. and Moore, R.J. (1987) Harry's Cosmeticology. 7th edn. Longman Scientific
& Technical, Harlow, 442 pp.
28. Spiess, E. (1991) The influence of chemical structure on performance in hair care
preparations. Parfiimerie und Kosmetik 72 370-376.
RAW MATERIALS 35
29. Sebold, U. (1993) Fabric softeners worldwide. 3rd World Conference & Exhibition on
Detergents, Montreux, American Oil Chemist Society.
30. Lochhead R.Y. and Fron W.R. (1993) Encyclopedia of polymers and thickeners. Cosmetics
& Toiletries 108 95-135.
31. Friberg, S. (1994) Mineral oil: A natural compound? Soap/Chemical Specialities (2) 40-43.
32. Fulton, lE. (1989) Comedogenicity and irritancy of commonly used ingredients in skin care
products. J. Soc. Cosmet Chem. 40321-333.
33. McCrae, A., Roehl, E.-L. and Brand, H.M. (1990) Bio-ester. Seifen-Ole-Fette-Wachse 116
201-205.
34. Brand-Gamy, E.E. and Sprenger, J. (1988) Bienenwachs-Neue Aspekte eines klassischen
Kosmetik-Rohstoffs. Seifen-Ole-Fette- Wachse 114547.
35. Spiess, E. (1989) Stabilizing W /0 emulsions. Proceedings of the 9th Latin American Iberian
Congress of Cosmetic Chemists. Volume 2, IFSCC, Santiago del Chile. pp. 157-170.
36. Desai, N.B. (1990) Esters of sucrose and glucose as cosmetic materials. Cosmetics & Toiletries
10599.
37. Debets, F. (1990) Health and environmental safety ofDME as an aerosol propellant. Aerosol
Report 29 16-22.
2 Hair-care products
J.J. SHIPP
2.1 Introduction
Before discussing product formulation, some general remarks about product

development are appropriate.
1. Make sure that the brief is clear. There is little point in developing a
wonderful product if it is not the one that was requested. The brief
should include, as a minimum:
(i) Required performance parameters in as much detail as possible
(ii) Benchmark products, unless the development is in a completely
new area
(iii) Guidelines on cost
(iv) Proposed claims, and how these might be justified
(v) The required timing
2. Do not produce a Rolls Royce when a Mini would suffice or vice versa.
On the one hand, the accounts department will be extremely unhappy.
On the other, the product being launched will fail to deliver its promised
performance.
3. Do not use new raw materials if ones from existing stocks will do the
job just as well; avoiding unnecessary proliferation of the raw material
stocklist will benefit purchasing, stock control, space and cashflow.
4. Specifications often appear virtually identical, while in practice similar
products from different suppliers do not perform identically. This can
be very important for detergents and emulsifiers. Alternative sources
of supply can be investigated as a separate issue.
5. Ensure reproducibility on scale-up to full production, making use of
suitable plant and equipment. Dialogue with experienced process plant
operators can be invaluable.
6. Keep formulations as simple as possible; there should be a sound reason
for the inclusion of each ingredient.
7. Try to develop products which can be made as cheaply as possible, i.e.
with minimum energy requirements (heating, stirring) and minimum
time in the tank. Large-scale processing equipment is very expensive;
HAIR-CARE PRODUCTS 37
careful formulation can help to optimise the use of tank space and
tank time.
2.2 Hair: structure and chemistry
Hair consists of three main layers:

(i) the central core or medulla, which is not always present and whose
function is not entirely clear;
(ii) the cortex, which contributes the bulk of the hair shaft and consists
of elongated keratinised cells, the whole structure having a fibrous
nature. Each fibre is in turn made up of bundles of small fibres until,
at molecular level, polypeptide chains are found to be twisted together
to form a helix, an arrangement often favoured by nature;
(iii) the cuticle, in the form of thin overlapping scales that cover the cortex
like tiles on a roof. The overlap is such that the hair is smoothest
from root to tip. Techniques such as back-combing, where the comb
or brush is used 'against the grain' of the cuticle can cause considerable
mechanical damage. Cuticular cells also consist mostly of keratinised
proteins but, in this case, in the form of thin plates; the main difference
between cortex and cuticle is more a question of geometry than
chemistry [1, 2].
There are, of course, other constituents of hair, e.g. water, lipids and minerals,
and some work on how these are affected by the application of toiletries has
been carried out [3,4]. However, the main concern in this chapter is the
interaction between hair-care products and the main protein structure of the
cuticle, and of the cortex where this is exposed because of damage, chemical
treatment, or weathering [5]. A great deal of finer structure has been revealed
by electron microscopy and this has some bearing on these interactions [6].
The conditions under which products are applied (e.g. the use of heat) may
also affect the integrity of the hair's structure [7,8].
The cosmetic chemist is always aiming to achieve a result which looks
good, and time should be given to examining the mechanical and optical
properties of the hair, and how these affect our perception of 'a good-looking
result' [9-11].
Hair does not grow continuously, but passes between the anagen (or
growing) phase and the telagen (or resting) phase via the relatively brief
transitional catagen phase. The relative time spent in each phase can vary
considerably depending on the site on the body, age, sex, general health, etc.
Each individual hair has its own sequence, which is unaffected by that of its
neighbours. Some accurate measurements have been made of hair growth
rates and the factor affecting them [12].
The size and shape of a hair is determined by the follicle from which it
grows. Most Caucasian and Oriental hair grows fairly straight follicles and is
approximately circular in cross-section, although varying in diameter,
Oriental hair typically being oflarger diameter than European hair. Negroid
hair differs most, however. It grows from curved cuticles that are also some-
what flattened in cross-section, producing hair with an elliptical cross-section
and a pronounced curl. This type of hair often requires different treatment to
European hair and a separate chapter in this book (see chapter 6) covers its
special needs.
The most important structures present in the scalp dermis and epidermis,
from the point of view of the hair-care formulator, are the sebaceous glands
which secrete sebum into the hair follicle. Sebum acts as a lubricant for the
emerging hair and as a protectant against invasion of the follicle by hostile
species (chemical, physical or microbiological). Greasy hair, caused by over-
production of sebum, is a subject which has attracted some attention and
various ingredients have been examined in an attempt to overcome this
problem [13, 14].
2.2.1 Structure of hair keratin

Keratin is a protein, a copolymer of a variety of amino acids, about 25 types
in all. Keratin differs from most other proteins in that quite a high proportion
(around 20%) of the amino acid units contain sulphur, notably in the form
of the disulphide bond present in cystine. The basic amino acid unit may be
represented as
/COOH
R-CH
"'-NH 2
where R can either be a simple aliphatic group, or may be more complex,

containing benzene rings, double bonds, heterocyclic rings, fused rings or
additional carboxylic acid or amino groups. The side chains are relatively
small, accounting for about one half of the weight of the protein molecule.
There is an excess of carboxylic acid groups over amino groups in the side
chains, leading to an overall negative charge on the surface of the hair. In
that sense, the behaviour of the hair may be likened to that ofa cation-exchange
resm.
There are three main types of bond present in hair keratin:
1. Hydrogen bonds-these may occur between numerous sites (e.g. NH
and C=O) in the same or adjacent protein chains. Individually they
are weak, but collectively they contribute significantly to the overall
strength of the hair. Water causes the hair to swell as water molecules
'insert' themselves into these hydrogen bonds, converting them into
chains of bonds with consequent loss of strength. The breaking of
hydrogen bonds and their subsequent reformation explains the temporary
setting effect achieved by water treatment.
2. Salt linkages-these will occur between acidic and basic groups present
in the side chains and, as with hydrogen bonds, may link groups
together in the same or (more usually) adjacent polypeptide chains.
3. Disulphide bonds-cystine is a 'double' amino acid, containing COOH
and NH z groups at both ends of the molecule, with a disulphide bond
in between. It can enter into the structure of two adjacent polypeptide
chains forming a disulphide bond between them:
~CO~CH~NH~
I
CH 2
I
S
I
S
I
CH 2
I
~HN~CH~CO~
These bonds are extremely strong and can only be broken under severe
conditions (e.g. powerful reducing agents at high pH as in most
permanent-waving lotions).
Cross-linking mechanisms ensure that the keratin helices are held together
in a fairly rigid structure. The order in which the side chains occur is very
variable; steric hindrance is minimised by most of the side chains adopting
an outward-facing position, such that reactive groups on the side chains are
more exposed to the possibility of chemical reaction with hair-care products.
2.3 Shampoos
Shampoos may be made in various physical forms, liquids, creams or pastes,

aerosol and dry. The majority are liquids, either clear or pearlised. The
principal constituents of most liquid shampoos can be classified as:
• Primary detergents
• Secondary detergents
• Thickeners
• Foam stabilisers and boosters
• Perfumes
• Preservatives
• Diluents (usually water)
• Conditioning agents
• Other additives (functional or otherwise)
• Pearlisers/opacifiers
• Colours
Many ingredients are multifunctional and therefore do not clearly fall into
anyone category [15].
2.3.1 Detergents
There is no clear distinction between a primary and a secondary detergent.
Primary shampoo detergents are usually anionic and inexpensive, with
sodium laureth sulphate being easily the most widely used (particularly in
Europe). A whole mass of different detergent materials are available including:
• Alkyl sulphates
• IX-Olefin sulphonates
Alkyl ether sulphates
• Paraffin sulphonates
• Isethionates
• Sarcosinates
•
• Taurides
• Acyl lactylates
• Carboxylates
Sulphosuccinates
• Protein condensates
•• Betaines
• Glycinates
• Amine oxides
• Alkyl polyglycosides
to name but a few.

Within these groups, there are many variants, depending on chain length,
chain-length distribution, degree of ethoxylation, chain branching and
numerous other variables. The properties of the different detergents have
been reviewed in great detail elsewhere [15-25]. Here, therefore, only specific
comments about the most commonly used materials will be made. In the case
of sodium lauryl ether sulphate (CTFA (Cosmetic, Toiletry and Fragrance
Association) dictionary name sodium laureth sulphate) the general formula
is R-(OCH2CH2)n-OS03Na+ where R is the alkyl chain of variable length,
predominantly C l2 (lauryl) and the average degree of ethoxylation n is equal
to 2 or 3. The various methods of preparation for this surfactant are referred
to in chapter I and, depending on feedstock and the method used, many
variations are possible. Consequently, the final product, although called by
the same name, can be a complex and variable mixture. In addition,
sulphation and neutralisation can leave varying minor amounts of free fatty
alcohols and ethers, which have an important effect on the thickening
behaviour of shampoos [26]. The higher ethoxylates behave as non-ionic
surfactants in their own right although they are present in insignificant
amounts in commercial grades of sodium lauryl ether sulphate. Today
sulphation is nearly always carried out directly by S03 gas in a continuous
sulphation plant, giving better control and improved yields compared with
the older method using chlorosulphonic acid. Hydrolysis during neutral-
isation of the half-ester formed at the sulphation stage can give rise to free
fatty ethoxylated alcohol and sulphuric acid, the latter being subsequently
neutralised to form sodium sulphate:
+ S03 -. R-(OCH2CH2),-OS03H
R-(OCH 2CH 2),-OH
R-(OCH2CH2),-OS03H + H 20-.R-(OCH 2CH 2 ),-OH + H 2S0 4
H 2S0 4 + 2NaOH -. Na 2S0 4 + 2H 20
Temperature and pressure control, plus the avoidance of high local concent-
rations of the reactants, are paramount in achieving a product with the
desired characteristics, i.e. near water white, low odour, active matter consisting
of a well-defined and carefully controlled blend of the various species possible,
low chloride, low sulphate, and controlled (generally quite low) free fatty
alcohol and alcohol ethoxylates. Lauryl sulphates and ether sulphates are
obtainable as solutions in the 25-30% range or as 'high-active' concentrates,
usually in the 60-70% active matter range. These products are hazy semi-gels
with a curious rheology due to the presence ofliquid crystals, which gives them
an anisotropic structure. They can also be quite difficult to handle since, on
dilution with water, they pass through a gel phase. The structure of these fasci-
nating surfactants is explained admirably in a booklet published by Albright
and Wilson [27]. The potential problems associated with changing the source
of key raw materials part of the way through a development are numerous.
In Europe, lauryl ether sulphates (especially the sodium salt) are the most
commonly used primary surfactants, with lauryl sulphates occupying second
place. Some comparisons of the properties of these materials are shown in
Table 2.1. Judicious blending can optimise these various properties and other
ingredients can be used to modify them. A common example is the use of
coconut fatty acid diethanolamide to stabilise the foam and improve the
coarse texture of the foam obtained with ether sulphates. In addition, the
diethanolamide will help prevent excessive degreasing ofthe hair (superfatting
effect). A very simple and cheap range of shampoos for dry, normal, and greasy
hair could therefore be formulated as shown in Table 2.2. Crude, but reason-
ably effective in their primary function of washing the hair, products of this
type are available on the market in the 'cheap and cheerful' sector. The
rationale behind such formulation is a progressive increase in 'active matter'
(i.e. overall detergent concentration) from dry to greasy variants, accompanied
Table 2.1 Properties of lauryl ether sulphates and lauryl sulphates
Sodium lauryl Sodium laureth (2) Sodium laureth (3)

sulphate (SLS) sulphate (SLES-2) sulphate (SLES-3)
Flash foam Moderate Good Good

Foam texture Dense, creamy Coarse and open Coarse and open
Detergency increasing
Solubility increasing
Irritancy increasing
Table 2.2 Typical shampoo formulations for dry, normal and greasy hair
Dry hair Normal hair Greasy hair
Sodium lauryl sulphate (SLS), 30% 5 10

Sodium laureth sulphate (SLES), 27% 27 25 23
Coconut diethanolamide 3 3 3
Preservative q.s. q.s, q.s.
Perfume q.s. q,s. q.s
Colour q.s. q.s, q.s
Thickener (usually salt) q.s. q.s. q.s.
Water to 100 to 100 to 100
by an increase in the proportion of the stronger detergent (SLS) in the mix

on the basis that greasy hair will require a shampoo with more powerful
soil-removal properties.
Another useful comparison that can be made between these surfactants is
the effect of changing the cation. Sodium lauryl sulphate for instance, has
only limited solubility; changing the cation to ammonium or monoethanola-
minium, or triethanolaminium has a dramatic effect on the physical properties
of the surfactant as shown in Table 2.3.
Triethanolamine lauryl sulphate (TLS) is notable for being particularly
difficult to thicken and having poor colour stability. Diethanolamine lauryl
sulphate, once widely used in the US is rapidly declining in use as a result
of fears concerning nitrosamine formation from diethanolamine. Mono-
ethanolamine lauryl sulphate (MLS), conversely quite popular as a primary
detergent in Europe, but little used in the US, offers greater ease of
thickening and generally does not have the same propensity to darken with
age as TLS. Substitution of one of these amine-neutralised lauryl sulphates
for the SLES in the dry-hair shampoo formulation shown in Table 2.2 will
give a product with much denser foam, although there will be less of it.
It is fashionable (and usually desirable) to adjust the pH of shampoos to
be mildly acid (e.g. pH 6-6.5) This is essential when using ALS, in order to
avoid hydrolysis with the concomitant liberation of ammonia. Many alkano-
lamides contain appreciable amounts of free amine, giving rise to quite high
Table 2.3 Effect of changing the cation on the physical properties of sodium
lauryl sulphate (SLS)
SLS ALS MLS TLS
Solubility increasing
Viscosity increasing - - - - - -
Ease of thickening increasing - - - - - -
SLS = sodium lauryl sulphate

ALS = ammonium lauryl sulphate
MLS = monoethanolamine lauryl sulphate
TLS = triethanolamine lauryl sulphate
pHs in the final product. Consequently when using these with ALS, a slight
excess of acid should be present before adding the alkanolamide in order to
prevent the pH from rising above 7 at any time. Other lauryl and laureth
sulphates are occasionally encountered (e.g. magnesium, said to possess a
particularly low irritation potential and to be an excellent foamer).
Practical alternatives to the lauryl ether sulphates are few and include
oc-olefin sulphonates (mainly in the USA) and sulphosuccinates [28, 29]
(generally very mild, but significantly more expensive). Without doubt, one
of the success stories in recent years has been betaines, mainly
cocoamidopropyl betaine:
~ H3 T
R-C-NH-(CH2h-N+ -CH 2-COO-
I
CH 3
These amphoteric surfactants (see chapter 1), once considered to be somewhat

esoteric specialities, have become commodity items and prices have fallen,
making them readily available to the formulator of all but the cheapest
products. The addition of a small amount of betaine to the dry-hair shampoo
formulation in Table 2.2 would much improve it by making it less stripping
and offer a practical marketing proposition as a basic or 'family' shampoo
(Table 2.4), performing quite well over a wide pH range.
Cost considerations usually dictate that speciality surfactants assume a
secondary role. Table 2.5 gives some formulations illustrating typical use
levels of some of these materials. Along with the betaines, most speciality
surfactants will improve the quality of the lather, the mildness (as measured
by skin and eye irritation), and, most important, the afterfeel of the hair
[30-33].
A particularly interesting amphoteric is sodium carboxymethyl tallow
polypropylamine-4, for which a considerable amount of data relating to its
very low eye irritation has been amassed [34, 35]. This molecule is rather
unusual in having a much larger and more mobile hydrophilic 'head' than
more conventional amphoterics and it is to this configuration that Lomax
[34,35] attributes many of its properties.
Table 2.4 Typical formulation for a family

shampoo
Sodium laureth sulphate, 27% 27

Cocoamidopropyl betaine, 30% 5
Coconut diethanolamide 3
Preservative q.s.
Perfume q.s.
Colour q.s.
Sodium chloride q.s.
Deionised water to 100
Table 2.5 Shampoo formulations illustrating typical use levels of selected speciality surfactants
Sodium lauryl sulphate 30% 7

Sodium laureth sulphate, 27% 21 24 20
Ammonium lauryl sulphate, 30% 30
Monoethanolamine lauryl sulphate, 33% 35
Cocoamidopropyl betaine, 30% 4 3
Cocodimethylamine oxide, 35% 2
Sodium lauroyl sarcosinate, 30% 6
Cocoamphocarboxy glycinate, 30% 5 6
Sodium carboxymethyl tallow 3
polypropylamine, 27%
TEA coco-hydrolysed animal protein 30% 3
Alkanolamide (usually coconut
dialkanolamide) 2.5 2.5 3 2.5 4
Preservative q.s. q.s. q.s. q.S. q.s.
Perfume q.s. q.s. q.s. q.s. q.s.
Colour q.s. q.s. q.s. q.s. q.s.
Thickener q.s. q.s. q.s. q.s. q.s.
Deionised water to 100%
There is a tendency for 'frequent use' shampoos to have higher levels of

milder secondary surfactants, but an overall lower level of active matter. The
examples shown in Table 2.5 could be described as suitable for 'frequent use',
either at full strength, or diluted to about 80% strength. All of these
formulations are very much 'middle of the road' in terms of overall quality.
Experimenting with different combinations of these secondary surfactants
can sometimes give excellent results. Many secondary surfactants exhibit
lower irritation to skin and eyes than the commonly used primary surfactants
and in some cases an apparently synergistic effect exists whereby a compara-
tively small addition of the secondary surfactant can lead to a significant
decrease in the level of irritation of the overall blend. A mechanism
explaining this effect is proposed by Lomax [36].
The surfactants used in a shampoo need to be selected on the basis of a
whole range of properties, including:
• Cost
• Foam height [37]
• Foam texture
• Detergency
• Irritancy (lack of)
• Ease of handling and mixing
• Compatibility with other ingredients
• Colour
• Odour
• Purity
• Biodegradability (not usually a problem) [38--40]
The relative importance of these parameters will depend on the end use, e.g.
irritancy will be of paramount importance in a baby shampoo, while ease
of handling might be critical in a plant equipped with only simple mixing
facilities.
2.3.2 Thickeners and foam stabilisers

There are several methods by which shampoos may be thickened:
• alkanolamides or their alternatives
• polymeric materials
• electrolytes
Many of these ingredients are multifunctional, and most products use more
than one.
By far the most commonly used alkanolamide in the UK is coconut
diethanolamide; in the US there has always been a preference for a narrower
cut, generally lauryl or lauryljmyristyl blends. Both monoethanolamides and
diethanolamides are widely used. Monoethanolamides are more effective,
both as foam stabilisers and as thickeners, but have the disadvantage of being
waxy solids requiring a hot process to incorporate them into the mix.
Monoethanolamide Diethanolamide
Diethanolamides are very dependent on the method of manufacture and can

vary considerably in composition from supplier to supplier. The so-called
Kritchevsky amides, based on a 1: 2 mole ratio of fatty acid: diethanolamine,
usually contain quite significant amounts of a whole range of other materials,
some undesirable, most of little benefit. Superamides, prepared from a 1: 1
mole ratio, are purer. Quite large amounts of glycerine can be present in
coconut diethanolamide prepared from coconut oil and, while this has the
effect of making the material easier to handle and incorporate into a batch,
the ultimate thickening effect is reduced, although a benefit is sometimes
more effective solubilisation of perfumes.
While lauric, lauric/myristic and coconut mono- and diethanolamides
dominate, other alkanolamides find more limited use, e.g. oleic and linoleic
diethanolamide in gel shampoos based on SLES (where their thickening
effect is remarkable), lauric monoisopropanolamide (probably the most
effective thickener and foam stabiliser of the group), stearamides (as part of
a pearlescing system) and ricinoleic diethanolamide, said to possess some
conditioning properties.
Some surfactant systems are notoriously difficult to thicken, not responding

well to electrolyte additions. Various raw materials manufacturers have
developed alternatives to alkanolamides which overcome this difficulty. These
include PEG-6000 distearate, PEG-55 propylene glycol oleate and PEG-120
methyl glucose dioleate (PEG stands for polyethylene glycol). These
materials can be particularly effective in systems based on some sulpho-
succinates, ethoxylated sorbitan esters, alkane sulphonates, lauryl sulphates
with particularly low levels of free fatty alcohol, or conventional systems
where a much higher than usual viscosity is required, e.g. the currently
fashionable childrens' 'wobbly bath gels'.
Most surfactant systems are non-Newtonian in behaviour and can exhibit
phenomena such as shear-thinning, shear-thickening, time-dependence and
yield points, to name but a few. The ultimate test is whether the viscosity of
the product is suited to the packaging in which it is sold, and meets the
consumer's expectation. Thickness is invariably equated to concentration,
value for money, and 'richness' in the layman's perception of the finished
product.
Polymeric materials used for thickening shampoos include a variety of
natural gums, such as guar, karaya, locust bean, carragheenan, and tragacanth.
In practice these materials, in unmodified form, find little use in today's
shampoos, and this class of thickeners is dominated by cellulosic derivatives,
such as hydroxyethyl cellulose, carboxymethyl cellulose, and hydroxypropyl
methylcellulose. These materials are usually dispersed in all or part of the
water in the formulation before adding the other ingredients. A disadvantage
with most of these materials when used on the production scale is the difficulty
of obtaining complete solution rapidly; there is an unfortunate tendency for
the gum to clump together and form 'golf balls' consisting of dry powder
surrounded by partially hydrated gum which can seem to take an eternity
to dissolve. Non-ionic cellulose derivatives, such as hydroxyethyl cellulose,
exhibit an inverse cloud point (cf. nonyl phenol ethoxylates and other similar
series) and this can be used to good effect by adding the gum to water heated
to a temperature above the cloud point. The gum, insoluble at this temperature,
will disperse to form a milky liquid which, on cooling, will give a clear and
lump-free solution. Some gums are available in a surface-treated form,
whereby each particle is coated with a solution-retardant chemical, thus
allowing the particles to disperse before substantial hydration takes place
and avoiding the formation of 'golf balls'. High-speed mixing is usually
recommended to initially disperse these materials, which should be sprinkled
into the vortex. Once initial dispersion is complete, stirring should be slowed
down to avoid unnecessary aeration. Very high-shear mixing is best avoided
since this can cause cleavage of the polymer molecules with consequent
adverse effect on performance.
Gum-thickened products have a different rheology to otherwise similar
electrolyte-thickened products. The temperature effect is less for gum systems
than for an electrolyte-thickened system. This feature can be useful when
formulating for climates where the product might be subjected to large
temperature variations in storage, distribution and use. In addition, gums
will often stabilise foam by strengthening the film at the air/liquid interfaces
in the matrix of bubbles. This also has the effect of making the foam feel
denser ('creamy') in use. This difference in tactile effect is not limited to the
foam-it is sometimes apparent as soon as the shampoo is poured into the
hand. There are, however, some disadvantages, namely high cost, lengthened
processing time (with higher energy consumption if a hot process is used),
and the difficulty of making viscosity adjustments afterwards. This last
problem can often be overcome by using a small amount of electrolyte for
final viscosity adjustment.
The effect of electrolytes on the viscosity of surfactant systems is a result
of the increase in ionic density of the solution with its consequent effect on
micelle size and shape. It is conventional to add an electrolyte with the same
cation as that ofthe primary anionic surfactant in the system, e.g. ammonium
chloride in ammonium lauryl sulphate based systems, and sodium chloride
in sodium lauryl ether sulphate based systems. This is logical since most of
the anionic surfactant is present in ionised form and the addition of, say,
sodium chloride to ammonium lauryl sulphate solution could partly negate
the reasons for choosing ALS instead of SLS.
Addition of electrolyte beyond a certain point will cause thinning, often
quite rapid, and an increase in cloud point. The point at which the maximum
in the viscosity/electrolyte curve occurs will depend on many factors,
including concentration, presence of alkanolamides, level of free fatty alcohol
or ether in the surfactants, and the effect of the perfume. Some typical curves
are shown in Figure 2.1. Note that the peak viscosity occurs at a lower salt
level when materials such as free fatty ether or alkanolamide are present. This
is probably due to the formation of mixed micelles. A well-formulated
shampoo will have a curve which is not too steep and which has a target
viscosity range in the centre (i.e. the most linear) part of the ascending curve
(see Figure 2.2). Shampoos which have gone 'over the top' of their curve can
often be rescued by the addition of water, or a blend of water and the primary
surfactant. Electrolytes should always be added as solutions (typically 25%
w! w for N aCI) to avoid high local concentrations that might lead to gelation
and, consequently, unnecessarily protracted mixing.
Occasionally one encounters shampoos which need thinning rather than
thickening. This usually occurs when the active matter is high, when the raw
materials already contain high levels of electrolytes or when large amounts
of some amphoterics are present and is simply solved by the addition of a
small amount of a short-chain alcohol or glycol. Ethanol or isopropanol
may be used; the glycols (less odorous and not so flammable) are preferred.
Propylene, butylene and hexylene glycols are effective and commonly
available.
10
% Sodium Chloride
Figure 2.1 Typical viscosity I electrolyte curves for a surfactant with high and low levels of free
fatty alcohol. 6, sodium lauryl ether sulphate, 11 % active; 0, sodium lauryl ether sulphate, 11 %
active + 1%laureth·3; 0, sodium lauryl ether sulphate, II % active + 3% cocamide-DEA (DEA
stands for coconut diethanolamide).
I
I
~ I ~-,
I /" ,
I 1/ \
___ II _________________ J I \\
I \
I \
Preferred I \
viscosity I \
range I \
I \
I \
I \
I \
/ \
I
-------------_/
I /
:,-- _ /
I .,/
I
% electrolyte
Figure 2.2 Viscosity I electrolyte curve for a well-formulated shampoo.

2.3.3 Perfumes
Perfumery is a complex subject in its own right (see chapter 8), but most of
the detailed knowledge is required in the creation of the fragrances; the more
mundane process of using these fragrance creations in the product formulation
requires less ability, although selection may not be so easy [41-44].
Occasionally, one is required to develop a shampoo as a line extension to
a fragrance-led range. Where the range already contains toiletry products it
may only be necessary to include an existing perfume at the appropriate
level. If, however, the range consists entirely of alcoholic-based perfumery
products, it may be necessary for the fragrance house concerned to modify
the perfume compound to achieve an acceptable performance in a detergent
base. At the other extreme, in very cheap shampoos, the perfume is sometimes
regarded as quite incidental. There have been attempts to market shampoos
with high levels of fragrance (although not part of a fragrance-led range),
even fragrances designed to persist on the hair after washing [45], but these
have met with limited success.
Fragrance can often be simply added to the shampoo after the completion
of any hot part of the process. If solubility is a problem, then the perfume
can be premixed with a suitable solubiliser before addition, the ratio within
the premix being determined by trial and error. There are many solubilisers
to choose from but some, for example polysorbates may cause thinning of
the product. In the author's experience, PEG-40 hydrogenated castor oil
often works well. Where the manufacturing method permits, premixing the
perfume with the alkanolamide, provided that this can be carried out at a
moderately low temperature (say < 40°C), will usually suffice.
2.3.4 Preservatives
As with perfumes, this subject merits a book in its own right. The main
concerns, as with all products destined for use on the human body, are
resistance to spoilage and protection of the consumer. In the case of sham-
poos, it is particularly important to ensure that the product contains
no pathogenic organisms, especially those capable of damaging the eyes. A
variety of preservatives are available to the formulator and all of those in
the following list have been commercially used in shampoos, either alone or
in various combinations.
• Parabens (the shorter chain esters are the most soluble)
• Imidazolidinyl ureas
• 2-Bromo-2-ni tropropane-l,3 -di 01
• 5-Bromo-5-nitro-l,3-dioxane
• Dimethyl dimethylol (DMDM)/hydantoin
• Methylchloroisothiazolinone and methylisothiazolinone
• Phenoxyethanol
• Diazolidinyl urea
• Methyldibromoglutaronitrile
• Quaternium-15
• Sodium iodate
• Glutaraldehyde
• Formaldehyde
Many of the surfactants used as raw materials for shampoo manufacture
are already preserved, and the contribution of this portion of the preservative
system must be taken into account. Provided that sufficient quantity is being
ordered, most manufacturers of surfactants are happy to consider alternative
preservative systems. Other ingredients, such as proteins and herbal extracts,
may also be preserved and it is therefore quite conceivable that a newly
developed shampoo may already contain a number of different preservatives.
Apart from the various performance-based choices inherent in selecting a
preservative system, which are well documented elsewhere [46, 47], there is
also the problem of legislation; it is vital to know in which countries the
product is to be sold in order to ensure that the product meets local requirements.
This is true of all raw materials, but preservatives, particularly formaldehyde,
(along with colours and ultraviolet absorbers) are a special case and are often
heavily regulated. The chosen preservative system should pass a recognised
(e.g. BP, USP) challenge test in the final formulation, preferably when freshly
prepared, and when aged. If such testing can be accompanied by meaningful
preservative assays, so much the better.
2.3.5 Opacijiers and pearlisers

Opacification of shampoos is usually used for aesthetic reasons, although it
is occasionally a useful technique to use when the product cannbt be made
completely clear. If a pastel colour is required, then opacification is a pre-
requisite. Opacification may be achieved simply by adding a small amount
of fine, intensely white polymer dispersion. Styrene/acrylate copolymers pre-
dominate, but many quite complex blends are available. Most contain some
surfactant, usually anionic, which should cause no problem in most shampoo
bases. Trials with different opacifiers at different levels will determine how
to achieve the desired effect. For ease of dispersion and subsequent product
stability, dilution of the opacifier to a 10% solution with water before addition
to the main mix is usually recommended.
The vast majority of opaque pearlescent products depend for their effect
on the suspension of various stearate crystals in the liquid base (the term
'stearate' as used here may cover a broader fatty acid cut than just C 1S )'
Different stearates give different effects; diethylene glycol monostearate, for
instance, gives a flatter, more opaque pearl than monoethylene glycol
monostearate, which has less opacity but more 'sparkle'. There are three
commonly used ways of achieving pearlescence using stearates.
1. To buy a ready-made pearlised base that simply needs dilution and the
addition of any other desired materials to make a finished shampoo.
Such products are, of necessity, very thick.
2. To add the chosen pearlising agent (most commonly ethylene glycol
mono-distearate) to the hot mix, or a substantial part of it, at a tempe-
rature of about 75°C and form the crystals in situ during the cooling
cycle. This method can be quite cheap on raw material costs, but expensive
on energy and tank time. The process is also sensitive to changes in,
for example, mixing equipment, stirrer speed and cooling rate, leading
to variable results.
3. To buy a highly concentrated pearlising agent in a liquid or semi-liquid
form that may be added to the batch as a cold mix. This is usually the
most cost-effective route and as little as 2% of such a concentrate can
give a good effect.
The main factors that affect the appearance of the 'pearl' are:
(i) Composition of the stearate ester
(ii) Presence of alkanolamides and other materials
(iii) Rate of cooling
(iv) Shear rate of stirring
(v) Composition of the base
An effective concentrated pearlising agent can be made in the laboratory to
the following formula:
%w/w
Ethylene glycol mono/distearate 20
Coconut monoethanolamide 20
Sodium lauryl ether sulphate, 27% 60
Hexylene glycol (to reduce viscosity) q.s.
This formula, prepared with high-shear mixing, will give high opacity and
low sparkle. The use of low-shear mixing will have the reverse effect. Rapid
force-cooling will also favour opacity, while slow cooling will favour sparkle,
i.e. any conditions which favour the growth of larger crystals will increase
sparkle at the expense of opacity. Changing the alkanolamide also has an
effect; coconut diethanolamide will give less sparkle and lauric mono-
isopropanolamide more. When left undisturbed for some time, a large visible
difference between the above variants is not apparent but, on pouring from
one container to another, the difference becomes more marked as the thin
plate-like stearate crystals align themselves with the direction of flow.
Although most of the pearl concentrates on the market are based on sodium
lauryl ether sulphate, some that are based on amphoterics or on non-ionics

are also available, thus increasing the scope for the use of these materials.
2.3.6 Conditioning agents

The concept of a conditioning shampoo is a paradox. The majority of active
conditioning agents are cationic surfactants and are therefore incompatible
with the anionic surfactants that are the basis of nearly all shampoos. To
take an extreme example, the addition of cetyl trimethyl ammonium chloride
to a shampoo based on sodium lauryl sulphate will result in the formation
of cetyl trimethyl ammonium lauryl sulphate, a very large and fairly useless
molecule which will do its very best to precipitate out of solution. The
properties of both the anionic and cationic molecules present can be modified
to make them more compatible; the base itself can also be made more
amenable to the inclusion of both of these seemingly antagonistic species.
1. The base can be made less anionic in character by including a reasonably
high percentage of amphoteric surfactant. (The amphoteric can be thought
of as analogous to a co-solvent, capable of uniting otherwise incompatible
materials, e.g. ethanol as a co-solvent for water and diisopropyl adipate.)
2. The charge density on the cationic and anionic can be reduced. Here,
Tab!e 2.6 Formulations for conditioning shampoos using polymeric cationic materials in
predominantly anionic bases
Ammonium lauryl sulphate, 30% 30 15

Sodium lauryl ether sulphate, 27% 30 27 35 15
Triethanolamine lauryl sulphate, 42% 5
Cocoamidopropyl betaine, 30% 6 6 8 5
Pearl concentrate (SLES based) 2.5 2
Cationic guar gum 0.2 0.5
Quaternised hydrolysed protein 2
PEG·15 tallow polyamine 2.5
Cocoamphocarboxyglycinate, 30% 8
Sodium carboxymethyltallow
polypropylamine-4, 27% 4
Cocoamidopropylamine oxide, 30% 2
Coconut diethanolamide 3 2 2.5 1.5
Lauric diethanolamide 3
5·Bromo·5-nitro-I,3-dioxane, 10% 0.2 0.1
Methy1chloroisothiazolinone and
methylisothiazolinone, 1.5% 0.05 0.1 0.1 0.05
Sodium chloride q.s. q.s. q.s. q.s.
Ammonium chloride q.s.
Hydroxypropyl methyl cellulose 0.5
Citric acid q.s. q.s. q.s. q.s. q.s.
to pH 5.5 6.0 6.0 5.5 6.5
ethoxylation is the universal panacea; sodium lauryl ether sulphate has
better compatibility with cationics than does sodium lauryl sulphate,
while ethoxylated cationics are generally more compatible with anionics.
3. A variation on theme (2) is the use of a polymeric cationic, with the
overall effect one of reduction of charge density. Some of the polymeric
cationics available are surprisingly substantive and can also provide
good afterfeel when used in products such as hair and body shampoos
[48,49].
4. The level of active matter can be made high enough for any anionic/
cationic complex to be solubilised by the large excess of anionic present
[50].
5. A sufficiently high level of non-ionic (really another variation on the
theme of coupling agents) will assist compatibility.
Some formulations where polymeric cationic materials are used in
predominantly anionic bases are shown in Table 2.6. The examples shown
in Table 2.7 illustrate the use of non-polymeric cationics in conditioning
shampoos.
Other means of conditioning, not based on cationic materials, are available.
Table 2.7 Formulations for conditioning shampoos using non-polymeric cationics

Ammonium lauryl ether sulphate, 27% 40 15 36
Ammonium lauryl suphate, 30% 30
Sodium lauryl ether (10 EO) carboxylate, 30% 15
Cocoamphocarboxyglycinate, 30% 6 4
PEG-3 cocoamide 3
Coconut diethanolamide 2.5 3
Lauric monoisopropanolamide 2
Pearl concentrate 2.5
Ethylene glycol mono-distearate 2
Stearamidopropyl dimethylamine lactate 2.5
Cetyl trimethylammonium chloride, 30%
N-(2-hydroxyethyl)-N,N-dimethyl-N-2-hydroxyethyl
ammonium chloride, 30% 2
y-Gluconamidopropyl dimethyl-2-hydroxyethyl
ammonium chloride, 60% 2
D-Panthenol 0.3
Dimethicone copolyol 0.6
Perfume q.s. q.s. q.s. q.s.
5-Bromo-5-nitro-l,3-dioxane, 10% 0.15 0.2 0.2
methylisothiazolinone, 1.5% 0.05
Hydroxypropyl methyl cellulose 0.8
Ammonium chloride q.s. q.s.
Sodium chloride q.s.
Colour q.s. q.s. q.s. q.s.
Citric acid q.s. q.s. q.s. q.s.
to pH 5.5 6.0 5.5 6.0
The substantivity of cationics is an electrostatic effect restricted to the

outside of the hair shaft where the charge lies. Cationics, therefore, will not
penetrate the hair shaft, the surface electrostatic attraction working against
this possibility. Consideration of molecular size leads to the conclusion that
deep penetration of the hair shaft by large species is improbable. Where there
is significant damage to the hair shaft, however, the story is different. Partially
hydrolysed proteins can be shown to be effective in 'repairing' split ends. In
this case, the large protein molecules are effectively bridging the gaps and
filling in the holes caused by physical damage. The implication of the above
argument is that a sufficiently small molecule of low polarity should be able
to penetrate the hair shaft, and this proves to be the case. Both panthenol
(a pantothenic acid precursor) and amino acids have been shown to penetrate
the undamaged hair shaft and, once there, to impart worthwhile conditioning
effects. Panthenol is well-documented and, properly formulated into a
Table 2.8 Formulations for a conditioning shampoos using non-quaternary conditioners
A B C D E
Sodium lauryl sulphate. 30% S

Sodium lauryl ether sulphate, 27% 30 36
Monoethanolamine lauryl sulphate, 33% 40
Ammonium lauryl ether sulphate, 30% 35 36
Cocoamidopropyl hydroxysultaine, 30% 5 4
Sodium carboxymethyltallow 6
polypropylamine-4, 27%
Lauric diethanolamide 2 2.5
Ricinoleic diethanolamide 3
Pearl concentrate 3
PEG-S5 propylene glycol oleate and 3 2.5
propylene glycol
Quaternium-80 0.2
Dimethicone copolyol 0.3 0.4 0.3
Cetyl dimethicone copolyol 0.2
PPG-S-ceteth-IO-phosphate S
Hydrolysed collagen protein 2
Keratin amino acids, SO% I
D-Panthenol 2 O.S 0.3
Dimethiconol and cyclomethicone I
Perfume q.s. q.s. q.s. q.s. q.S.
Sodium chloride q.s. q.s. q.s.
DMDM-hydantoin 0.2
2- Bromo-2-nitro-1 ,3-propandiol 0.05 O.OS
Methyldibromoglutaronitrile and 0.1 0.1
phenoxyethanol
Citric acid q.S. q.s. q.S. q.s. q.S.
to pH 7.0 7.0 6.5 6.0 6.5
product, can justify claims for moisturising and hair thickening, as well as
conditioning. Sufficient active ingredient must be used to justify any claims
made.
A variety of other materials have been used as conditioning agents in
shampoos, including various vegetable oils, vitamins, lanolin and its
derivatives, herbal extracts and some speciality silicones. The speciality
silicones merit examination since they are currently popular, offer an
alternative to cationic materials and should be less prone to 'build-up' or
'over-conditioning'. Silicone glycol copolymers can assist gloss and
conditioning and seem to be substantive, to a degree, from shampoo bases,
although they do reduce viscosity. More recently, very high viscosity
dimethiconol dissolved in cyclomethicone has become more popular,
although 'build-up' problems with shampoos using this ingredient have been
reported. Build-up, together with the relative merits of various silicones and
silicon derivatives in shampoos, is discussed in more detail by Sejpka [51]. An
even more recent system advocates the use of several silicones together, at
quite low levels, to give an optimised conditioning effect (see formulation C
in Table 2.8).
2.3.7 Colours and colour fading

A large number of colours are available, but the list is restricted by the
regulations governing their use wherever the product is sold. Whilst higher
purity colours are more expensive than technical grades, it is preferable to use
colours which meet both the EC and US specifications whenever possible;
such colours will be acceptable virtually anywhere in the world. The cost
premium is minimal.
Some aspects of colour stability, e.g. stability to pH variation and light,
can be predicted but, unfortunately, the number of possible interactions
involving the colour in a base as complex as a modern shampoo means that
colour stability (especially to light) must be individually evaluated for each
formulation. This can be carried out in natural sunlight or under accelerated
conditions in a purpose-built apparatus using a xenon arc lamp or similar,
with suitable filters to give simulated high-intensity sunlight. The instrument
may be calibrated by using a product of known stability as a standard or
by using blue wool to BS 1006 [52].
Colour fading can usually be minimised by incorporation of a suitable
UV absorber. Water-soluble absorbers usually work best in shampoos, the
most popular being benzophenone-4 and benzophenone-2. However, it is
always worth trying others, both UV-A and UV-B absorbers. Usage levels
are low, generally 0.05-0.1%.
Colours should be added in solution and not as solid material. Aqueous
solutions of colours require preservation -an aqueous/alcoholic base is safer.
2.3.8 Other additives

Sequestrants, such as EDTA (ethylene diamine tetra-acetic acid) salts, are
sometimes added at low levels to aid rinsing in hard water and boost the efficacy
of preservatives. The majority of other shampoo additives are not truly active
ingredients, being included for marketing reasons rather than performance.
Anti-dandruff shampoos have been a growth area in recent years, with
various active ingredients having been used. Selenium sulphide is sometimes
encountered, but is mainly restricted to prescription products. Coal-tar
extracts and phenolic derivatives have been used but are not very effective
and traditionally find their place in 'medicated' shampoos. Their use is
declining due to doubts about the safety of coal-tar derivatives. Derivatives
of undecylenic acid, in particular the sodium salt of undecylenic acid
monoethanolamide sulphosuccinate, have been found to have some degree
of effectiveness. The widespread adoption of zinc pyridinethione as an active
ingredient has substantially increased the use of anti-dandruff shampoos. This
ingredient is usually supplied as a 48% dispersion and is a very dense solid
which needs to be suspended in the product. To obtain stability this requires
a suitable clay- or gum-type suspending agent, with fairly high yield-point,
and restricts the formulator to producing an opaque product. A more recently
available anti-dandruff agent is piroctone olamine, which is water-soluble
and therefore much easier to use.
The nature of dandruff, and its causal relationship with scalp flora,
particularly pityrosporum ova Ie, has given rise to much speculation. The
exact nature and cause of dandruff, and its definition as a clinical condition,
has not been fully established [53-58]. Consequently, the classification of
anti-dandruff products as cosmetics or pharmaceuticals remains unresolved,
except in the USA where they are clearly OTC drugs. The formulations
shown in Table 2.9 illustrate various types of anti-dandruff shampoo.
Baby shampoos form another important category. Babies' hair does not
require a high level of detergency to clean it and, above all, the products
must be non-irritant to eyes and skin, or as close to this ideal as possible.
In this sense, baby shampoos have a close affinity with frequent shampoos,
the latter often lying between baby shampoos and conventional shampoos
in terms of formulation. Baby shampoos are discussed in more detail in
chapter 5.
Other specialist shampoos are shown in Table 2.10 and include swimmers'
shampoos, containing a reducing agent (usually sulphite or thiosulphate) to
neutralise the chlorine from the water in swimming pools, and UV-protection
shampoos. Unfortunately, most UV absorbers are not very substantive to
the hair when applied from a shampoo base. Dimethyl p-amino benzoic acid
(PABA) ethyl cetearyldimonium tosylate, however, is a modified PABA
derivative that is cationic in nature and can give better results, although its
poor solubility characteristics are somewhat restrictive [59].
The final class of shampoos that will be mentioned here-anti-build-up
Table 2.9 Typical formulations for anti-dandruff shampoos
Sodium lauryl ether sulphate, 27% 40 25

Ammonium lauryl ether sulphate, 30% 20
Triethanolamine lauryl sulphate, 40% 42 15
Cocoamphocarboxy glycinate, 30% 5 6
Lauric/myristic diet hanoi amide and
propylene glycol (80/20) 4
Coconut diethanolamide 2.5 1.5 2 3
Diethylene glycol mono-/distearate 3.5
Pearl concentrate 2.5
Sodium undecylenic acid
monoethanolamide sulphosuccinate, 50% 5
Zinc pyridine thione, 48% 2 4 2
Piroctone olamine 0.7
Hydroxyethyl cellulose 0.5
Magnesium aluminium silicate I
Bentonite
Carbomer 934 0.25
Sodium hydroxide q.s.
to pH 5.5
Citric acid q.s. q.s
to pH 6.5 6.0
Colour q.s. q.s. q.S. q.s. q.s.
Preservative q.s. q.s. q.s. q.s. q.s.
shampoos~is perhaps the simplest. As the name suggests, these shampoos

are formulated to help remove excess build-up of conditioning l1;gents and
styling aids. Consequently, they are usually quite simple systems (Table 2.10),
with good detergency and containing no conditioners. Since most conditioners
(whether from shampoos, conditioners or styling aids) are applied to the hair
under acid conditions, anti-build-up shampoos are left alkaline. (This can
also help remove acid resins.) For the same reason, 'lacquer-removing' shampoos,
the ancestors of this class of product, usually contained an excess of mild
alkali (e.g. TEA). A means of measuring the efficacy of these products in
removing deposited polymers from the hair shaft is discussed by Sendelbach
et al. [60].
Before leaving shampoos, the question of impurities should be considered.
Most surfactants contain small amounts of numerous by-products. Of
particular concern are the nitrosamines and l,4-dioxane.
Nitrosamines are potent carcinogens derived from the reaction of nitrite
and secondary amines. The most important in cosmetics and toiletries is
nitrosodiethanolamine (NDELA), which is formed, under some circumstances,
from diethanolamine. To avoid this, lower grades of triethanolamine
(which can contain substantial amounts of diethanolamine) should be replac-
ed with a higher grade (99% + purity). As mentioned earlier, some coconut
Table 2.10 Formulations for swimmers', UV-protection, and anti-build-up shampoos
Swimmers UV -protection Anti-build-up

shampoos shampoos shampoos
Sodium lauryl ether sulphate, 27% 36 40 40 24 20

Sodium lauryl sulphate, 30% 10
Sodium lauryl sarcosinate, 30% 6
Triethanolamine lauryl sulphate, 42% 2S
Cocoamphocarboxy glycinate, 30% 6
Cocamine oxide, 3S% 3
Pearl concentrate 2.S 2
Coconut diethanolamide 2.S 3 4 2
Lauric diethanolamide 2
Panthenol 0.4
Polyquaternium-7, 8% 2
Octyl dimethyl PABA 0.3
Benzophenone-4 0.2
Dimethyl PABA ethyl cetearyl dim onium
tosylate
Urea 2
Sodium thiosulphate 0.3
Citric acid q.s. q.S. q.s.
to pH 7.0 6.S 6.0
Hexylene glycol q.s.
Triethanolamine to pH- 8.S 8.S
Sodium chloride q.s. q.S. q.s. q.s.
Methylchloroisothiazolinone (and)
methylisothiazolinone, 1.5% 0.03 O.OS
Phenoxyethanol (and)
methyldibromoglutaronitrile O.OS O.OS
Propylene glycol (and) S-bromo-S-nitro-
1,3-dioxane O.lS 0.1
diethanolamides, especially the Kritchevsky type, can contain quite large

amounts of diethanolamine and it is advisable to replace these with other
alkanolamides or alternative thickeners/foam boosters.
l,4-Dioxane is a cyclic dimer of ethylene oxide and can arise whenever
ethoxylation is used in the manufacture of a surfactant. Like NDELA, it has
been identified as a carcinogen and some European countries are now tending
to use non-ethoxylated surfactants to minimise dioxane levels. Control can
be exercised at each stage of surfactant manufacture and it is now possible
to buy 27% active SLES with dioxane < 25 ppm [61-65]. A briefreview of
some of the more modern shampoo ingredients is given by Woodruff [66].
2.4 Conditioners
Harry [67] attempts to distinguish between conditioners, rinses and tonics,

but such classifications have been overtaken by events, with terms such as
rinse, conditioner, deep conditioner, balsam, hair mask, cream rinse, being
used interchangeably by the public and industry alike. Classification requires
a definition for 'conditioning' and, since this term means many things to
many people, e.g. reduction of fly-away, gloss, sheen, manageability, ease of
handling, or simply general overall appearance, the issue is best avoided by
grouping all such products together.
The basic mode of action of hair conditioners has been touched upon in
section 2.3.6. In a conditioner, the properties of cationic surfactants can be
fully exploited without having to consider the question of compatibility with
anionics. Consequently, cationics with high charge density, and properties
undiluted by ethoxylation or polymerisation, feature prominently among the
preferred active ingredients. Before examining the formulation of hair
conditioners in detail, the properties that hair conditioner should impart will
be considered.
(i) Improved wet combing
(ii) Improved dry combing
(iii) Reduced fly-away (i.e. antistatic)
(iv) Increased gloss
(v) Increased volume
In addition, more specific claims, e.g. improved curl retention, repair of
damage of the hair shaft, or moisturising, may be required.
The most common physical form for a conditioner is the thick opaque
liquid, although clear liquids have recently become popular. Gels sprays and
non-pourable creams are available, while 'leave-on' conditioners (usually in
spray form), as opposed to the more common 'rinse-otT products, are also
in demand.
Classification of the raw materials into neatly defined categories is not as
straightforward as with shampoos, but a suggestion is as follows:
• Primary surfactants (nearly always cationic)
• Polymers
• Bodying agents
• Auxiliary emulsifiers
• Oily components
• Other 'active' ingredients
• Thickeners
• Perfumes
• Preservatives
• Diluents (usually water)
• Colours
• Other non-functional ingredients
Many of the ingredients are multifunctional within the formulation, and not
all need be present.
2.4.1 Cationic surJactants

The most common principle active ingredients in hair conditioners are
quaternary ammonium compounds (or 'quats') corresponding to the formula
R+
12
R I- - N - R3 X
1
R4
where X, the non-surface active anion, is commonly chloride and R 1 , Rz, R3
and R4 are alkyl or other groups. Normally two or three of these groups
are methyl, and one or two are derived from long chain fatty acids, e.g. tallow
or coconut oil. Typical examples are
+
CH 3
1 Cl-
!H
CI6H~N-CH3
Cetyl trimethylammonium
3 chloride
+
CH I6H33
CI6H33--I-CH3
I cr
CH3 Dicetyl dimethylammonium
chloride
+
CH 3
H-~-O'
C 18 37 1 -
cr
Stearyl dimethyl
CH3 benzylammonium
chloride
It is notable that, while the optimum length for most anionic surfactants for
shampoo use is around C 12/C 14, in the case of cationics for conditioners,
this rises to C 16/C 1S . More recently, there has been considerable interest in
quats with longer chains, e.g. C zz , behenyl. Fuller details ofthe many available
quats are given by Hunting [68], the CTFA Cosmetic Ingredient Dictionary
[69], and elsewhere [9, 70-73]. Some quats are relatively poorly biodegrad-
able. A more recently introduced type of quat, the 'ester quat' is claimed to
be better in this respect. As the name suggests, the side chains contain ester
linkages:
o CH 3
II I
R~C~O~CH2~CH2~N~CH2~CH2~O~C~R , Where R = alkyl, usually C 16- 18
I II
CH 3 0
Clearly, the properties of the various quats differ and this is governed by
some rules of thumb. The properties can often be related to charge density;
a highly charged cationic will be more strongly attracted to the negatively
charged hair surface but, once on the hair surface, the number, shape and
size of the fatty chains in the molecule are the determinants. A 'quat' with
two fatty chains will provide more lubricity than a quat with one, while a
long chain may be a more effective lubricant than a shorter one. As a result,
it is quite common to encounter single fatty-chain quats in products designed
to be used on greasy hair or for frequent use, and twin fatty-chain quats in
products intended for dry or damaged hair. The fatty chains may be derived
from more exotic sources such as mink oil, lanolin acids, glucamic acid
(contains many hydroxyl groups and is very water-soluble), oleic acid,
isostearic acid, etc., as well as from coconut oil or tallow. At the other end
of the molecule, there may be a number of nitrogen atoms, among which
the positive charge centre may be distributed. The amidoamines are a form
of 'do-it-yourself' quat that can be neutralised in situ by an acid of the
formulator's choice. The conditioning effect is quite light, comparable with
a conventional single fatty-chain quat. Examples are stearamidopropyl
dimethyl amine and stearamidoethyl diethylamine. An interesting com-
parison between the properties of various types of quat is made by Allandic
and Gummer [74].
A hair conditioner might be made by simply diluting down a suitable quat
with water. The stability and effectiveness may, however, be limited, therefore
it is common to use quats in conjunction with fatty alcohols, usually C 16 -C 1e .
Very thick emulsions can be obtained with quite low solids content, and an
effective product made at low cost. Formulae A and C in both Tables 2.11
and 2.12 illustrate this type of product. There are some drawbacks, including:
(i) The appearance of the emulsion, which may be coarse and grainy in
texture.
(ii) The low opacity. While this need not be considered disadvantageous,
the translucent nature of such emulsions can be unattractive.
(iii) The rheology of the system, normally highly non-Newtonian, with a
high yield-point making controlled use of the product difficult. A
further problem is the frequently encountered increase of viscosity
with time.
Table 2.11 Formulations for conventional cationic conditioners
A B C D
Behenyl trimethylammonium chloride

Cetyl trimethylammonium chloride, 30% 4
Dimethyl dihydrogenated tallow ammonium chloride,
7S%
Stearamidoethyl diethylamine
Stearyl dimethyl benzyl ammonium chloride, 7S% 1.2
Cetyl alcohol 2.2 4
Cetostearyl alcohol 3.S 2
Mineral oil 1.2 0.4
Cetomacrogol 0.3 0.3
Glyceryl stearate O.S
Methyl para ben 0.1 0.1
2-Bromo-2-nitro-1,3-propanediol 0.03 O.OS
Methylchloroisothiazolinone and
methylisothiazolinone, 1.S% O.OS 0.03
Citric Acid to pH 4.S S.O 4.S O.2S
Colour q.s. q.s. q.s. q.S.
Table 2.12 Formulations for conditioners based on less common cationics
A B C D E
Steapyrium chloride 1.8 0.8

Quaternium-70, SO% 1.4
Stearamidopropyl dimethylamine 0.8
Amodimethicone, 3S% 2
Quaternium-S2, SO% 2.S
PEG-S stearyl ammonium chloride, 30% 4
Quaternium-33, SO%
Cetyl alcohol 1.8 3.2 3.5
Cetostearyl alcohol 4 3
Stearic acid 1
Ethylene glycol stearate I.S
Cetomacrogol 0.2S 0.4
PEG-S-ceteth-IO-phosphate 0.8
Mineral oil I.S 0.8
Panthenol O.S
Hydrolysed protein 1.5 0.5
Quaternium-1S 0.1
DMDM hydantoin 0.1
2-Bromo-2-nitro-1,3-propanediol 0.04 O.OS
Methylchloroisothiazolinone and O.OS
methylisothiazolinone, I.S%
Citric acid to pH 4 0.18 3.5 4 3.S
Sodium chloride 0.4
Colour q.S. q.s. q.s. q.s. q.s.
-flAIR-CARE PRODUCTS 63
(iv) The sensitivity of the product to changes in manufacturing method,
in particular variations in high-shear stirring input, small changes in
which can produce very large viscosity variations.
These problems can usually be minimised in a number of ways.
(i) Introduction of other waxy components, such as esters. The structural
viscosity arising from hydrogen bonding with the hydroxyl groups of
the fatty alcohols is thereby reduced.
(ii) Addition of a small amount of oil, which smooths out the emulsion
and increases the opacity, while reducing the overall melting point of
the oil phase. This facilitates processing and makes it easier to obtain
repeatable viscosities from batch to batch.
(iii) Addition of a non-ionic emulsifier. In most hair conditioners the
cationic has a dual role: that of an active ingredient and that of an
emulsifier. A small amount of non-ionic emulsifier can assist greatly
in the emulsification, freeing the quat for optimum use in its primary
role. The increase in stability resulting from the cationic/non-ionic
blend may be due to the formation of mixed micelles and to the
presence of mixed surfactants at the oil/water interface of the emulsion.
Formulations Band D in Table 2.11, and B, D and E in Table 2.12
illustrate the use of such forms of stabilisation.
2.4.2 Cationic polymers and other active ingredients

This class of compounds, used extensively in conditioning shampoos, has
also become widely used in hair conditioners, alone or together with ordinary
quats. The 'backbone' structure of these polymers, on to which are grafted
Table 2.13 Formulations for polymer-based conditioners
Polyquaternium-22. 40% 2.5

Polyquaternium-6 2
Methylvinylimidazolium chloride/vinyl pyrrolidone
copolymer, 40% 1.5
PEG-15 tallow polyamine, 50'l~ 3
Cetostearyl alcohol 5 4.2 3.5 2
Glyceryl stearate 1.2
Glyceryl stearate and PEG-100 stearate 5
Cetomacrogol 0.5 0.4 1.6 0.4
Mineral oil 1.4 4
Quaternium-15 0.1 0.07
2-Bromo-2-nitro-1 ,3-propanediol 0.08 0.04
Behenyl trimethylammonium chloride
Citric acid to pH 4 4.5 0.15 4
Colour q.s. q.s. q.s. q.s.
Deionised water to 100%
quaternary ammonium groups and, where necessary, fatty chains, may have
various derivations, including partially hydrolysed protein, cellulose, starch,
guar gum, silicones, chitosan and various synthetics. The synthetics may be
homopolymers such as polydimethylaminomethyl methacrylate or dimethyl
diallyl ammonium chloride, or copolymers such as dimethylaminoethyl
methacrylate/vinyl pyrrolidone or hydroxyethylcellulose/dimethyl diallylam-
monium chloride. The positively charged sites occurring at intervals along
the polymer molecules permit an electrostatic attraction to the hair shaft in
the same way as monomeric quats. However, because the polymer may be
modified by the inclusion of more or less quaternary groups and a variable
number and length of side chains, its properties may be tailored to emphasise
any particular aspect such as charge density, substantivity and lubricity.
Polymeric quats can possess one quality that is absent in their monomeric
Table 2.14 Formulations for composite conditioners
Dimethyl distearylammonium
chloride, 75% 0.8 1.2
Stearamidopropyl
dimethylamine
Cetyl trimethylammonium
chloride, 30% 4 2 1.2
Hydroxypropyltrimonium guar 0.5
Polyquaternium-22, 40%
Quaternium-SO O.S 0.5
Quaternium-22, 60% 2.5
Dimethicone propyl
PG-betaine, 50% 2.5
Steartrimonium hydrolysed
protein 1
Mineral oil 1.5 1.5 0.5
Cetomacrogol 0.4 0.3 0.5 1.2 0.3
Cetostearyl alcohol 4.5 4 5 3.5 1.8 4
Vitamin E acetate 0.4
Vitamin A palmitate, 1 mIU/g 0.1
Stearic acid 1
Hydrolysed protein 1
Keratin amino acids, 50%
Panthenol 0.5 0.2
DMDM hydantoin 0.1 0.1
Methyl para ben 0.1 0.15 0.15 0.1
2-Bromo-2-nitro-l,3-
propanediol 0.03 0.05
Methylchloroisothiazolinone and
methylisothiazolinone, 1.5% 0.05 0.08
EDTA 0.1
Perfume q.s. q.s. q.s. q.s. q.S. q.S.
Colour q.s. q.s. q.s. q.s. q.S. q.s.
Citric acid 0.25 0.2 q.s. q.s.
to pH 4.5 4.0
siblings-that of film forming; indeed, for this reason, many also find a use
in hair-fixative products. Conditioners, particularly when used by those with
naturally greasy hair, can leave the hair rather lank and with a tendency to
re-soil rapidly. To some extent, this can be overcome by formulating with
cationic polymers with few, if any, fatty side chains. The polymetic quats
rarely have the emulsification power of the monomers and will therefore
often require the help of an auxiliary emulsifier. In most other respects they
can be dealt with as ordinary quats. The formulations in Table 2.13 illustrate
their use. Much more information about these materials is available,
predominantly from manufacturers' published literature [75].
The formulator may well wish to utilise the properties of both polymers
and conventional quats, which can be freely mixed to get the best of both
worlds. Conventional quats will often provide the necessary additional
emulsifying power. The formulations in Table 2.14 are examples of
conditioners formulated with more than one active ingredient.
Although the vast majority of conditioners are based on the established
properties of cationics, a few products are not. Anionic systems are
occasionally encountered (Table 2.15, formulation B), as are systems based on
high levels of protein (Table 2.15, formulation C). A variety of exotic oils,
Table 2.15 Formulations for non-quaternary conditioners
A B C
Carbo mer 934 0.5

Hydroxypropyl methylcellulose 0.7
Sorbitan mono palmitate 0.4 0.2
Polysorbate 40 0.6 0.25
Polysorbate 20 3
Mineral oil 3 3.5
Lanolin oil 1
Avocado oil 3
Wheatgerm oil 3
Paraffin wax 2.5
Sodium cetyl sulphate 0.6
Stearic acid 2.5
Triethanolamine 0.5
Acetamide *MEA and LAMEAt 2 1
Panthenol 1 0.4
Hydrolysed protein 2 8
Keratin amino acids 0.5 2
Glycerine 3
Methyl para ben 0.1 0.2 0.15
Propyl paraben 0.1 0.1
Quaternium-15 0.1 0.2
Methylchloroisothiazolinone and methylisothiazolinone. 1.5% 0.04
* MEA, mono ethanolamide;

t LAMEA, lactamide mono ethanolamide.
vitamins and other materials have been proposed, but their substantivity
from non-ionic or anionic emulsion bases must be considered questionable.
Amino acids and panthenol are widely used, as in shampoos. A variety of
humectants, for example acetamide MEA, lactamide MEA, polyols and
sodium pyrrolidone carboxylate, are often included but 'moisturising' as
applied to hair is not as well defined or documented as when applied to skin.
The argument that, since hair consists of dead tissue, hair and skin must be
treated quite differently, is frequently used. Nevertheless, many ingredients
with non-proven action continue to be widely used in hair preparations that
apparently satisfy consumer demands. A concise up-to-date review of active
ingredients used in hair conditioners is given by Woodruff [76], who also
illustrates their use with example formulations.
2.4.3 Bodying agents

As with shampoos, conditioners are perceived to be more effective when
thick and creamy. This is usually achieved by using quite high levels of fatty
alcohols along with other waxy esters, and hair conditioners containing only
lipids that are solid at room temperature are common. The function of the oils
and waxes is not merely one of giving body. A comparison between a simple
formula, such as formula A in Table 2.11, and an aqueous solution of a quat
will clearly demonstrate significant improvement in handle of the hair,
especially wet combing, indicating that the fatty alcohols have substantivity
to the hair when applied from a cationic emulsion.
2.4.4 Auxiliary emulsifiers

Depending on the hydrophilic lipophilic balance (HLB) and the steric
properties of the molecule, some quats are good emulsifiers, while others are
not. Their use with anionic emulsifiers is clearly prevented by incom-
patibility; where sufficient emulsion stability cannot be obtained with the
cationics alone, non-ionics are the preferred addition. There is a huge range
to choose from, but ethoxylated fatty alcohols seem to be particularly
effective. Structurally akin to the fatty alcohols present, they can form a
harmonious blend, very much in line with the work of Griffin [77], who
suggested blends of two emulsifiers (one with high and one with low HLB)
chosen from a series whose members had related chemical structures.
2.4.5 Oil components

The effect of oils on ease of manufacture and product stability has already
been referred to. In most formulations, such non-polar ingredients, used at
typically low levels, can be interchanged without greatly affecting stability.
Small quantities of exotic oils with attractive names may be included,
although any sound technical reason for doing so is not always obvious.
There has been a recent fashion for 'oil-free' conditioners; in the case of
emulsion-based products this need have little, if any, impact on product
performance.
2.4.6 Thickeners
Cationic emulsions, which are inherently thick for any given solids content,
do not usually require thickeners. They may be readily manipulated by
modifying manufacturing conditions. Although they usually respond to salt
in a similar way to shampoos, this method of thickening must be treated
with extreme caution if irreversible emulsion breakdown is to be avoided. The
following rules should be observed.
(i) Add only very small amounts of salt solution at one time, since the
viscosity will peak at much lower salt levels than that of typical
shampoos.
(ii) Add salt solution only when the emulsion is cold (maximum
temperature 30°C).
(iii) Use dilute salt solution (10% maximum) and add very slowly with
constant stirring.
(iv) Investigate the effect of the rate of stirrer shear when the salt solution
is added. A combination of a small amount of salt solution and
high-shear mixing will often achieve a viscosity that cannot be obtained
by one method alone.
(v) If working on a full-scale batch, always try a sample in the laboratory
first and be careful to take into account any effects of scaling-up.
Gum-type thickeners, the norm in clear conditioners (see section 2.4.11) may
also be used. Cellulose derivatives dominate and generally work very well.
Carbomers are rarely encountered because of their established incompatibility
with most cationics.
2.4.7 JJerjfun1es
Conditioners usually require only low levels of perfume. Typically, a perfume

which is present in shampoo at 0.5% will perform equally well in conditioner
at only 0.2%.
A number of quats on the market use isopropanol as a solvent and this
can sometimes leave a persistent odour which may be hard to mask. The
best remedy is to select a grade of quat which does not suffer from this
problem. Conditioners are fairly easy to perfume, but the stability of the
perfume in the often quite strongly acidic environment of hair conditioners
must be checked.
2.4.8 Preservatives
Most of the remarks made in section 2.3.4 on shampoos also apply here,
except that few ingredients used in conditioners will normally contain
preservatives (proteins and herbal extracts are exceptions). Many, indeed
most, cationic surfactants are active to some degree against micro-organisms.
Consequently, conditioners are fairly low-risk from a microbiological
viewpoint and serious problems are mercifully rare.
2.4.9 Colours
The addition of colours to shampoos is perfectly straightforward using stock
solutions (which must be adequately preserved) added to the batch. Most of
the widely used colours are, however, anionic in character and, if added in
the same way to the conditioner, will give rise to intensely coloured spots.
There are several ways, alone or in combination, of avoiding this.
(i) Add the colours when the bulk is still hot. Unfortunately the product
will normally whiten on cooling, especially if high-shear stirring is used,
making the colour appear lighter.
(ii) Use warmed colour solutions.
(iii) Use very dilute colour solutions ( < 0.1 % strength) and add slowly,
avoiding the creation of high local concentrations.
A few colours, such as rhodamine, because of their cationic nature, are fully
compatible with conditioners.
2.4.1 0 Manufacture
Traditionally, emulsions are made by heating oil and water phases separately,
combining them when hot, and then cooling them. Many conditioners can,
however, be made by adding all of the remaining ingredients to the heated
water and stirring fairly vigorously until an emulsion is formed, before cooling
as usual. Furthermore, because of their high water phase/oil phase ratio,
these products lend themselves well to low-energy emulsification methods
as advocated by Lin and co-workers [78-82]. In this method, only part of
the water is heated and a concentrated emulsion is first formed. The remaining
water is added cold under controlled conditions. A high-shear mixer, whether
bottom or top entry, or in-line, is always useful when making these products.
2.4.11 Clear conditioners

These are usually thickened, aqueous solutions of quats, polymers, or both,
often containing other active ingredients such as panthenol and water-soluble
silicone derivatives. Many of these products develop quite a strong lather
when worked into wet hair. If desired, this can be enhanced by the addition
Table 2.16 Formulations for clear hair conditioners
A B C
Cetyl trimethyl ammonium chloride, 30% 4.S 3

Cetyl pyridinium chloride 1.5
Cocoamidopropylamine oxide, 3S% 3
Polyquaternium-22, 40% 2.S
Panthenol O.S
Hydrolysed protein O.S 1
Dimethicone copolyol O.S
Glycerine 3
Hydroxyethyl cellulose
Hydroxypropyl methy1cellulose 1.2 1.2
EDTA 0.1 0.1
2-Bromo-2-nitro-l,3-propane diol 0.Q2
Phenoxyethanol (and) methyldibromoglutaronitrile 0.04 0.04
PEG-40 hydrogenated castor oil 0.6
Perfume 0.1 O.1S
Colour q.s.
Citric Acid to pH4.S 4 4
of amine oxides or betaines as foaming agents. Both will be predominantly

cationic in character at low pH and may well also contribute to the
conditioning effect. The formulations in Table 2.16 are examples of this type
of product. Formulation C in Table 2.15 is also clear, but is a non-quaternary
based product.
2.4.12 H air thickeners

These products vary in popularity according to the dictates of fashion. Hair
can be made thicker by causing it to swell, or by coating it to increase its
diameter. Hair will swell in water, more so under alkaline conditions and
although direct application may be impractical, powerful humectants may
be used to increase the moisture content of the hair. Swelling of the hair
shaft as a result of the application of panthenol solution is documented [83].
Almost any polymer exhibiting a degree of substantivity will cause the
hair-shaft diameter to increase, particularly in a non-rinse-off product.
Examples of thickener formulations are given in Table 2.17.
2.4.13 Leave-on-conditioners
Some of the early popular conditioners were 'leave-on' products presented
in the crude pump-spray packs available at that time. This type of product
is now returning to the shelves, greatly assisted by considerable advances in
pump-spray technology, which have been promoted by concern over .ozone
depletion. For ease of dispensing, a leave-on conditioner should be water-thin
and, to avoid formulating a product which will be too 'heavy', i.e. leave too
Table 2.17 Formulations for hair thickeners and leave-on conditioners
Thickeners Leave-on conditioners
Vinylpyrrolidone/vinyl acetate copolymer, 60/40 2.5 2

Polyquaternium-ll, 50% 1.5
Steartrimonium hydrolysed protein 2.5 2.5
Polyquaternium-22, 40% 2 1
Quaternium-80 0.5
Hydroxyethyl cellulose 0.9 1.1
Dimethicone copolyol 0.5
Oleth-20 0.5 0.4
Cetyltrimethylammonium chloride, 30% 0.25 0.2
Keratin amino acids, 50% 0.4
Lactamide-MEA 1.2
Panthenol 0.25 1.2 0.1
Propylene glycol 2
Perfume 0.15 0.1 q.s. q.s.
Methylchloroisothiazolinone (and)
methylisothiazolinone, 1.5% 0.05 0.05 0.05
2-Bromo-2-nitro-l,3-propandiol 0.05
Methyldibromoglutaronitrile and phenoxyethanol 0.1
much residue on the hair, a low solid content must be used. Water contents
therefore tend to be extremely high and raw material costs low. The greater
emphasis on moisturisers in this product category is quite logical, since
omission of rinsing enables sufficient contact time for such materials to
perform and ensures that 100% of material applied remains on the hair.
There are some leave-on products in the form of thick liquids and creams
but these are usually restricted to intensive treatments for severely damaged
or extremely dry hair. Some examples of formulations for pump-spray,
leave-on conditioners are given in Table 2.17.
2.4.14 'Hot oils', tonics and other conditioners
2.4.14.1 Hot oils Most 'hot oils' are neither hot nor oily. While the
misnomer might be construed as misleading, most of the products actually
perform quite well. A simple blend of oils, including 'exotics' such as avocado,
wheatgerm, rosehip andjojoba, can be effective when applied hot to extremely
dry hair. However, most of the products on the market are water solutions
based on conventional quats. The formulations already given to illustrate
clear conditioners could equally well be used with less thickener.
A few self-heating products have begun to appear on the market. These are
based on the exothermic dissolution of hydroxy compounds such as alcohols
and glycols in water. The products are, of necessity, anhydrous and are
usually based on polyethylene glycols or PEG/polypropylene glycol (PPG)
copolymers. Quats, panthenol and other suitably soluble materials can be
incorporated. The products are applied directly to wet hair and give an
immediate and readily perceivable temperature rise.
2.4.14.2 Tonics Many conditioners can work quite well as pre-shampoo

rather than post-shampoo treatments, provided that the subsequent
shampooing is not too fierce. Some products of this type have been marketed
with limited success as hair and scalp conditioners, or as tonics; formulations
A and B in Table 2.18 are examples.
In the days before strict controls there were numerous 'hair tonics' on the
market, many making quite outrageous claims, often promising cures for
baldness, or at least implying this. The widespread recognition that treatment
for hair loss by topically applied products has a long history of abject failure
means that these products now represent only a tiny fraction of the total
hair-care market (except in Japan [84]). In any case, such treatments are
outside the remit of the cosmetic chemist.
Not all hair tonics are so blatantly misleading and, in some cases, they
form convenient vehicles for the application to the scalp of a wide range of
beneficial additives. These include vitamins such as Vitamin E acetate and
nicotinate inositol, Vitamin A palmitate, Vitamin B6, panthenol, panto-
thenates and panthenyl esters, D-biotin, vasodilators such as nicotinic acid
esters, coal-tar extracts, herbal extracts, camphor, menthol, allantoin and
sulphur. The positioning of many hair tonics places them firmly in the growing
Table 2.18 Formulations for hair tonics
A B C
Panthenol 1 1.5 0.25

D-Biotin 0.02
Vitamin E nicotinate 0.2
Methyl nicotinate 0.05
Allantoin 0.05
Vitamin E acetate 0.4
Camphor 0.1
Menthol 0.05
a-Bisabolol 0.1
Carbomer 940 0.4
Carbomer 934 0.3
Polyquaternium-ll, 20% 0.3
Triethanolamine 0.45 0.25
Oleth-20 1
Nonoxynol-9 3
Capric/caprylic triglyceride 3
Propylene glycol 5 4
Ethanol B96 25 50
Colour q.s. q.s. q.s.
Perfume q.s. q.s. q.s.
Methyl paraben 0.1
2-Bromo-2-nitro-l,3-propanediol 0.03 0.04
grey area of 'cosmoceuticals', and the rationale for including such products
in a purely cosmetic range is questionable. The use of hair tonics as dandruff
treatments is more established. N on-rinse-off products are well suited for this
application and recent work describes use of piroctone olamine as the active
ingredient [85]. Hair tonics in general are dealt with at greater length in
Harry [86].
2.4.14.3 Other conditioners An interesting treatment of the conditioning

concept has been proposed [87], in which it is claimed that a hydrolysed
keratin protein containing cystine/cysteine residues, applied part-way
through the permanent-waving process, covalently bonds with the hair via
broken disulphide bonds in the hair keratin.
UV absorbers may be added to conditioners. The few studies carried out
indicates that efficacy varies with the nature of the sunscreen [88, 89]. In order
to be effective, a significant amount of sunscreen would need to be deposited
on the hair and this would seem to be practical only from a leave-on product
such as a styling aid. The effect ofUV radiation on hair is discussed more fully
in section 2.5.1.6.
2.5 Styling aids
2.5.1 H airsprays
The simplest of styling aids, these products are usually applied to dry hair and
hold it in place by a combination of coating each hair with a thin deposit of stiff
polymer, and 'gluing' hairs together at points where they cross. Such products
evaporate rapidly and the effect is 'instant', i.e. the product is applied to the
finished hairstyle to hold it in place. Hairsprays were revolutionised by the
introduction of the aerosol with its concomitant huge increase in product
performance. The pump-spray revolution has been altogether quieter, though
no less effective, with concern over ozone depletion adding to already
increasing sales. It is now possible to achieve a very fine spray, a choice of
spray angles and different delivery quantities per stroke by careful selection
of the most suitable pump. Further legislation to control the emission of
volatile organic compounds (VOCs) may ultimately favour pump sprays at
the expense of aerosols, although water-based aerosol sprays using lower
levels ofVOCs are being developed [90].
The degree of hold given by a hairspray may be varied quite easily and
is dictated by fashion; more-natural styles require only a light degree of hold,
while complex styles may require a very stiff finish to hold them in place.
Various descriptive terms, such as light hold, medium hold, strong hold,
ultrahold, megahold, have been used, the only apparent limitation being the
degree of imagination of the marketing department. There is, of course, a
HAIR -CARE PRODUCTS 73
Table 2.19 Formulations for a medium hold hairspray
A B C D E F
Ethanol B96 to 100%

Octylacrylamide/acrylates/butylaminoethyl
methacrylate 1.7
Ethyl ester of vinylmethyl ether/maleic 7
acid, 50%
Butyl ester of vinylmethyl ether/maleic 6 3.5
acid, 50%
Vinyl pyrrolidone/vinyl acetate 2.5 8
copolymer, 30170, 50%
Vinyl acetate/crotonic acid copolymer 4.5
Quaternium-43 0.1
2-Amino-2-methyl-propane-I-ol 0.4 0.1 0.3
Triethanolamine 0.25 0.15
Phenyl dimethicone 0.3 0.2 0.25
Panthenol 0.1 0.25
Dimethicone copolyol 0.1 0.4
Oleth-20 0.4 0.3
Silk protein hydrolysate 0.15
Perfume 0.2 0.15 0.2 0.15
Deionised water 2 6 7 5
limit to the degree of hold which may be obtained but, in practice, this limit
is high enough to permit the formulation of a range of products covering
normal usage requirements. Typical formulations for medium hold and
strong hold hairsprays are given in Tables 2.19 and 2.20.
Table 2.20 Typical formulations for a strong hold hairspray
Ethanol B96 to 100%

Octylacrylamide/acrylates/butylaminoethyl
methacryla te 3.2
Ethyl ester of vinylmethyl ether/maleic
acid, 50% 9
Butyl ester of vinylmethyl ether/maleic
acid, 50% 10
Vinyl acetate/crotonic acid copolymer 6
Vinyl pyrrolidone/vinyl acetate copolymer,
30/70,50% 14
Vinylcaprolactam/vinyl pyrrolidone/
dimethylaminoethyl methacrylate, 37% 6
Lauryl pyrrolidone 0.1
Phenyl dimethicone OJ
Diisopropyl adipate 0.3
Dimethicone copolyol 0.4 0.1 0.2
Panthenol 0.1
Quaternium-33 0.1
2-Amino-2-meth yl-propane-I-ol 0.4 0.12 0.45 0.5
Perfume 0.2 0.25 0.2 0.2
Deionised water 6 5
The main ingredients in a hairspray are:
• Solvent
Polymer
• Plasticiser
• Neutraliser
• Perfume
• Other additives
•
The available polymers will be considered first.
2.5.1.1 Polymers Early hairsprays used shellac in either its natural or its
dewaxed form to provide the hold (hence the name lacquer). Shellac gives a
brittle film that flakes off easily yet is difficult to remove completely. It has
now been displaced by modern synthetics, most of which are derived from
acetylene [91, 92]. The first of these to make a big impact on the hair-care
market was polyvinyl pyrrolidone (PVP). This is widely available in different
degrees of polymerisation, which are usually referred to by the K number,
derived from the viscosity of a dilute solution of the PVP relative to that of
water. K numbers between 30 and 90 are common.
PVP is very hygroscopic and absorbs sufficient water from humid atmo-
spheres to appreciably soften the deposited film and render it unacceptably
tacky. Copolymerising the vinyl pyrrolidone with a harder, more hydrophobic
material, such as vinyl acetate overcomes this, and copolymers in which the
ratio of VP to VA can be varied at will, e.g. from 80:20 to 20:80, are freely
available. At levels above 40% VA, the copolymer loses water solubility.
However, higher VA levels are commonly used in hairsprays.
More recently, resins have continued to improve on the balance of
properties obtainable, but such optimisation always gives rise to trade-offs
of properties. Ideally, a hairspray polymer should be soluble in ethanol, and
be hydrophilic enough to be easily removed from the hair by shampooing,
but hydrophobic enough to be compatible with hydrocarbon propellants for
aerosol use. It should give powerful hold without brittleness, yet be easily
removed by combing or brushing, and must have good adhesion, yet not be
sticky. All these properties preferably should be combined with antistatic
and conditioning properties, and a competitive price. The following polymers
are commercially available and widely used.
• Vinyl pyrrolidone/t-butyl acrylate copolymer
• Vinyl pyrrolidone/t-butyl acrylate/methacrylic acid copolymer
• N-t-butylacrylamide/ethyl acrylate/acrylic acid copolymer
• Vinyl acetate/crotonic acid copolymer
• Vinyl acetate/crotonic acid/vinyl neodecanoate copolymer
• Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer
• Ethyl ester of vinyl methyl ether/maleic acid copolymer
Table 2.21 Effect on most polymers of varying the degree of neutralisation
Low percent neutralisation High percent neutralisation
Water solubility increasing

Hydrocarbon compatibility increasing
Firmness of hold/brittleness increasing
Stickiness in high humidity increasing
Ease of removal by shampooing increasing
Ease of removal by brushing increasing
• Butyl ester of vinyl methyl ether/maleic acid copolymer

• Vinyl pyrrolidone/dimethylaminoethyl methacrylate copolymer
• Vinylcaprolactam/vinyl pyrrolidone/dimethylaminoethyl methacrylate
copolymer
The last of these polymers is particularly good where a virtually colourless
product is required. Although most of the above resins initially give a very
light colour in solution, the development of colour with age is very common
and difficult to overcome. Formulation B in Table 2.19 illustrates a
water-white, fragrance-free product based on this material.
Some polymers have free acidic groupings in their molecules and can be
fully or partly neutralised with a suitable base, modifying their properties
considerably. The bases most commonly used are 2-amino-2-methyl-
propane-l-01 (AMP), 2-amino-2-methyl-l,3-propanediol (AMPD), triethano-
lamine (TEA), triisopropanolamine (TIPA) and tris (hydroxymethyl) amino
methane (Tris). The effects on most polymers of varying the degree of
neutralisation are shown in Table 2.21. In most cases, a fairly low percent
neutralisation gives the best combination of properties for a hairspray (but
not necessarily for other styling aids based on the same resin).
For any given polymer system, an increase in solids will give a firmer hold.
However, the relationship is not always linear and, where very firm holds
are required, better results can sometimes be obtained from a mixture of
polymers. The viscosity of the formulation should be kept as low as possible
and a suitable pump spray chosen (the lower the viscosity, the easier it is to
obtain a fine spray).
Hairspray polymers can be quite difficult to handle. Many are sold as
concentrated, highly viscous solutions (usually in ethanol), which are hard
to empty out of drums and have a remarkable propensity to stick to anything
and everything. Those supplied in solid form are more amenable, although
more efficient stirring may be required and batch processing times may be
longer.
2.5.1.2 Solvents For non-aerosol products, there is really only one

solvent-ethanol either alone or diluted slightly with water. It has a suitably
rapid evaporation rate, inoffensive odour that is not too difficult to mask,
excellent solvent properties for most resins, and is reasonably priced.

Isopropanol has been used in some countries with a high excise duty on
ethanol, but has a slightly slower evaporation rate and an objectionable
smell. Ethanol B, denatured with Bitrex (CTF A name denatonium benzoate)
and marked with t-butyl alcohol, is now standardised throughout the EC.
In some countries (e.g. Norway and Sweden) additional denatonium benzoate
must be added to comply with requirements for alcohol denaturing.
The addition of water to the solvent system may be necessary:
(i) to improve the solubility of an ingredient not fully soluble in ethanol;
(ii) to retard evaporation rate;
(iii) to reduce cost; and
(iv) to prevent precipitation from an acid-resin based system that has been
neutralised to a high level. A high percent neutralisation will often
increase water solubility and reduce alcohol solubility and, in some
cases, a colloidal solution results. In the long term, precipitation can
occur when the colloidal particles coalesce.
2.5.1.3 Plasticisers Plasticisers are used to modify the properties of the

polymer film, making it more flexible. Only small quantities are normally
required; 5% of the dry weight of polymer is a good rule of thumb. A huge
number of different materials have been used as plasticisers, including a
variety of esters (usually liquid), various silicones (phenyl methyl silicones
have good alcohol solubility and are especially useful), silicone glycol co-
polymers, proteins, polyols, lanolin derivatives, etc. It should be remembered
that other materials in the formulation, for example perfume, may act as
plasticisers, even if that is not the purpose of their inclusion.
A poor choice of plasticiser may have adverse effects such as weakening and
dulling of the film. This can occur when the plasticiser is not fully miscible
with the resin, leading to a discontinuous film with high local concentrations
of plasticiser. A useful check is to examine some evaporated product on a
glass microscope slide to check whether the deposited film is dull or
discontinuous. Although plasticisers are not always necessary, the stiffer
the polymer film, the more plasticiser is likely to be needed.
2.5.1.4 N eutralisers The amount of neutraliser required for a given percent

neutralisation can either be obtained from polymer manufacturers' literature,
or simply be calculated from the acid value of the resin. The polymer
properties may be modified by the neutraliser used, and it is wise to follow
the polymer manufacturers' recommendations.
2.5.1.5 Perfume Hairsprays are not difficult to perfume, in that there is

not usually a solubility problem. Perfumes should be strong in odour and,
to avoid interference with the plasticising of the resin, should be used at low
levels. The raw odour of the ethanol may be quite difficult to mask and the
residual odour on the hair may need careful control.
2.5.1.6 Other additives Preservatives are unnecessary in ethanol-based

products such as hairsprays. Many other additives, such as vitamins, proteins,
amino acids and herbal extracts, are used. Most of these are present in very
small amounts and cannot seriously be expected to dramatically affect
product performance. Ultraviolet filters have become a fashionable addition
and some work has demonstrated that they may be of value in leave-on
styling products [88, 93, 94], although some of the studies have used unrealis-
tically high levels of UV filters.
There seems to be little doubt that hair can be damaged appreciably by
ultraviolet light (and other environmental influences). The nature and extent
of this damage, which includes photo-oxidation, loss of mechanical strength,
increased alkaline solubility and colour changes are examined by Dubrief
[94].
2.6 Setting lotions
The fundamental difference between hairsprays and setting lotions is that

the latter are intended for application to wet hair. Water-soluble polymers
are therefore used and the alcohol content, tends to be lower. Completely
water-based products are possible since drying time is not so critical. Use
Table 2.22 Formulations for a setting/blow-dry lotion
Ethanol B96 40 40 18 30
Polyquatemium-11,50% 2
Hydrogenated tallow dimethyl benzyl
ammonium chloride, 75% 0.2
Sodium polystyrene sulphonate, 50% 2.2
Vinyl pyrrolidone/vinyl acetate copolymer,
60/40 1.2 2
Vinyl acetate/crotonic acid copolymer 1.2
Quatemium-22, 60% 0.4 0.2
Methylvinylimidazolium chloride/vinyl
pyrrolidone copolymer 95/5, 40% 0.5 0.25
Nonoxynol-9 0.25 0.3
Perfume 0.1 0.05 0.15 0.1 0.1
Panthenol 0.2 0.1 0.2
Oleth-20 0.5 0.25
Denatonium benzoate, 2.5% solution 0.005
2-Bromo-2-nitropropane-1,3-diol 0.03 0.01
methylisothiazolinone, 1.5% 0.05
of acidic polymers with a higher degree of neutralisation is another widely

practised option. Some products are marketed specifically as blow-dry
lotions, but are essentially similar. Since the action of these products is not
'instant' in the manner of a hairspray, and since levels of hold are generally
lower, there is more scope to incorporate conditioning ingredients; a blend
based on a cationic polymer plus a hairspray-type resin can give good results.
A strongly anionic resin, sodium polystyrene sulphonate, has been success-
fully used since its highly conductive film is effective in reducing static. This
can be important during blow-drying, when, towards the end of the process,
the hair is virtually dry and can exhibit 'fly-away', making styling difficult.
This problem is not as obvious with other forms of heating devices such as
tongs and heated curlers. Typical formulations for a setting/blow-dry lotion
are shown in Table 2.22.
2.7 Other styling aids in spray form
Names such as 'spritz', 'spray gel', 'sculpting spray', etc. are usually hairspray
or setting lotion variants of one sort or another. Often a 'wet-look' or glazed
effect is desired, and this usually demands a high resin content in a water or
water/ethanol base. Since styling of the wet hair is carried out, the product
must not dry too quickly and must be compatible with water. Especial care
must be taken with the high-gloss products not to reduce gloss by injudicious
choice of plasticisers. Likewise, the high solids contents of some formulations
may restrict pump-spray choice. Typical formulations for wet-look styling
sprays are given in Table 2.23. The products are popular in other physical
forms such as gels and creams (see sections 2.8 and 2.9).
A few other spray products, claiming specific properties such as volume
enhancement and gloss, are available (see Table 2.24). Almost any hair-styling
aid enhances volume by virtue of the deposited polymer, which increases the
diameter ofthe hair shaft, This is much more obvious in the case of products
applied to dry hair; 'wet-look' and sculpted styles tend to reduce volume by
sticking adjacent hairs together in parallel lines, whereas a more random
orientation of the individual hairs gives a more bulky appearance. Over a
Table 2.23 Formulations for wet-look styling sprays (applicable to wet hair)

Vinyl caprolactam/vinyl pyrrolidone/dimethylaminoethyl
methacrylate. 37% 6.5 6
Vinyl pyrrolidone/dimethylaminoethyl methacrylate, 20% 4
Lauryl pyrrolidone 0.3
Cetyl trimethyl ammonium chloride, 30% 0.3
2-Bromo-2-nitropropane-1 ,3-diol 0.04
Methyldibromoglutaronitrile (and) phenoxyethanol 0.05
Table 2.24 Formulations for miscel1aneous spray products
Volume Gloss Non-aerosol

spray sprays mousse
Vinyl pyrrolidone/vinyl acetate 2.5

copolymer, 60/40
Steartrimonium hydrolysed protein 0.75
Panthenol 1
Vinyl caprolactam/vinyl pyrrolidone/
dimethylaminoethyl methacrylate, 37% 6
Lauric diethanolamide 0.3
Ammonium nonoxynol-4 sulphate, 30% 4
Phenyl dimethicone 20
Dimethicone copolyol 10
Ethanol B96 40 80 77.7 8
Perfume 0.1 0.4 0.3
Deionised water to 100 10 to 100
2-Bromo-2-nitro-I,3-propanediol 0.05
Light mineral oil 40
C 7 - 8 isoparaffin 59.6
Quaternium-80, 50% 2
period of time, panthenol can cause swelling of the hair shaft, and this
contributes to 'volume'.
Gloss, a fashion-related characteristic, may be achieved either by careful
selection of polymers, as in wet-look products, or by the application of a
light, oil-based spray after styling. Aerosol products containing straight
mineral oil are sometimes used but silicone-based sprays are probably more
popular. Dimethicones with volatile silicones as diluents, or a phenyl methyl
fluid or a dimethicone copolyol in an alcohol base, may be used.
A final category of spray product is the non-aerosol mousse (see Table 2.24).
These products depend on the product being mixed with air when the bottle
is squeezed. The addition of a suitable foaming agent to the formulation
gives a foam of rather coarse and wet texture. Such foams are aesthetically
quite inferior to those generated by aerosols, which continue to dominate this
sector of the market.
2.8 Hair gels
Traditionally male-oriented, gels are nevertheless also widely used by women.

The earlier types of gel, aimed specifically at men, were oils gelled by the
use of metallic stearates or silica. Such gels behave like hair cream, giving
high gloss and low levels of hold. The chosen base is mineral oil, which has
low odour and colour, good oxidative stability, and is cheap. Transparent
colloidal gels, invariably relying on high levels of non-ionic surfactant, are
an alternative, but high levels of non-ionics, can give irritation, especially
Table 2.25 Formulations for oil-based hair gels
A B C D
Mineral oil 60 to 100 IS 50

C S /C'2 triglyceride 33.4
Fumed silica 6
Aluminium stearate 5
Microcrystalline wax 4
Oleth-5 10 5
DEA-oleth-3 phosphate 7
2-0ctyl dodecanol 25.2
Carbomer 940 2
Propylene glycol 6
Perfume 0.5 q.s. q.s. q.s.
Butyl para ben 0.1 0.05
Methyl paraben 0.2
2-Bromo-2-nitro-I,3-propanediol 0.05
Cocamine 5.8
Ethanol B96 12
eye irritation. The irritation potential of individual ethoxylates may vary

considerably (e.g. oleth-lO is much more irritant than 0leth-5 or 0Ieth-20)
and careful checking of final formulations is necessary. Carbomers, neutralised
with long-chain fatty amines instead of the more usual materials [e.g.
triethanolamine (TEA) and aminomethyl propanol (AMP)] can thicken oils
to gel consistency, provided that sufficient polar solvent, such as ethanol, is
present. Note that oils gelled with metallic stearates (see formulation A in
Table 2.25) require very high processing temperatures (up to 130 a C), and
appearance and stability can vary with cooling rate and stirring.
The majority of gels on the market are aqueous, or, occasionally, aqueous/
alcoholic. Carboxyvinyl polymers are the most important and, while their
prime function is to create the clear gel base, they also have some fixative
powers and contribute to the overall hold of the formulation. A wide range
of polymers are normally included as the primary film-formers. The basic
requirements are for good water solubility, clarity in solution and compa-
tibility with the carbomer resins. The final property, although precluding the
use of highly cationic polymers, allows some polymers of relatively low charge
density to be used, thus enabling conditioning properties to be added. Typical
formulations for styling gels are shown in Table 2.26. Formulations A and
B are for 'soft hold' gels, while formulations C to F give a firmer hold.
Carbo mer 940, which gives the clearest gels, is compatible with many other
polymers only when fully or partly neutralised. This must considered when
manufacturing such products. Polymers used should be diluted with water
before addition and added slowly after about two thirds of the neutraliser
has been added to the carbomer, (see earlier general remarks on gum
dispersion).
Table 2.26 Formulations for styling gels
A B C D E F
Carbo mer 940 0.8 0.7 0.8 0.9 0.6 0.65

Vinyl pyrrolidone/vinyl acetate
copolymer, 60/40 3.3
Polyquaternium-ll,20% 1.5 5.5 1.5
Polyvinyl pyrrolidone, K30 1.8 3.5
Vinyl pyrrolidone/vinyl caprolactam/dimethyl
aminoethyl methacrylate, 37% 6
Benzophenone-4 0.05 0.05 0.05 0.05 0.05 0.05
EDTA 0.1 0.1 0.1 0.1 0.1 0.05
Phenoxyethanol and 0.03 0.05 0.05
methyldibromoglutaronitrile
Methyl para ben 0.1 0.1 0.1 0.1
Quaternium-15 0.07 0.07 0.07
Triethanolamine 0.96 0.8 0.9 1.1 0.7 0.7
Perfume 0.1 0.1 0.15 0.1 0.25
Polysorbate 20 0.5 0.75
Nonoxynol-9 0.4 0.5 0.5
Full exploitation of clear gel aesthetics requires transparent packaging,

which poses problems since carbomers are degraded by UV light. Loss of vis-
cosity and clarity results. This problem may be overcome by including a UV
absorber (benzophenone-4 usually works well). Carbomer gels are sensitive
to transition metal ions, which can catalyse gel degradation. EDT A or a
similar sequestrant is an effective remedy. The vigorous agitation required
to dissolve the unneutralised carbomer can cause aeration problems since,
even prior to neutralisation, the solution has an appreciable viscosity and a
relatively high yield-point. The viscosity is very pH dependent, therefore the
inclusion of a UV absorber and a sequestrant can be turned to advantage
by adding (strongly acid) benzophenone-4 and EDT A (in its free acid form)
to water before the carbo mer. A thin solution results, and entrained air is
easily expelled by standing the mix for a while before neutralisation. Acrylic
polymers, suitable for the formulation of clear gels, are available in liquid
form (acrylates/steareth-20 methacrylate copolymer) and in pre-neutralised
form.
Gels prepared from carbomers are influenced by the choice of neutralising
agent. Sodium hydroxide gives a very stiff gel, while amines give a softer gel.
The hydroxy amines, predominantly TEA, are the most widely used. Problems
associated with carbomer gels, and suggested remedies are summarised in
reference [95]. One such problem is uncontrolled aereation. A large number
of very small air bubbles will make the product look opaque, but a small
number of large bubbles can be attractive. Controlled aeration is difficult to
achieve during mixing but easier to achieve during transfer from mixing
vessel to intermediate bulk container, or from intermediate bulk container
to filling machine. An air bleed can be introduced at a low pressure point

such as the inlet side of a pump, where varying air flow rate and orifice size
can give the desired effect.
2.9 Styling creams and glazes
Styling creams and glazes (see Table 2.27) are variations on the formulations
shown in Table 2.26. Opacification to produce creams may be achieved either
by the inclusion of a small amount of opacifier of the styrene/acrylate
copolymer type, or by using a conventional oil phase plus emulsifier. The
presence of a large amount of carbomer aids emulsion stability, and the
choice of emulsifier type and level is not as critical as in a non-gum thickened
emulsion. Oil phases inevitably have a plasticising effect and may result in
reduced hold. Styling creams are often packed in polystyrene jars, therefore
the inclusion of esters such as isopropyl myristate, which might react with
the plastic, should be avoided. The leaching-out of plasticisers, or the sorption
of ingredients due to product/packaging interaction can occasionally lead to
interesting effects such as a loss or increase of product opacity around the
edge of the jar. Glazes or hair-sculpting gels tend to contain high amounts
of polymer (analogous to their spray counterparts) and aim at a high gloss
or wet-look finish.
Table 2.27 Formulations for styling creams and glazes
Styling creams Glazes
Vinyl pyrrolidone/dimethylaminoethyl methacrylate 6

copolymer, 20%
Vinyl caprolactam/vinyl pyrrolidone/ 3 8
dimethylaminoethyl methacrylate
copolymer. 37%
Cetyl trimethylammonium chloride, 30% 0.6
Polyquaternium-ll,20% 4
Carbomer 940 0.7 0.8 0.7
Styrene/acrylate copolymer 0.2
PVP K30 2.2
Mineral oil 1.5 0.5
Sorbitan mono palmitate 0.1
Polysorbate-40 0.18
Glyceryl stearate (and) PEG-lOO stearate 2
Phenoxyethanol and methyldibromoglutaronitrile 0.05 0.03 0.05
Ethanol B96 25
Perfume q.s. q.s. 0.15 0.15 0.1
Nonoxynol9 0.45 0.45 0.4
2-Bromo-2-nitro-l,3-propanediol 0.05
EDTA 0.1 0.1 0.1 0.1
TEA 0.85 0.9 0.85 1.15
2.10 Hair oils/brilliantines/pomades/styling waxes
Hair oils and brilliantines are alternative non-spray gloss enhancers consisting
principally of mineral oil or petroleum jelly, depending on the final physical
form of the product. Other oils, such as castor oil, recognised as imparting
good gloss, are also used [96]. For a liquid product, the main ingredient is
mineral oil of the appropriate viscosity, coloured and perfumed. For a
pomade, petroleum jelly with similar additives would be used. In the latter
case the product is filled into jars in its liquid state, at elevated temperature.
After solidification it is customary to 'flash' the surface by passing the product
under a heater. This gives a smooth concave meniscus. These products,
however, are considered old-fashioned and represent a dwindling sector of
the market. A more modern approach is to produce a styling wax by adding
ingredients that will give some degree of hold and make the product harder.
In the examples shown in Table 2.28, methyl hydrogenated rosinate and
lanolin wax are used for this purpose. In these formulations, perfume should
be added as late as possible Gust before filling) to minimise perfume degradation,
which occurs at the temperatures encountered (typically> 70°C).
Table 2.28 Formulations for styling waxes
Methyl hydrogenated rosinate 10 12

Lanolin 4
Petroleum jelly 30
Castor oil 25.1 20
Microcrystalline wax 30 20
Lanolin wax 5
Perfume 0.8 1.5
Mineral oil 21.4
Butyl paraben 0.1 0.1
Paraffin wax 20
2.11 Hair creams
Hair creams are emulsion products providing modest hold and high gloss,
rather old-fashioned, but made in surprisingly large quantities-mostly for
export to countries that are not subject to the rapidly changing fashions of
western Europe. An effective hair cream is an emulsion that breaks down
quite readily on application. The emulsion must, however, be stable for the
anticipated shelf-life of the product under variable storage conditions, often
at extremes of temperature. Achieving such a delicate balance is not always
easy and, perhaps surprisingly, the ancient beeswax/borax and beeswax/lime
water systems perform well in this context. Hair creams, which may be O/W
or W/0 systems, rarely contain 'exotic ingredients' and generally sell at low
price points. Consequently, formulations need to be produced cheaply.
Table 2.29 Formulations for hair creams
A B C D E
Mineral oil 35 40 30 IO 16
Lanolin 3 2 1
Beeswax 2.2 3 4.5
Lanolin alcohols 2
Petroleum jelly 30
Paraffin wax 5 2
Stearic acid 1.2 5
Myristyl myristate 3
Glyceryl stearate 3 3.6
Cetostearyl alcohol 1.6
Dimethicone 2
Sorbitan sesquioleate 2.5
Ceteareth 20 0.4 0.5
Borax 0.7 0.5
Calcium hydroxide 0.12
Carbo mer 934 0.5
Triethanolamine 1.5
Glycerine 5
PEG-400 2
Magnesium sulphate heptahydrate 0.7
Methyl paraben 0.1 0.15 0.1 0.1 0.1
Propyl paraben 0.1 0.05 0.05
DMDM hydantoin 0.1 0.1
Quaternium.15 0.07 0.1
Occasionally, polymers are used to increase hold but, more frequently, the
natural tackiness of the oil phase is relied on to provide the required effect.
Typical formulations for hair creams are shown in Table 2.29.Formulations
A, Band Care W/O emulsions and are therefore made by adding water
phase to oil phase, very slowly at first. A limited amount of high-shear mixing
will improve the appearance of the emulsion but over-application of high
shear may cause emulsion breakdown. Formulation D is an 0IW system in
which the carbomer should first be dissolved in the water phase (see earlier),
with a small portion of the water being kept back to dilute the triethanol-
amine, this solution being added immediately after the oil phase. Formulation
E is a conventional O/W emulsion. A further discussion of hair styling
products, with example formulations is given by Alexander [97].
2.12 Permanent waving
Permanent waving is not truly permanent due to the fact that the hair is
constantly growing. There is, however, a fundamental difference between
permanent-waving preparations and the styling products that have already
been discussed. This difference is the chemical reaction that occurs between
the product and the protein of the hair shaft; covalent bonds cross-linking
the protein chains are broken. Clearly, quite severe conditions are required
to rupture such high-energy bonds and this can only be achieved with an
element of risk. For this reason, permanent-waving products are primarily
sold through professional outlets and are applied by qualified hairdressers.
The home-perm market is a relatively small proportion of the total and the
products sold for home-use tend to be weaker, thereby reducing the risk of
severe hair damage if the process should go wrong.
Historically, various processes have been used. These include heat treatment,
with or without various 'alkalis' [98~ 100], and, later, a whole series of redu-
cing agents, [101]. However, the major reductant is thioglycollic acid, usually
as the ammonium salt.
In simplistic terms, the mode of action is as follows:
(i) Reduction of ~s~s~ bonds between cystine amino acid groupings on

adjacent polypeptide chains.
(ii) Rearrangement of the hair into its 'new' position by wrapping around
rollers, or other mechanical means. The stresses imposed shift the
polypeptide chains relative to each other.
(iii) Reforming of the ~S~S~bonds by oxidation. At this point the various
~SH residues will be linked to 'new partners' on the adjacent chains,
and the strength of these new bonds will make the hair retain its new
shape.
The chemistry involved is in fact much more complex, with a multitude of

side reactions occurring at both the reduction and oxidation stages. These
are discussed in more detail elsewhere [100~104]. Clearly, only a percentage
of the bonds originally broken will be reformed; any residues from the
reduction process that do not form new cross-links will be converted to a
variety of small side chains on the polypeptide matrix. Quite apart from the
chemistry, it is obvious that, from purely geometric considerations, not all
of the bonds will be reformed. Typically, between 17% and 43% of the hair's
cystine is reduced during processing, with a permanent degradation of up to
30% [102]. This damage includes lipid reduction [105] as well as protein
damage [106], and can result in a reduction in strength of the hair fibres by
20% [107]. Cystine appears to be the only amino acid in the hair's polypeptide
chains that is changed during the perming process [102]. The plotting of
strain/stress curves for hairs before and after treatment can be useful. The
elongation of hair under tension initially obeys Hooke's law, i.e. the response
is linear. It then passes into a zone of high yield, and finally enters the
post-yield zone in which the hair exhibits more resistance to further applied
stress before untimately breaking. It has been suggested that analysis of the
post-yield slope can help to optimise formulations [107].
The factors affecting the efficacy of the product are the same as those
determining the potential hair damage.
(i) Processing time

(ii) Processing temperature
(iii) Concentration of reducing agent
(iv) Ratio of lotion to hair quantities
(v) Penetration of the lotion
(vi) pH
(vii) The nature and condition of the untreated hair
Other variables, such as the number and diameter of the rollers, the tension
of the hair on the rollers and the speed at which the operation is carried
out, are highly pertinent but are all related to hairdressing technique and
are beyond the scope of this chapter. Each of the factors listed above will
be considered in turn.
Processing time should be no longer than is necessary to achieve the

required result. Home perms will generally be designed to allow for a longer
processing time, since the home-user will not be as quick as a professional in
manipulating the hair.
Processing temperature will be ambient for most products. Those designed
for hot use are invariably restricted to the professional market. For these
products, heat may be supplied either by external means (electrical or hot
air), or by mixing the ingredients just before use to achieve an exothermic
chemical reaction.
Concentration of active ingredients will be determined by the manufacturer
and will not be changed during use except by dilution, either intentional or
accidental (e.g. arising from excessive wetness after pre-shampooing). A wide
range of concentrations is available, depending on the hair type for which
the product is intended.
The ratio of lotion to hair will only become problematic when very long
hair is involved, and when there is insufficient lotion to treat the whole head.
This would appear to be more ofa problem in Europe than in the US [108].
The penetration of the lotion will often be enhanced by the inclusion of a
surfactant, of which a wide variety, mostly non-ionic and anionic, have been
used. Penetration may also be enhanced by the inclusion of a hydrogen-bond
breaker, such as urea, in the formulation.
pH can be critical-if it is too low, the product will not work well; if it
is too high, severe hair damage might result. Although maximum bond
cleavage is thought to occur at pH 9 [106], above pH 8.S bond reformation
is less complete. At pH < 7.S the amount of bond cleavage is low but
reformation is more complete. Apart from the protein damage and lipid
depletion already referred to, there is an overall loss of sulphur from the
hair, again more pronounced at higher pH. In most permanent-waving
lotions, the thioglycollic acid is neutralised either by ammonia, or by a
mixture of ammonia and a hydroxy amine (e.g. TEA). Some ammonia will
evaporate during use of the product, leading to a gradual pH drop, which
is a useful safeguard against overprocessing. In practice, initial pH is usually
approximately 9.2 ± 0.2 for a conventional ammonium thioglycollate lotion.
pH is currently restricted by law to a maximum of9.5 and total thioglycol-
late (expressed as free acid) to 8% (11 % for professional products).
Hair type and condition must be considered by the formulator, and products
can be designed for different hair types. Coarse hair will require a more
severe treatment, and fine or damaged hair a gentler one. There will be
considerable variation from person to person as well as between ethnic
types. Hair that has been damaged should not be treated with waving
products until it has recovered its strength and condition. Variation also
occur across the scalp of an individual and from root to tip of individual
hairs. Bleached hair tends to be very porous and should be treated
with care.
Various mechanical means are used to protect parts of the hair and scalp
during perming. These include the application to desired areas of an absorbent
wrap coated in lotion, and pretreatment of susceptible areas with a
conditioner or barrier-type product. Conditioners may be incorporated into
the waving lotion; good results have been reported for amine functional
silicones in this application.
The use of a high molecular weight keratin hydrolysate (with or without
added fatty quaternary groups), used after rinsing out the waving lotion but
before neutralisation, has been suggested [87]. Covalent bonding of the
protein to the hair shaft is claimed to give a 'permanent' conditioning effect,
i.e. lasting through a number of shampoos. This is an attractive concept and
seems to work well in practice, although a criticism might be that any sites
on the hair shaft used to bond with the protein are no longer available to
bond with other sites on the hair.
Permanent-waving lotions are available in various physical forms, e.g. clear
or cloudy liquid, cream or lotion, gel or thickened liquid. In each case it is
important to use only low-conductivity, demineralised water and to use
equipment made of 316 (or equivalent) grade stainless steel or poly-
propylene/polyethylene for all contact parts. Although other plastics may
also be suitable, it is imperative to avoid heavy metal contamination, which
may decompose the product and produce discoloration, both in the product
and, in extreme cases, on the hair. For this reason, sequestrants are added,
and trace heavy metals in other raw materials used should be minimised. In
the case of emulsion or gel-type products requiring hot manufacture
Table 2.30 Formulations for permanent-waving lotions
Clear Clear Condi- Cream Opaque Gel

lotion lotion tioning gel/cream
Ammonium thioglycollate. 60% 12 14

Thioglycollic acid 6.5 7.5 5 5
Dithiodiglycollic acid, 60% 1.5
Ammonia, 0.880 10.8 11.6 1.8 2.2 8.0 8.4
to pH9.2 9.3 9.2 9.1 9.1 9.2
Ammonium bicarbonate 4
Laureth-12 0.5 0.75
Stearamidopropyl dimethylamine
lactate 0.5
Oleth-20 0.6 0.4
Laneth-75 0.6
Cetyl alcohol 0.8 0.4
PEG-IS cocamine 0.5
Mineral oil 5 2
Lanolin oil I
Glyceryl stearate (and)
PEG-IOO stearate 2.5
Carbomer 941 1.6 1.6
Magnesium aluminium silicate 1.2
Disodium EDT A 0.1 0.1 0.1
Sodium heptonate 0.15 0.1 0.1
Perfume 0.3 0.25 0.5 0.25
processing, thioglycollate should be added last, after cooling the mix. These
products can be extremely difficult to perfume since (i) the product is at high
pH and strongly reducing-a formidable combination; and (ii) the sulphide
odours emitted during processing of the hair are very hard to mask (see
chapter 8).
The examples shown in Table 2.30 are based on thioglycollates, but various
other active materials, such as glyceryl thioglycollate, thioacetic acid, 2-amino
thioethanol, sulphites and bisulphites, have been added. Cysteine deriva-
tives, particularly N-acetyl-I-cysteine are used as primary actives, but are
almost exclusively found in products designed for the Japanese market. Their
history and mode of action are reviewed by Iwasaki [109].
2.12.1 Neutralisation
The reforming of the -S-S-bonds by oxidation is quite straightforward,
although any bonds that are unable to realign may be oxidised to form
various residual side groups on the hair's polypeptide chains. Oxidation is
commonly carried out by hydrogen peroxide, although sodium per borate,
sodium or potassium bromate, urea peroxide, and sodium or ammonium
persulphates have been used. Hydrogen peroxide may be used either as a
straightforward solution (sometimes buffered and frequently stabilised by the
addition of materials such as phenacetin or sodium stannate), or with a
Table 2.31 Formulations for neutralisers
Hydrogen peroxide, 35% 4.5 6 6 5

Sodium bromate 10
Phenacetin 0.Q2 0.Q2 0.04 0.02
Sodium stannate 0.005 0.005 0.005
Phosphoric acid 0.06 to pH3 to pH3
(to pH3)
Citric acid to pH 3.2
Nonoxynol-9 I 0.5
Ethanol B96 3
Hydrolysed protein 2
Glyceryl stearate (and) PEG-IOO stearate 6
Sodium styrene/acrylates/divinylbenzene 0.2
copolymer (and) ammonium nonoxynol-4
sulphate
surfactant added to enhance penetration. The solution may also be clouded

or produced in the form of a pourable emulsion. Bromates (the second most
popular type of 'neutraliser') may also be supplied in solution but are more
frequently presented in solid form in sachets, the contents of which are then
dissolved in water just prior to use. This is a popular approach with home
perms. A large excess of neutraliser is normally used, and this ensures that
the equilibrium point of the reaction is shifted far enough to enable as
complete an oxidation of the broken bonds as possible. Other important
factors are the contact time, temperature, concentration of oxidising agent,
and penetration. Air oxidation has been proposed, and products based on
this principle have been marketed. However, the process is very slow and
the results leave much to be desired. Examples of some typical types of
neutraliser are shown in Table 2.31.
Since both waving lotions and neutralisers usually have quite extreme pHs
and exhibit considerable redox potential, they are not particularly susceptible
to microbiological contamination. Consequently, products may sometimes
be unpreserved if good manufacturing practices are adhered to. If preserva-
tives are used, however, their stability under the conditions just described
should be checked carefully.
The effectiveness of perms may be evaluated by various techniques, of
which salon-based tests are the most important. Alternatives and sup-
plementary methods have been suggested [110, Ill], but professional
hairdressers' opinions must predominate. A general review of permanent
waving is given by Alexander [112, 113].
2.13 Bleaches
Bleaches are virtually always based on hydrogen peroxide, rarely at

concentrations above 12%, and generally lower. To maintain stability,
Table 2.32 Formulation for a bleach base (to

be mixed 1: 1 with hydrogen peroxide)
Oleic acid 22
Ammonia solution, 0.880 6.6
Isopropanol 7
hydrogen peroxide solutions must be acidic, and additional stabilisers are

usually added. Most of the formulations already given for peroxide-based,
permanent-wave neutralisers (Table 2.31) will work equally well as hair
bleaches. The extra stability conferred on the peroxide by the acid medium
reduces its effectiveness as a bleach. (To bleach by oxidation it must of
necessity decompose.) As with most chemical reactions, the process is more
rapid in the presence of heat. Acidic solutions of this kind are used as spray-in
products (non-aerosol), the gentle bleaching effect of which is accentuated
by the use of a hair drier or by the sun's heat.
A stronger effect is achieved by mixing the peroxide solution with ammonia
solution just prior to application (see Table 2.32). This increases the alkalinity.
If the final blend is in the form of a lotion, cream or gel, it is much less likely
to drip or run and is easier to use. A solution of an ammonium soap plus
free ammonia, sometimes containing coconut or oleic/linoleic diethanolamides
in a suitable solvent, and formulated to thicken to a soft gel when diluted
with the hydrogen peroxide solution, may be used. Hydroxyamines (e.g. TEA)
may be used instead of ammonia, but have the disadvantage of not eva-
porating off (and therefore lessening the risk of hair damage) in the event of
overlong processing.
Even stronger bleaching action may be achieved by mixing per-salts (e.g.
ammonium or potassium persulphate) with the peroxide/ammonia bleach.
The per-salts are normally supplied in sachets, blended with diluents
which may also act as alkaline buffers; sodium silicate is often used (see
Table 2.33). These blends are extremely powerful oxidising agents and care
must be taken to exclude organic material (e.g. some colours) from the mix
and to select packaging with adequate moisture barrier properties.
Strong bleaching of hair is a harsh process and should not be carried out
too frequently. As with permanent waving, some degradation of the hair
occurs at each treatment, and hair damage, especially near the tips, is the
Table 2.33 Formulation for a bleach 'booster'

sachet
Ammonium persulphate 30
Potassium persulphate 30
Sodium silicate 40
inevitable result of over-bleaching. As well as lightening the hair, bleaching
often causes some reddening. This is because the hair pigmentation consists
mainly of eumelanin (black) and pheomelanin (red), and the latter is less
easily oxidised.
Even if there is not obvious damage, some additional porosity will result,
and the use of a conditioner, preferably protein based, is strongly recom-
mended. As with permanent waving, various mechanical means are used
to protect the hair when only part of it is to be treated (e.g. for tipping or
streaking). These include plastic hoods through which portions of the hair
can be pulled, and the use of bleach-soaked porous pads which may be
applied selectively.
Before bleach and permanent-wave products are marketed, careful trials
must be carried out to check their safety. In addition, the consumer package
must carry suitable instructions for use, and warnings against misuse.
2.14 Hair dyes

Hair dyes are conveniently grouped into temporary, semi-permanent and
permanent, the distinction usually arising more as a result of the dye system
used, rather than the longevity of the colour.
2.14.1 Temporary dyes

Almost any soluble colour can be used here [111]. Penetration of the hair
shaft by the colour does not occur to any significant extent, and the overall
effect is to add only a slight additional coloration to the hair. A means of
keeping the colour on the hair is required, and a setting lotion base is a
popular choice-all of the examples quoted earlier might be used for the
purpose. Complete removal by a single shampooing is usually possible.
Another means of temporarily colouring the hair is to apply finely ground
metals by means of a 'puffer' spray. Such metals, which include brasses,
bronzes and aluminium, both untreated and anodised in various colours, are
widely used by the paper and board converting industry, and by printing-ink
and paint manufacturers. They provide a metallic effect when applied to hair,
and are used for highlighting rather than whole-head treatment. Hairspray
is used to prevent the powder brushing off easily. Organic and inorganic
pigments can be suspended in gum-thickened or emulsion bases and streaked
on to the hair. Bright reds, blues, yellows and greens are possible and appli-
cation may be by means of mascara-type brushes, nail-varnish type packs,
or even in the form of sticks.
Temporary hair colouring (or, on highly bleached hair, semi-permanent
colouring) may also be achieved by using the leuco derivative of a basic dye
such as crystal violet. This is formed by reducing an aqueous/alcoholic
solution of the dye with sulphur dioxide (an objectionable process, which
should be carried out with due regard to operator safety). The product is
either applied directly to the hair, or is diluted to form a rinse. This is followed
by rapid air oxidation to give a 'blue rinse' effect. Complexes of acid dyes
with cationic surfactants have also been used [114].
Temporary dyes represent only a small portion of the hair colourants
market, which is dominated by permanent and semi-permanent colourants.
2.14.2 Semi-permanent colourants

A wide variety of dyestuffs have been tried over the years [114], including
azo dyes, either preformed or formed in situ by coupling on the hair, and
reactive dyes [115-117]. This latter class is based on groups such as mono- or
dichlorotriazine, which can react directly with the hair and to which an
appropriate chromophore is attached. A good effect is difficult to obtain
under practical application conditions. Other systems involving the use of
strong reducing agents (e.g. permanent-waving lotions) to break bonds within
the hair shaft and provide a reaction site for hair dyes have been proposed,
but have not proved to be commercially realistic.
In practice, most semi-permanent hair dyes are based on basic dyestuffs,
whose cationic character gives them a natural affinity for the hair, or on
metallised dyestuffs, often in combination with nitro derivatives of aromatic
diamines or aminophenols. Shampoo is the most commonly used base and
presents no problems with metallised dyes provided that the active level
of anionic surfactant, the presence of which retards the dyeing process, is
low. Metallised dyes are not very compatible with salt, therefore a blend of
amphoteric/cationic/non-ionic surfactants with low salt levels is preferred.
Performance of all semi-permanent dyestuffs may be enhanced by the
inclusion of solvents. Water causes considerable swelling of the hair shaft,
but aqueous solutions of some solvents cause even more, leading to greatly
increased dye uptake. Widely used solvents include benzyl alcohol, butyl
alcohol, and methyl, ethyl and butyl ethers of monopropylene or dipropylene
glycols. Levels are rarely above 5%. Various patents, some quite recent, cover
such solvent-assisted systems, which have been in use for at least 25 years.
Increased penetration may also be achieved by using the hydrogen-bond
breaking properties of urea. Since hair tends to be more porous near the
ends than at the roots, and bleached or permed hair tends to be more porous
than untreated hair, quite large variations in dye uptake may occur. This
can be overcome, as in textile dyeing, by using levelling agents; the inclusion
of a small amount of non-ionic, e.g. 0Ieth-20, often helps. Pohl [118]
recommends the use of a mixture of high and low molecular weight dyestuff.
Typical formulations for semi-permanent hair colourants are shown in
Table 2.34.
In theory, virtually any colour could be achieved by using a combination
of, say, suitable red, yellow and blue dyes. In practice, dyes absorb on the
Table 2.34 Formulations for semi-permanent hair colourants
Liquid Cream Shampoo Shampoo
Metallised dyes
o-Nitro-p-phenylene diamine } total < 2.5} total < 2
p-Nitro-o-phenylene diamine
Basic dyes < 1.0 < 1.0 < 1.0
Cetyl trimethyl ammonium chloride, 30% 3 4 2
Cocoamidopropyl betaine, 30% 15
Oleth-20 0.5 0.2 0.5
Coconut diethanolamide 2 2.5
Cetostearyl alcohol 3
Glyceryl stearate (and) PEG-IOO stearate 3
Hydroxypropyl methylcellulose 0.8 0.5 0.5 0.4
Triethanolamine to pH 8 to pH 8 to pH 8.5
Citric acid 0.3 0.25
Preservative q.s. q.s. q.s. q.s. q.S.
Perfume q.S. q.s. q.s. q.S. q.s.
Benzyl alcohol 3 2
PPG-2 butyl ether 2
Deionised water to 100 to 100 to 100 to 100
hair shaft at different rates, and are removed at different rates by shampooing.
Consequently, products containing a mixture of dyestuffs can produce
different colours when applied under different conditions (time, temperature,
pH, etc.). In addition, the colour achieved may vary considerably from one
type of hair to another, and after application and subsequent shampooing.
Minimising these variations can be achieved by using colours that are close
together; this approach is less likely to produce any unexpected (and usually
unwanted) colours.
Basic dyes are more substantive from slightly alkaline bases, and metallised
dyes from quite strongly acidic ones. Since salt can reduce substantivity,
thickening, where required, is usually achieved by means of gums. Light-
fastness is not usually a problem with semi-permanent colours (it can be
with some of the temporaries) but scalp staining can occur, more so with
solvent-assisted systems.
2.14.3 Permanent hair dyes

Permanent, or oxidation, dyes are fundamentally different to the other classes
of dyestuffs that have already been considered. The dyes are formed during
the dyeing process and are not present, as such, in the solutions before
application. The products consist of two parts-a dye intermediate solution
and an oxidising agent, the latter almost always being hydrogen peroxide.
Dye intermediates are blends of primary intermediates and coupling agents,
or modifiers, in a suitable base. During the permanent dyeing of hair the
dye intermediate solution and the oxidising solution are mixed and applied
to the hair. The primary intermediates are gradually oxidised and then
undergo coupling reactions with the modifiers. The primary intermediates
are all small molecules that can, to a degree, penetrate the hair shaft,
particularly under the wet, alkaline conditions prevailing during the dye
application. The subsequent oxidation and coupling reactions produce much
larger molecules, many of which are then 'trapped' within the hair shaft,
thereby making the effect 'permanent'. The primary intermediate should be
an aromatic compound with at least two electron-donating groups in the
1,2 or 1,4 positions. The most effective combinations are either two amino
groups or one amino and one hydroxyl group, attached to a benzene or
toluene ring. Other substituents may be present, either on the ring or
N-substituted, and the ring itself may be non-benzene derived (e.g. pyridine).
The most commonly used are:
OH
p-phenylene p-toluylene p-aminophenol
diamine diamine
Oxidation then takes place to form a quinonimine, e.g.
..
OH
..
Coupling agents require the substituting groups to be in the 1, 3 positions.
They are not easily directly oxidised, but will undergo oxidative coupling
with the quinonimines formed from the primary intermediates.
Coupling agents may be based on benzene rings, (substituted or otherwise),
multiple ring systems, (fused or unfused), or heterocyclic rings. More than
one stage of oxidative coupling may occur, sometimes leading to some very
large molecules [118]. The possible reactions, even starting from a blend of
relatively few primary intermediates and coupling agents, are numerous. The
hair itself may modify or even take part in some of the reactions. The original
theory that Bandrowski's bases were intermediates in the dying of hair
with oxidation dyes is now widely discounted. As well as reaction within the
hair shaft, oxidation and coupling simultaneously take place in the solution
outside the hair. The multitude of reactions and reaction rates may give rise
to some strange intermediate colours in the solution (and sometimes on the
hair!). For this reason, it is important to determine and stick to, the correct
length of contact time. Unwanted shades are more likely to arise from
underprocessing than from overprocessing.
The complex chemistry and reaction kinetics involved mean that the
development of specific shades is to a large extent empirical, although general
rules covering certain combinations of primary intermediate and modifier
exist. Yellow, orange and red shades can be obtained with the nitro derivatives
already referred to in section 2.14.2; otherwise it is quite unusual to mix
oxidative dyes with other types. Permanent dye systems are able to colour
hair to a lighter shade than the original. Peroxide and ammonia, present in
excess to ensure complete and controlled oxidation of the dye intermediates,
simultaneously bleach the hair. A further increase in the peroxide emphasises
the bleaching effect. Permanent dyes are also capable of 'evening-out' the
differences in colour between individual hairs. This is especially effective on
grey hair, which consists of mixed coloured and white hairs, and is impossible
to colour evenly by any other means.
A high pH is necessary and is usually achieved with ammonia, often
buffered. If significant lightening is not required (i.e. for dark shades),
hydroxyamines such as TEA can be used, and the pH kept a little lower. As
with the semi-permanent dyes, solvents are sometimes used to increase hair
swelling and dye penetration. Some cream products are available but
shampoo-in bases with good wetting properties, obtained using a wide variety
of surfactants (often in conjunction with ammonium oleate), ensure even dye
distribution and are most popular.
Some of the dye intermediates and modifiers are very readily oxidised in
alkaline solution, even by the air and, for this reason, water-soluble reducing
agents such as sulphites, bisulphites, dithionites or ascorbic acid are added
to the base. Batches of these products are often prepared under a blanket of
nitrogen. Opaque or brown glass packaging helps to disguise the inevitable
batch-to-batch colour variation of the dye solution.
Permanent colourants cause some hair damage; an increase of alkaline

solubility from 6% (natural hair) to 10% (after five applications of oxidative
dye) has been reported [119] but is really quite minor. The incorporation
of conditioning agents into the base, and the use of post-dyeing shampoos
and conditioners allows very good aesthetic effects; leaving the hair not only
coloured (lighter or darker) but glossy and with good handle. Oxidative dyes
are able to smooth out unevenness in natural hair colour, although caution
should be exercised since extra porosity is conferred by bleaching or
permanent waving. Hair should not be dyed until several weeks after perming
or bleaching.
In developing a range of shades, testing should be carried out on various
different hair types, both bleached and unbleached. A variety of colours of
human hair tresses can be purchased for this purpose. Initial screening may be
carried out on wool, which has a structure closely akin to hair, but final
colour tests need to be carried out on real hair. Perceived colour will vary
according to the hair type, style, gloss, etc. and also between different ethnic
groups [120]. Evaluation is usually carried out by eye, preferably in a light
cabinet fitted with 'north daylight' fluorescent tubes to provide standardised
viewing conditions. Instrumental colour measurement may also be used
[121].
The range of possible intermediates and modifiers is numerous and
constantly changing. Some materials once used are now banned, while others
are restricted. In the UK, the most up-to-date legislation covering this is The
Cosmetic Products (Safety) Regulations 1989, S.1. No. 2233 (1989) and the
Cosmetic Products (Safety) (Amendment) Regulations 1993. These are the
latest enactments of the EC Cosmetics Directive and include Schedule I
(materials not permitted) and Schedule 2 (restricted substances). Currently
the total concentration of most of the dye intermediates is restricted both
individually and in combination. In the USA, the use of colours in cosmetics
is controlled by the FDA. Phenylene diamines, diamino phenols, a-naphthol,
pyrogallol and resorcinol are all, for instance, restricted. Oxidation hair dyes
are also required to carry a warning since many of the intermediates and
modifiers are allergens and sensitisers. The warning must appear in the
Table 2.35 Formulations for oxidation hair-dye bases
A B
Isopropanol 7.5
PPG-2 methyl ether 1.8
Oleic acid 22 4
Coconut diethanolamide 10 11
Salt q.s.
Deionised water to 100 to 100
Ammonium, 0.880 6.6 2
statutory form as prescribed by the Regulations. Hair dye intermediates have
generated a huge number of patents and due regard must be paid to these
when deciding a formula.
Table 2.35 gives typical formulations for oxidation hair-dye bases. In
formulation B the salt level must to be adjusted to give the required viscosity
on dilution with an equal volume of hydrogen peroxide solution. The dye
intermediates themselves can have a considerable impact on the viscosity,
and base may need to be varied from shade to shade to compensate for this.
2.14.4 Other hair dyes

Some hair colourants do not fall neatly into the temporary/semi-
permanent/permanent classification. These include the vegetable dyes, mostly
based on henna [122]. The dried leaves of the henna plant are powdered
and applied as a paste to the hair, either alone or mixed with other plants
such as indigo or camomile. (Diluents, fillers, thickeners, etc. can also be
added.) A less satisfactory alternative is the preparation and use of an aqueous
extract of henna leaves as a base. The use of henna as a hair dye has a
number of disadvantages-the limited range of shades attainable (all reddish
when using henna alone), build-up on repeated use (leading to rather
unnatural colours), a long contact time, and the need to apply the product
hot to obtain the best effect. Advantages are that the product is 'natural'
and has a good record of non-irritancy. The main active ingredient is lawsone
(2-hydroxy-l,4-naphthaquinone), also present in walnuts. The optimum pH
is mildly acid.
Most women, when faced with greying hair, will simply dye it to the colour
oftheir choice. Most men in the same situation will either persuade themselves
that greying hair looks distinguished or assuage their vanity by using a
lead-sulphur dye. These products consist of a solution of lead acetate and
precipitated sulphur, both at 1-1.5% in an aqueous base, usually with a small
amount of a wetting agent, humectant, and sometimes a little solvent. The
products are applied regularly and left on the hair, where a slow reaction
takes place, leading to a gradual build-up of a brownish colour. The effect
is not always very natural looking and the hair may be left a little dull. The
exact mechanism of the reactions is not clear. The products are toxic and
should be handled with care.
2.14.5 Dye removers

No dye removers are completely successful. Semi-permanents, by their very
nature, will eventually wash out, whereas permanent dyes will usually only
fade slightly as they 'grow out' naturally. A limited degree of success may be
obtained with sulphites and other related reducing agents, in particular
sodium formaldehyde sulphoxylate. The use of activated charcoal can
improve the effectiveness of such bases but is unsightly and messy [117].
2.15 Product evaluation and testing
The experienced formulator will normaliy have a fairly accurate idea

of the performance that might be expected from a newly formulated product.
The less-experienced will have difficulty. Even when working in known
territory, there can be surprises-perhaps hitherto unreported synergism
between raw materials, unexpected incompatibilities, or simply the fact that
the formulator's assessment of product performance differs considerably from
that of the end-user. Methods for testing and evaluating products are essential
to confirm that products are meeting the requirements of the original brief.
Such methods can be grouped into two main types.
(i) In vitro methods, which are laboratory-based, and can be quite
objective. Although instruments can often be used to produce a quanti-
fiable result, the substrate is not the same as hair growing on the head,
and the conditions of the tests may be too far removed from real condi-
tions of use.
(ii) In vivo methods, which overcome the problems associated with in vitro
methods but at the expense of producing less-easily quantifiable results
under less-reproducible conditions.
A combination of both approaches is often used, with laboratory-based
instrumental techniques for initial screening, foliowed by salon or consumer
testing for final selection. Many test methods and protocols, covering many
aspects of product performance, have been used [37,123-127].
2.15.1 Stability testing

The EC cosmetics directive specifies that products should remain safe and
effective for two and a half years. Clearly, product testing for this duration
is not commercially acceptable, and accelerated tests are widely used. The
legal requirement is not concerned with changing attributes, for example loss
or degradation of colour or perfume, although in practice, these are most
likely to suffer. Many test methods, such as high- and low-temperature storage,
freeze/thaw cycling, centrifugation and high-intensity light irradiation, are
available to the development chemist. Such tests and their interpretation,
although straightforward, require skill and experience. Monitoring of the
first production batches should complement work carried out at the
development stage. Specifications for production batches are mostly based
on laboratory stability results and should be confirmed on large-scale
production [128-130]. Compatibility testing should also be carried out. Two
sets of tests run in parallel, one set in the actual containers to be used (or
containers made from the same material), the other in inert containers, usually
glass, give valuable comparative data.
2.15.2 Claims justification
If specific claims are to be made for the product, the manufacturer must
be able to justify them. This can often be based on known properties
of the raw materials used, provided that usage levels and conditions of use
are consistent with those of the study on the raw material. Other cases
may require laboratory testing, salon trials, or consumer panel tests to verify
that the proposed claims are indeed true. In any panel test, the number and
type of subjects used must be adequate, and the results must be subjected
to an appropriate significance test. When selecting the best test method, each
case must be treated individually. However, the previous comments made
about the relative merits of different evaluation techniques are equally
relevant. This whole area is one which will doubtless attract more attention
when the forthcoming 6th Amendment to the EC Cosmetic Directive comes
into force, with its requirement for creating a 'product information package'
for each product.
2.15.3 Product safety

Last, but certainly not least, every development laboratory should have a
review procedure to ensure the safety of new products. This procedure should
include the examination of all formulations for safety. If a formulation is a
'standard' one, no further action may be necessary. If new raw materials or
unusual combinations of materials are used, or if any ingredient is
present at an unusually high level, the recommendation may be that the formu-
lation should be externally vetted. The opinion of a qualified dermatologist,
ophthalmologist or toxicologist may be an invaluable back-up to the cosmetic
chemist's judgement. In cases where there is real doubt about the total safety
of the product (including foreseeable conditions of misuse), further testing
may be required, preferably in the form of a human volunteer study. Large
companies may have departments dedicated to this, but it is essential that
smaller companies can, and do, ensure the safety of people coming into
contact with the product, not least the end-user.
2.16 Summary
This chapter has concentrated on the most important products in a

concise manner. For those interested in acquiring more in-depth information,
the references given wi11lead to more references, including a wealth of patents.
Patents have not been quoted extensively in the chapter, since much of the
information contained therein relates to formulations which have never been
commercially produced. A huge amount of published material, including
formulation guidelines is available from the majority of reputable raw
material suppliers. The best of this material offers an excellent technical

support service.
References
1. Harry. R.1. (1982) Harry's Cosmeticology. 7th edn. Chapter 23, p. 397. Longmans, London.
2. Alexander, P. (1990) The structure of the hair. M anuJacturing Chemist 61(2) 20.
3. Shaw, D.M. (1979) Hair lipid and surfactants. Int. J. Cosmet. Sci. 1(6) 317.
4. Weigmann, H.D. and Kamath, Y.K. (1986) Modification of human hair through fibre
surface treatments: characterisation by wettability. Cosmet. Toilet. 101 (6) 37.
5. Tolgyesi, E. (1983) Weathering of hair. Cosmet. Toilet. 98(10) 29.
6. Swift, J.A. (1990) Fine details on the surface of human hair. Presented at the SCS symposium
on The Future oj Hair Care Technology, Harrogate, November 1990.
7. Bories, M.F., Martina, M.e., Bobin, M.F. and Cotte, J. (l984) Influences des
variations thermiques sur la structure du cheveu. Int. J. Cosmet. Sci. 6(5) 201.
8. Bories, M.F., Martina, M.e., Bobin, M.F. and Colle, J. (1984) Influences des variations
thermique sur les proprietes mecaniques du cheveu. Int. J. Cosmet. Sci. 6(5) 213.
9. Stamm, R.F., Garcia, M.L. and Fuchs, lJ. (1977) The optical properties of human hair: I
Fundamental considerations and goniophotometer curves. J. Soc. Cosmet. Chem. 28,
(9) 571.
10. Stamm, R.F., Garcia, M.L. and Fuchs, J.1. (1977) The optical properties of human hair:
II: The lustre of hair fibres. J. Soc. Cosmet. Chem. 28(9) 601.
11. Henderson, G.H., Karg, G.M. and O'Neill, lJ. (1978) Fractography of human hair. J. Soc.
Cosmet. Chem. 29(8) 449.
12. Report on 16th IFSCC Congress (1991) Soap, PerJumery Cosmet. 64(1) 37.
13. Maes, D., Leduc, M., Nadvorkin, I.M., Reinstein, J.A., Turef, B.A. and Vieu, M. (1979)
Some aspects of hair regreasing. Int. J. Cosmet. Sci. 1(3) 169.
14. Knott, e.A., Daykin, K. and Ryan, J. (1983) In vivo procedures for assessment of hair
greasiness. Int. J. Cosmet. Sci. 5(3) 77.
15. Hunting, A.L.L. The Encyclopaedia oj Shampoo Ingredients. London Micelle Press.
16. Rieger, M. (1988) Surfactants in Shampoos. Cosmet. Toilet. 103(3) 59.
17. Milwidsky, B. (1989) Soapless shampoo actives. Household and Personal Products Industry
26(9) 58; 26(10) 52; 26(11) 55.
18. Lomax, E. (1989) An introduction to surfactants. CTMS XIV 15; XV 21; XVI 15; XVII 31.
19. Harry, R.J. (1982) Harry's Cosmeticology. 7thedn. Chapter 24, p. 433. Longmans, London.
20. Donaldson, B.R. and Messenger, E.T. (1979) Performance characteristics and solution
properties of surfactants in shampoos. Int. J. Cosmet. Sci. 1 71.
21. Alexander, P. (1986) The Miranol amphoteric surfactants, carboxylates and sulphonates,
their chemistry and application. Soap. PerJumery Cosmet. 59(9) 493.
22. Lomax, E. (1988) Newpolyfunctional amphoterics. CTMS 1(4) 18.
23. Mizayawa, K. and Tamura, U-hei. (1993) N-Acyl-N-methyllaurates. Cosmet. Toilet. 108(3)
81.
24. Salka, B. (1993) Alkyl polyglycosides, properties and applications. Cosmet. Toilet. 108(3) 89.
25. Kamegai, J. and Onitsuka, S. (1993) Alkylsaccharides, use in shampoo. Manufacturing
Chemist 64(9) 20.
26. Shell Routes to Detergents. Shell Chemicals leaflet, Shell.
27. High Active SurJactants. Albright Wilson booklet, Albright & Wilson, White Haven, UK.
28. Milwidsky, B. (1987) Sulphosuccinates and related compounds. Household and Personal
Products Industry 24(8) 52.
29. Schoenberg, (1989) Sulphosuccinate surfactants. Cosmet. Toilet. 104(11) 105.
30. Petter, P.J. (1983) Fatty acid sulphoalkyl amides and esters as cosmetic surfactants.
Presented at the symposium on SurJactants in Cosmetics and Toiletries, Coventry, April 1983.
31. Dominguez, J.G., Balaguer, F., Parra, J.L. andPelejero, C.M. (1981) The inhibitory effect of
some amphoteric surfactants on the irritation potential of alkylsulphates. Int. J. Cosmet. Sci.
3(2) 57.
32. Surfadone surface active pyrrolidones (1988) CTMS 1(4) 33.
33. Miyazawa, K., Ogawa, M. and Mitsu, T. (1984) The physico-chemical properties and
protein denaturation potential of surfactant mixtures. Int. J. Cosmet. Sci. 6( I) 33.
34. Lomax, E. (1989) Irritation and micellar properties of surfactants. CTMS XI 13.
35. Lomax, E. (1988) New amphoteric formulations. Soap, Perfumery Cosmet.61(11).
36. Lomax, E. (1992) The mechanism of surfactant detoxification. Soap, Perfumery Cosmet.
65(11) 37.
37. Domingo Campos, F.J. and Druguet Tantina, R.M. (1983) Evaluation of the foaming capa-
city in shampoos; efficacy of various experimental methods. Cosmet. Toilet. 98(9) 121.
38. Larson, R.I, and Bishop, W,E, (1988) New approaches for assessing surfactant biodegrada-
tion in the environment. Household and Personal Products Industry 25(5) 84.
39. Carson, H.C. (1990) Surfactants-environmental issues. Household and Personal Products
Industry 27(6) 41.
40. Gilbert, P.A. and Pettigrew, R. (1984) Surfactants and the environment. Int. J. Cosmet. Sci.
6(4) 149.
41. Grandval, G. (1986) Evaluating and choosing fragrances for functional products. Cosmet.
Toilet.lOl( 6) 69.
42. Harding, N. (1986) Evaluation of perfume submission from expert to consumer-A review
of approaches. Cosmet. Toilet 101(6)73.
43. Aarts, P. (1986) Evaluation of fragrances from both captive and external sources. Cosmet.
Toilet. 101(6) 79.
44. Beeding, J. (1993) Formulating and fragrancing multi-functional shampoos. Manufacturing
Chemist 64(11) 18.
45. Blakeway, J.M. and Fabrizi, G. (1983) Substantivity of perfume materials to hair. Int. J.
Cosmet. Sci. 5(1) 15.
46. Orth, D.S. (1989) Microbiological considerations in cosmetic formula development and
evaluation. Cosmet. Toilet. 104(4) 49.
47. Cosmetics preservatives encyclopaedia-antimicrobials (1990) Cosmet. Toilet. 105 49.
48. Busch, P., Hase, c., Schutze, R., Hensen, H. and Lorenz, P. (1987) Hair conditioning effect
of guar hydroxypropyl trimethylammonium chloride. Cosmet. Toilet. 102(5) 49.
49. Smith, L.R. and Gesslein, B.W. (1990) The functions and formulations of conditioning
agents in shampoos-past, present and future. Presented at the SCS Symposium on The
Future of Hair Care Technology, Harrogate, November 1990.
50. Patel, c.u. (1983) Antistatic properties of some cationic polymers used in hair care
products. Int. J. Cosmet. Sci. 5(5) 181.
51. Sejpka, J. (1993) The silicone story. Soap, Perfumery Cosmet. 66(4) 29.
52. Needs, S.G. (1984) Methods oflight fastness testing. Presenting at the SCS Symposium on
Product Stability, Coventry, November 1984.
53. Van Abbe, N.J., Head, D., Reed, J.V., Murrell, E.A. and Baxter, P.M. (1986) Dandruff:
infection or not? Int. J. Cosmet. Sci. 8(1) 37.
54. Van Abbe, N.J., Baxter, P.M., Jackson, J., Bell, M.A. and Dixon, H. (1981) The effect of hair
care products on dandruff. Int. J. Cosmet. Sci. 3(5) 233.
55. Francois-Poncet, G.A. (1983) Trends in antidandruff preparations. Cosmet. Toilet. 98(9)
101.
56. Kligman, Lowe and Maibach (1984) Scalp disorders. Soap, Perfumery Cosmet. 57(11) 569.
57. Lansdown, A. (1986) Observations on zinc pyrithione as an effective treatment. Soap,
Perfumery Cosmet. 59(9) 499.
58. Shuster, S. (1988) Dandruff, seborrhoeic dermatitis and pityrosporum ovale. Cosmet. Toilet.
103(3) 87.
59. Hair Sunscreen Study VD-OJ-85. VanDyk&Co.
60. Sendelbach, G., Liefke, M., Schwan, A. and Lang, G. (1993) A new method for testingremo-
vability of polymers in hair sprays and setting lotions. Int. J. Cosmet. Sci. 15(4) 175.
61. Colipa: Document 88/085 (1988) Traces ofNDELA in cosmetic products.
62. Dunnett, P.C. and Telling, G.M. (1984) Study ofthe fate ofbronopol and the effects of anti-
oxidants on N-nitrosamine formation in shampoos and skin creams. Int. J. Cosmet. Sci. 6(5)
241.
63. Telling, G.M. and Dunnett, P.c. (1981) The determination of NDELA at trace levels in
shampoos and skin creams by a simple rapid colorimetric method. Int. J. Cosmet. Sci. 3(5)
241.
64. Taylor, P. (1989) Nitrosamines-occurrence, toxicology and analysis; avoiding their

presence in cosmetics. Presented at the CTPA Autumn Conference, 1989.
65. Komp, B. and Reng, A.K. (1989) Developing ether sulphate-free surfactant formulations.
Cosmet. Toilet.l04( 4) 41.
66. Woodruff, J. (1994) Shampoo takes a professional lead. Manufacturing Chemist 65(2) 18.
68. Hunting, A.L.L. Encyclopaedia of Conditioning Rinse Ingredients. CTFA (1991) London
Micelle Press.
69. CTFA (1991) International Cosmetic Ingredient Dictionary, 4th edn. CTFA, Inc.,
Washington, DC.
70. Milwidsky, B. (1990) After shampoo preparations. Household and Personal Products
Industry 27(5) 78.
71. Idson, B. and Lee, W. (1983) Update on hair conditioner ingredients. Cosmet. Toilet. 98(10)
41.
72. Quaternary ammonium compounds and their application in hair conditioners (1988) CTMS
1(4) 6.
73. Lunn, A.C. and Evans, R.E. (1977) The electrostatic properties of human hair. J. Soc.
Cosmet. Chem. 28(9) 549.
74. Allandic, A. and Gummer, G. (1993) Hair conditioning-quaternary ammonium
compounds on various hair types. Cosmet. Toilet. 108(3) 107.
75. Alexander, P. (1987) Cationic polymers for skin and hair conditioning. Manufacturing
Chemist 88(7) 24.
76. Woodruff, J. (1994) Staying in condition. Manufacturing Chemist 65(3) 18.
77. Griffin, W.G. (1949) J. Soc. Cosmet. Chern. I 311.
78. Lin, T.J. (1978) Low energy emulsification I: principles and applications. J. Soc. Cosmet.
Chem.29117.
79. Lin, T.J. (1978) Low energy emulsification II: evaluation of emulsion quality. J. Soc. Cosmet.
Chem. 29 745.
80. Lin, T.J., Akabori, T., Tanaka, S. and Shimira, K. (1980) Low energy emulsification III:
emulsification in the high alpha range. Cosmet. Toilet. 95(12) 33.
81. Lin, T.J., Akabori, T., Tanaka, S. and Shimira, K. (1981) Low energy emulsification IV:
effect of emulsion temperature. Cosmet. Toilet. 96(6) 31.
82. Lin, T.J., Akabori, T., Tanaka, S. and Shimira, K. (1983) Low energy emulsification V:
mechanism of enhanced emulsification. Cosmet. Toilet. 98(10) 67.
83. Driscoll, W.R. (1975) Drug Cosmet. Industry 11 642.
84. Oba, K. (1988) Cosmetic products affecting hair growth. Cosmet. Toilet. 103(5) 69.
85. Futterer, E. (1983) Antidandruff tonic containing piroctone olamine. Cosmet. Toilet. 103(2)
49.
86. Harry, R.J. (1982) Harry's Cosmeticology. 7th edn. Chapter 26, p. 498. Longmans, London.
87. Chester, J. and Mawby, G. (1987) Permanent hair conditioning. Manufacturing Chemist
58(4) 53.
88. Giesen, Hollenberg, Hubbuch, Kalh6fer, Maier, Martin, Miinzig, Schwan, Sperling and
Tennigkeit. UV Filters for Hair Protection. Faschgruppe, Haarbehandlung Publication
BASF.
89. Saettone, M.F., Giannaccini, B., Morganti, c., Persi, A. and Cipriani, C. (1986) Substan-
tivity of sunscreens: an appraisal of some quaternary ammonium sunscreens. Int. J. Cosmet.
Sci. 8(1) 9.
90. Tazi, M. and Login, R.B. (1990) Progress in water-based hairspray. Presented at the SCS
symposium on The Future of Hair Care Technology, Harrogate, November, 1990.
91. Petter, P.J. (1987) Trends in hair care products. Soap, Perfumery Cosmet. 60(95) 29.
92. Petter, P.J. (1989) Acetylene derived polymers and their applications in hair and skin care.
Int. J. Cosmet. Sci. 11(1) 35.
93. Georgalas, A. (1993) Photoprotection of hair. Cosmet. Toilet. 108(3) 107.
94. Dubrief, C. (1992) Experiments with hair photodegradation. Cosmet. Toilet. 107(10) 95.
95. Carbopol Trouble-Shooting Guide (1988) B.F. Goodrich leaflet, B.F. Goodrich, Middlesex,
UK.
97. Alexander. P. (] 99]) Dressing up hair. Manufacturing Chemist 62(3) 26.
98. Alexander, P. (1988) Permanent waving. Manufacturing Chemist 59(4) 42; 59(5) 61.
99. Lee, A., Bozza, J.B., Huff, S. and de la Mettrie, R. (1988) Permanent waves: an overview.
Cosmet. Toilet. 103(5) 37.
100. Harry, R.J. (1982) Harry's Cosmeticology. 7th edn. Chapter 28, p. 555. Longmans,
London.
101. Chesebrough-Ponds (1986) European Patent 0190834.
102. Gumprecht, J.G., Patel, K. and Bono, R.P. (1977) Effectiveness ofreduction and oxidation
in acid and alkaline permanent waving. J. Soc. Cosmet. Chem. 28(12) 717.
103. Puri, A.K. (1979) Recent trends in the formulation of permanent waving products for the
hair. Int. J. Cosmet. Sci. 1(1) 59.
104. Chiodi, F. (1989) Modele mathematique pour l't\tude des equilibres physico-chimiques de
permanentes. Int. J. Cosmet. Sci. 11(6) 283.
105. Hilterhaus-Bong, S. and Zahn, H. (1989) Lipid chemical aspects of permanently waved
hair. Int. J. Cosmet. Sci. 11(4) 167.
106. Hilterhaus-Bong, S. and Zahn, H. (1989) Protein chemical aspects of permanent waving
treatments. Int. J. Cosmet. Sci. 11(5) 221.
107. Cannell, D.W. and Carothers, L.E. (1978) Permanent waving products: utilization of the
post-yield slope as a formulation parameter. J. Soc. Cosmet. Chem. 29(11) 685.
108. Marti, M.E. (1990) Comparison of permanent waving: USA vs Europe. Cosmet. Toilet.
105(5) 113.
109. Iwasaki, A. (1994) Cysteine waving lotions. Cosmet. Toilet. 109(3) 69.
110. Watanabe, K., Minel, M. and Horikushi, T. (1985) US Patent 4,510,951.
111. Harry, R.J. (1982) Harry's Cosmeticology. 7th edn. Chapter 27. Longmans, London.
112. Alexander, P. (1993) Waving hair with greater care (part 1). Manufacturing Chemist 64(4)
33.
113. Alexander, P. (1993) Waving hair with greater care (part 2). Manufacturing Chemist 64(5)
40.
114. Fishman, H.M. (1988) Non-permanent hair dyes, a review. Household and Personal
Products Industry 25(4) 62.
liS. Broadbent, A.D. (1963) American Perfumer and Cosmetics 78(3) 23.
116. Shansky, A. (1966) American Peljumer and Cosmetics 81(121) 23.
117. Shipp, J.J. (1968) Unpublished work.
118. Pohl, S. (1988) The chemistry of hair dyes. Cosmet. Toilet. 103(5) 57.
119. Bauer, D., Beck, J.P., Monnais, C. and Vayssie, C. (1983) Contribution to the quantifica-
tion of the conditioning effects of hair dyes. Int. J. Cosmet. Sci. 5(4) 113.
120. Bustard, H.K. and Smith, R. W. (1990) Studies offactors affecting light scattering by indi-
vidual human hair fibres. Int. J. Cosmet. Sci. 12(3) 121.
121. Gerrard, W.A. (1989) The measurement of hair colour. Int. J. Cosmet. Sci. 11(2) 97.
122. Forrestier, J.P. (1981) Un sene, cassia obovata, utilise comme cosmetique: Ie 'henne
neutre'. Int. J. Cosmet. Sci. 3(5) 211.
123. Callingham, M. (1983) Shampoo evaluation, Parts I and II. Soap. Perfumery Cosmet.56(4)
177; 56(5) 220.
124. Scandel, J., Reinstein, J.A. and Brudney, N. (1979) Studies on the cosmetic criteria of hair
after shampoo. Int. J. Cosmet. Sci. 1(2) 111.
125. Scandel, J., Reinstein, J.A. and Brudney, N. (1983) Shampoos and their aesthetic effects.
Int. J. Cosmet. Sci. 5(5) 157.
126. Ryan, J. (1990) Understanding product performance. Presented at the SCS symposium on
The Future of Hair Care Technology, Harrogate, November 1990.
127. Joy, M. and Lewis, D.M. (1990) The use ofFTIR in the study of surface chemistry of hair
fibres. Presented at the SCS symposium on The Future of Hair Care Technology,
Harrogate, November 1990.
128. Cadwallader, D.E. (1989) Stability Testing. Cosmet. Toilet. 104(11) 87.
129. Toler, J.C. Preservation with safety. Presented at the SCS symposium on Product Stability,
Coventry, November 1984.
130. Ford, D.M. (1983) The responsibilities and ethics of product testing. Cosmet. Toilet. 98(2)
23.
3 Skin-care products
W.H. SCHMITT
3.1 Introduction
The technology of skin care is broad and differs from many other cosmetic
categories because of the functional nature of many of the products. There
are products that primarily have cosmetic effects and products that have
very significant pharmacological effects. All products, however, are designed
to interact and treat the largest organ of the body-the skin. To understand
the need for the category, one must understand the business. The skin-care
business is very large worldwide, with total sales of over 10 billion dollars
divided between mass and prestige distribution. Mass is roughly 60% and
prestige roughly 40%. The largest markets are Japan, at 3.5 billion dollars,
the US at 2.5 billion dollars, and western Europe at 3 billion dollars.
Further divisions within the business are products based in sub-categories
within the skin-care market. As an example, the US market is 23% hand and
body moisturizers, 34% facial moisturizers, 13% suncare and 24% cleansers
(excluding bar soaps). These ratios vary between mass and prestige, and from
market to market, depending on national distribution patterns, usage habits
and the number of products used by consumers on a regular basis. With the
exception of hand lotions, sunscreens and lip protection products, and
excluding bar soaps, the market usage and purchase is dominated by women,
who account for over 80% of the usage and perhaps 90% of purchase.
3.2 Anatomy and physiology of the skin
The skin is the largest organ of the body. It is an organ that has diverse
functions, including barrier function [1], protection from radiation, control
of body temperature and transmission of stimuli from its abundant network
of nerves.
An excellent reference text on the skin is provided by Montagna and
Parakkal [2]. This text concentrates on the science of skin, which must be
understood as a foundation before products affecting the skin can be
appreciated or formulated. Our knowledge of the skin and its function
expands every year, therefore it is imperative that one continues to study
SKIN-CARE PRODUCTS 105
current literature, in order to remain informed. An excellent example of the
progress of the science is the evolution of the knowledge that the outermost
layer of skin, the stratum corneum is 'alive'. It had previously been accepted
that the stratum corneum was a collection of dead cells, with no ongoing
activity beyond barrier function. It is now known that many functions do
take place and may originate in this layer.
In cosmetic chemistry and the business of skin care, we are primarily
concerned with the outermost layers of skin (epidermis) and, in particular,
those areas that are visible, such as face, hands and legs. To understand the
overall anatomy and physiology of the skin, the cross-section shown in
Figure 3.1 should be referred to throughout the following sections.
We are all familiar with our own skin. Closer examination reveals that it
is varied in appearance, structure and function in different areas of the body.
The skin is generally hairy, except for the palms and soles of the feet. Hair
follicles vary in density and function, for example large terminal hair follicles
on men's scalps and beards, to small vellus hair follicles on womens' faces
and are all associated with sebaceous glands.
Figure 3.1 Cross-section of the skin showing epidermis (I); dermis (II); hypodermis (III); stratum
corneum (1); stratum granulosum (2a); stratum spinosum (2b); stratum basale (2c); hair shaft
(8); sebaceous gland (13); eccrine sweat gland (7); and hair bulb (II).
3.2.1 Epidermis
The epidermis consists of several layers and varies in surface topography
and thickness. The epidermis on the soles of the feet and palms of the hands
is thickened; on the scalp and face it is less thick, while on the trunk and the
interior surface of the limbs it is thin.
3.2.1.1 Stratum corneum The outermost layer of the epidermis is the

stratum corneum. This is the visible layer, and the one on which cosmetic
chemists focus most attention. It consists of about 15 to 20 layers of flattened
cells (keratinocytes), which become disassociated and ready for shedding or
desquamation as they migrate to the surface. These cells are distinguished
by not having nuclei or normal cell contents, and were thought to be dead,
but they do have function and organization, and they can be controlled and
managed.
3.2.1.2 Stratum granulosum The next layer within the epidermis is the
stratum granulosum or granular layer. As cells progress to the surface, they
form the characteristic granules of this layer.
3.2.1.3 Stratum spinosum Beneath the stratum granulosum is the stratum

spinosum or spiny layer. This layer of cells is distinguished by a spiny
appearance and the presence of desmosomes. This is the area where the
intercellular lipid is formed. This lipid material is extruded between the cells
of the stratum corneum as they migrate to the surface. The cells are looked
upon as bricks, and the epidermal lipids as the mortar which helps hold the
cells together. The lipids are similar to sebum, except for a lack of wax esters
and squalene, and the presence of ceramides.
3.2.1.4 Stratum basale This is the innermost layer of the epidermis and is
also known as the germinative layer. It is in contact with the dermis. It is
in this layer that epidermal cells originate through the formation of keratino-
cytes, which differentiate as they migrate to the surface. This layer also
produces Langerhans cells, which playa role in the immune system and the
body's defense mechanisms. The entire cycle of formation, differentiation,
migration and exfoliation from stratum bas ale to shedding by the stratum
corneum takes from 40 to 75 days. The stratum corneum cycle is about
one-third that of the total epidermis.
3.2.2 Dermis
The epidermis is dependent on the dermis for its source of nutrition. The
dermis is a connective tissue that provides a support system for the epidermis.
All of the skin's blood, nerves, lymph and external structures, such as hair
follicles with sebaceous glands, and eccrine and apocrine sweat glands, are
based in the dermis.
3.2.2.1 Fibroblasts, collagen and elastin The dermis has a fibrous com-
ponent of various identifiable materials. The primary fibrous material is
collagen, with a lesser content of elastin and smaller proportions of other
fibrous structures. These fiber bundles and structures form an interwoven
network that lends support, flexibility and suppleness to the skin. The source
of these fibrous materials, the fibroblast, is the most numerous type of cell
in the dermis.
3.2.2.2 Mast cells Mast cells are the second most numerous cells in the
dermis. They are granular in nature and are most numerous near the
capillaries. Mast cells participate in the release of enzymes and materials
to control function or respond to injury.
3.2.2.3 Blood supply The blood supply for the dermis is abundant and
consists of a complex of arterioles and capillaries that are drained by the
venous system. The blood supply does not extend into the epidermis. The
purpose of this complex network is not only for cellular nourishment, but
also for temperature control, as demonstrated by flushing (dilation) and goose
bumps (constriction) at opposite extremes of the body's temperature control.
3.2.2.4 Hair follicles and sebaceous glands The combination of hairs, and
their follicles and attendant sebaceous glands is known as the pilosebaceous
system. The hair follicle consists of epidermal tissue that extends into the
dermis for its biological needs. There it obtains a source of nourishment
from an abundant supply of blood, attaches to nerves and in the case of
large terminal hairs, has an attachment to the arrectores pilorum muscle.
This muscle can raise hairs in response to cold, or emotional signals.
In general, a sebaceous gland is associated with a hair follicle. For the
purposes of this review, the activity of the sebaceous gland, and not the hair,
will be focused on. The majority of sebaceous glands occur on the head and
upper torso of the body, and are only absent from the palms and soles of
the feet. Most sebaceous glands associated with hair follicles open inside
the pilosebaceous canal. On the face, some large sebaceous glands either
associated with fine velus hairs, or without hairs, can open directly on to
the surface of the skin. The sebaceous glands form and secrete sebum, a
unique blend oflipid materials not found anywhere else in the body. The size,
maturity and amount of secretion is triggered by hormonal activity, which
peaks in the teenage years [3]. Sebum is synthesized within the sebaceous
gland and consists of triglycerides, fatty acids, wax esters, squalene, and
cholesterol esters. The sebaceous glands, when active, produce a continuous
flow of secretion without regard to the condition of the skin and hair, or the
level of previously secreted sebum on the surface [4].
The sebaceous glands are a site for the development of acne. Even although
the glands are controlled, and enlarge and develop by hormonal activity
within the body, acne is dependent on many other factors beyond the
development and activity of the glands [5]. This will be discussed later
(section 3.9).
3.2.2.5 Sweat glands Two types of sweat glands are present in the human
[6]. The most prevalent (more than two million) are the eccrine sweat glands,
which have a primary function of controlling body temperature. The eccrine
glands are also responsive to other triggers such as stress and sunlight. They
extend from the epidermis into the dermis and, in the dermis, are surrounded
by blood vessels. The sweat secreted by the eccrine system is relatively low
in solids, consisting primarily of sodium chloride.
The apocrine glands are found primarily under the arms and associated
with the sex organs. They are, like the sebaceous glands, primarily associated
with hair follicles, usually opening into the pilosebaceous canal. These glands
are much larger than eccrine glands but, like eccrine glands, originate in the
dermis. The sweat produced, much less in quantity than that produced by
eccrine glands, is higher in solids and of a more complex nature. It is viscous
and milky, and contains high levels of protein, along with cholesterol, steroids
and other lipids. It does not have a pronounced odor on secretion, but
develops a distinctive odor due to enzymatic activity on the skin [7]. The
purpose of aprocrine glands is unknown, but has been speculated to be
sex-related, or a means of identification or communication through odor.
This is the function of similar glands in other mammals.
3.2.3 Skin color

The color of the skin and hair is primarily due to the existence of pigment
bodies known as melanin. Melanin is produced by the melanocyte cells
present in the stratum basale. These melanocytes are present in this basal
layer in great abundance and the number does not differ greatly in people
with more or less melanin pigment or color in their skin. Melanin may be
produced in either a yellow/red or black/brown color, and the color of the
skin is determined by the amount and type of melanin produced. Melanin
production is increased by exposure to the sun and plays a role in protecting
the skin from sunlight.
3.3 Test methods

In addition to a basic understanding of the anatomy and function of the
skin, a good foundation and understanding of various tests available for
the function of the skin, as well as tests for product performance, is essential.
The cosmetic chemist has been aided by many new test methods to help
determine performance of skin-care products. These methods vary from
in vivo observational or instrumental test methods to a wide variety of in vitro
test methods.
3.3.1 Efficacy testing

The majority of skin-care products are sold to improve the appearance
and feel of the skin, and are broadly classified as moisturizers. The condition
and appearance of the skin is a function of its softness and flexibility, which
is adversely affected by loss of water [8]. Tests for moisture content and
moisture transmission, as well as the viscoelastic response, ultrasound
techniques, and electrical properties of skin have been the subject of much
study, with the development of increasingly sophisticated instrumentation
to show the condition of the skin and its water content. Most of these new
methods have evolved to help evaluate the potential performance of products,
and are very useful in screening formulations, levels of ingredients and other
stepwise formula variables. However, experience has shown that none of the
available test methods totally replace in vivo application, professional
observation and sophisticated consumer research utilizing both professional,
and self- or consumer-evaluation of performance.
3.3.1.1 In vivo observational tests for moisturizers One of the primary

and most valuable in vivo tests used, especially to test hand and body
lotions, is the regression test method developed by Kligman [9]. This test
is run in a location where the ambient relative humidity is conducive to
development of dry skin. Panelists are 'dried down' by washing with a
non-fatted bar soap for one week, without use of a moisturizer on the test site,
which is either hands or lower lateral legs. The hands or legs are then observed
and graded. The test protocol calls for use of product by some panelists,
with others acting as non-treatment controls. At various times, during a
two-week period, the condition of the skin is evaluated for dryness, flaking
and redness. Treatment is then withheld for one week, and the rate of return
to a dry condition is observed. This testing yields a good evaluation of the
treatment potential of moisturizer products and their duration under severe
conditions. The method has recently been improved as reported by Boisits
et al. [10].
The condition of the face and its response to moisturizer products have
also been evaluated by a variety of methods. A widely used method is the
superficial facial line test, developed by Packman and Gans [11,12]. This
test has been developed for use by trained judges and also by untrained
panelists. The standard method utilizes scoring, by trained judges, of
superficial facial lines for depth ofline in each offour areas in a half-face study.
The other half of the face acts as a non-treatment control. The study is four
days long, with no treatment on the first day and treatment twice a day on
days 2, 3 and 4. The authors also discuss the use of self-evaluation by twelve
untrained evaluators, who evaluate superficial facial lines in a similar test
method.
3.3.1.2 Cell turnover testing A very useful test to determine cell turnover
rate utilizes the dansyl chloride test [13], in which dansyl chloride, which
fluoresces under a long-wave UV or Woods lamp, is applied to the skin.
This material penetrates the stratum corneum to a uniform depth. The cell
turnover rate, or transit time, is determined by disappearance of the stain
compared to a non-treatment site.
3.3.1.3 In vivo instrumental tests An in vivo instrumental test that is

proving to be of great value is profilometry, which is especially useful in the
assessment of the changes to the skin's surface caused by the anti-ageing effect
of retinoid therapy on sun damaged skin [14]. Two primary methods are
used in profilometry. One method employs replicas and the other uses
photographs. Fully hydrated skin has altered surface characteristics, as
measured by both lower peaks and greater distance between peaks. This is
also the case with skin that has fewer lines and wrinkles due to effects other
than hydration. In evaluation with a replica, an instrument with a stylus
produces a tracing of the topography of the skin, based on a replica produced
by dental impression material. With two-dimensional photographs, compu-
terized image analysis techniques are used to review the image [15].
The gas-bearing electrodynamometer (GBE), has been widely used to
evaluate the viscoelastic properties of the stratum corneum, both in vivo and
in vitro [16,17]. More recently computer handling of data generated by this
device has improved its utility [18]. The Twistometer® device measures
resistance to torsion of the skin, as applied by a rotating disc inside an
external ring, which acts as a stator. This device is used to evaluate the skin's
softness and suppleness [19]. There has been a long history of the
measurement of not only the water content of skin, but also the flow of
moisture from the skin, which is known as the moisture vapor transmission
rate (MVTR) or the moisture/water loss or trans epidermal moisture loss
(TEML). MVTR is a technique that has shown continual refinement. Early
papers by Berube and co-workers outlined theory and practice [20-22].
Progress has continued to the more recent development of a well-accepted
instrument, the Servo-Med® evaporimeter [23]. Most of the work on the
direct measurement of water content in skin has utilized an infrared (IR)
spectrophotometer. An excellent review is given by Potts [24].
3.3.1.4 In vitro testing for moisturizers Many in vitro tests are cited in the
literature. An excellent overall review covering both in vivo and in vitro
techniques has been written by Salter [25]. A technique for conducting the
in vitro moisture vapor transmission rate was usefully outlined by Reiger
and Deem [26]. Measurement of occlusivity by these techniques is useful
and, in general, quite reproducible. The tests consist of the flow of moisture
through a barrier, which is often a synthetic film with a transmission rate
similar to that of skin. This technique (MVTR) combined with a water-
holding technique to measure hydration, or the ability of the formula or test
material to maintain humectancy, is very useful [27,28] in evaluating or
predicting potential in vivo results.
Test methods other than MVTR and water-holding capacity have been
outlined by Quattrone and Laden [29]. They include scanning colorimetric
techniques, scanning electron microscopy (SEM) and biomechanical
properties of skin under various in vitro conditions. In vitro test methods
can be instructive when their correlation to in vivo performance has been
established. In the author's experience, a battery of tests and an excellent
history of correlation are necessary for the tests to be of predictive clinical
value. The problem is that, when in vitro tests are used with excised skin or
a synthetic.membrane, unlike the human skin, there is a lack ofthe biological
underpinnings of the epidermis, which is anything but an inert, static or dead
layer.
3.3.1.5 In vivo test for sebum An in vivo device for measuring the oiliness
of the skin has been developed [30]. This device (Sebutape) is a film that
visualizes and traps sebum. The tape can then be analyzed, and total relative
sebum amount computed using image analysis. If quantification is not the
only requirement, the sebum can be solvent-extracted, gravimetrically
analyzed and broken down into component parts. This can be a very useful
technique for assessing the instant removal of sebum by cleansers, or the
effect on sebum production of various treatments.
3.3.1.6 In vivo test for cleanser mildness A wide variety of cleansers are
available on the market and will be covered within this chapter. Tests for
cleansers have focused primarily on testing soap or detergent formulations
for mildness. In the past, mildness has been evaluated by the Soap Chamber
Test [31]. In this test, dilute solutions of soaps or test solutions are maintained
in a cup held against the skin of human volunteers. The skin is then evaluated
for redness, scaling, and fissuring, often against high irritancy (non-fatted
soap bar) and low irritancy (fatted sodium cocoisethionate bar) controls. A
more recent modification [32] of this method calls for a shorter test, and
measures the increase in MVTR by a Servo-Med® evaporimeter. This has
shown close correlation with the longer duration visual assessment technique.
The authors of the Soap Chamber Test cautioned as to the limitations of
the test and recommended, in addition to this method, the use of exaggerated
washing tests, commonly known as forearm wash tests [33]. These methods
differ from the Soap Chamber Test in that the Forearm Test adjusts frequency
for humidity, while the Flex Test [34] is reported to be unaffected by humidity.
For evaluation of facial cleansers of all types for mildness and drying
potential, the method outlined by Frosch [35] utilizes half-face testing with
realistic use conditions. In order to obtain suitable dryness scores, this test
is best run during periods oflow relative humidity. Cleanser tests for efficacy,
evaluating soil and make-up removal, as well as esthetic properties and
after-cleansing skin-feel, must also be done to obtain a complete picture.
A combination of all these test methods, together with adequate clinical and
consumer trial and observation, should enable one to have a great insight
not only into the performance of products but, more importantly, as to how
and why products work, and how variations in formula affect performance.
This is necessary for the enlightened formulator.
3.4 Formulation
Throughout the remainder of this chapter, formulas will be presented as

examples of particular formulation categories. These will be prototypical
examples, taken from experience or from suppliers. They are only intended
to give the formulator a general idea of typical formulas and constituents by
category, and are neither tested for performance or stability, nor ready for the
market. This would require considerable experimental work and testing. In
addition, many new raw materials with functional and emotive benefits are
available from raw material suppliers and should be reviewed on an ongoing
basis during development.
Formulation is an art and a science, and requires close attention to detail
and trial and error before proficiency becomes routine. The formulator must,
first of all, make a product that has characteristics required by the ultimate
consumer of the product. These requirements will vary depending on the
specific usage, demographics of the consumer, expectations, claims, class of
trade and packaging. The formula must be fit for use by the consumer at
any point during its expected shelf-life. During formulation, this requires
adequate stability trials and examination for microbiological integrity. It must
also be possible to make the product using reasonable manufacturing
equipment on a scale that is appropriate for anticipated demand. Further
areas that are becoming increasingly important are safety under all conditions
of use and potential misuse, and regulatory and environmental acceptability.
These aspects of formulation will be discussed in the following sections.
3.4.1 Formula information

Much formula information, from a variety of sources, is available to the
cosmetic chemist. Excellent background information and general formulation
information may be obtained from the several reference books kept in most
industrial libraries or large public libraries. The nature of these texts will
generally give excellent historical data, but, the most up-to-date formulation
data can be found from other sources. The first of these are the many
periodicals that are published for the technologist in the cosmetic industry.
These periodicals often have formulation articles and review articles cover-
ing a specific category, and also provide another valuable resource, i.e.
identification of, and advertising from raw material suppliers. Raw material
suppliers frequently publish information on starting formulas and give specific
help with formulating. They are a rich source of ideas and guidance and
some will even provide formulation assistance in their own laboratories. One
must keep in mind, however, that the goal of the supplier is to sell the raw
material.
An excellent starting point for the formulator is to review listed
ingredients on the labels of finished formulas of market leaders' target
products sold where ingredient disclosure is required, such as in the US where
all cosmetic products must list all ingredients in descending order of content.
It is helpful to review these ingredient lists, perhaps assay for a material or
two, and speculate on the formula based on other sources of starting formulas.
An assay for water, total lipid material and, if incorporated, humectant, will
give much information about a formula that has already proven to be
acceptable to consumers. The ingredient list in the US also uses accepted
nomenclature from the US trade association, the Cosmetic Toiletry and
Fragrance Association (CTF A) in its Cosmetic Ingredient Dictionary [36].
This is an excellent reference, as it lists not only the generic CTF A name,
but provides technical information on the raw material, and lists suppliers
of it. Another good source of information is to join and participate in local
cosmetic chemists' organizations and attend their meetings. Seminars are
held frequently and are attended by suppliers to the industry.
3.4.2 Consumer testing

Consumer testing and input is a must for the formulator. This should take
place before and after product development. Once a prototype formulation
has been developed, determined safe for use by consumers, and adequately
preserved, it should undergo initial testing for consumer acceptance. Most
commercial organizations have standards for consumer testing, which are
usually organized by the marketing department. It is, however, very helpful
to the formulator to seek consumer input at all stages during development
of a product, for instance to develop an enlightened view of consumer
requirements by talking to target consumers about their needs before
development is initiated. This can be done informally or formally, either
one-to-one, or with groups of consumers. Another useful technique is to give
representative consumer users and non-users of the leading product in a

category, an unidentified sample of the market leader to use for a week.
Following this, the way in which the consumers used the product, the results
of product use, and the likes and dislikes can be discussed on an open-ended
basis. Attribute comments and areas of dissatisfaction with the target product
should be noted. The information can then be used as a base line for later
examination of a developed prototype. Another useful technique, known as
a sequential monadic, is, at the next stage of development, to have target
consumers use both the prototype formula and the market leader or
competitive benchmark product. Half the panel first uses the prototype for a
period of time, and then uses the competitive benchmark product or
market leader; the rest of the panel uses the products in reverse order.
With this technique, a good comparison of the prototype's performance
versus the benchmark product on an attribute-by-attribute basis is obtained.
At this stage, testing should be an on unidentified basis, since the requirement
is for performance and attribute data as a guide to formulation.
In larger concerns, testing of finished products on an identified basis with
advertising or concept, is usually handled by the marketing or market
research department. It is possible, however, for the cosmetic chemist or
formulator to have this work done for them by independent market
research firms, or by advertising agencies.
3.4.3 Stability testing
Stability testing is done to ensure that a developed product will be fit for
use during its expected life. Stability testing should be done early in the
development cycle to remedy any problems before final testing. A well-run
stability trial can provide much information about a product in a relatively
short period of time. Prototype products in packaging, representing the
ultimate trade package material, can be placed at ambient, and elevated (e.g.
37°C and 45°C) temperatures, refrigerated and cycled through freeze/thaw
cycles, and placed in high humidity chambers. During these trials, testing
should focus on attributes most important to the product's performance, or
on the integrity of any active ingredients. In addition, there should be physical
testing, for example pH and viscosity, chemical content of active ingredients,
water content, etc. The formulator must not overlook attributes relating to
consumer perception, such as fragrance, color, rub-in characteristics and
appearance. Two or three months of successful elevated temperature testing
and three or four freeze/thaw cycles will usually indicate that products will
have an adequate shelf-life. It is important, however, to continue testing for
longer periods at ambient temperature, to obtain an understanding of the
product's ultimate shelf-life. Further testing whenever changes are made to
the supply of raw materials or to the formulation is essential.
3.4.4 Microbiological testing
During the development phase, close attention should be paid to the micro-
biological integrity of the formulation. Professional advice should be sought
from a well-trained industrial microbiologist. If this is not immediately
available, input and guidance on preservatives from the suppliers' staff and
consultants should be sought. Suppliers will often have more than one
preservative and can make recommendations about particular types of
formulation. Another method of finding appropriate preservatives is to review
ingredient labeling on similar types of products that are available from
reputable manufacturers and which have similar constituents, pH and
package types. This, coupled with a microbiologist's or a preservative
vendor's input can often give several trial systems. Finished products are
usually tested using a challenge technique. If this essential testing is not
available in-house, a qualified contract lab can assist. The test involves adding
large numbers of a variety of organisms to the product and checking the
ability of the product to reduce them to an acceptable level. To ensure that
the product retains its ability to remain preserved, adequacy of preservation
should also be checked during stability testing.
3.4.5 Manufacturing trials
A product cannot be a commercial success unless it can be made with

large-scale equipment, therefore as soon as a prototype develops beyond its
earliest stages, and at all subsequent stages of development, manufacturing
should be considered. If an engineering group is available, it should be
consulted, and should participate in a laboratory batch of the new product
on a bench scale. This, if possible, should compare the compounding of the
product, heating and cooling cycles, phase additions, etc., with a similar type
of product that is already being manufactured. Any significant deviations from
norm should be noted and investigated for possible change or for special
attention during scale-up. Scale-up can represent large changes in batching
times, time at temperature, etc. It is advisable to scale-up in increments,
preferably not greater than lO x at any stage. For instance, going from a
1 kg lab batch to a lOkg lab batch, then to a lOOkg pilot batch and lOOOkg
manufacturing batch would be a logical sequence. Any significant problem
at each stage should be investigated and, at the very least, abbreviated
stabilities should be run with product from each stage.
When final manufacturing is initiated, the development chemist or engineer
should stay with the process until several batches have been made without
problem. It is helpful, during the life of the product, to return to manufacturing
and continuously improve the process. Time should be spent with veteran
compounders, as they often have great insight into how a process can
be improved. Product from first production trials should also be put through a
complete stability test, comparing results to those obtained during develop-

ment, and addressing any problems that may occur.
3.4.6 Safety testing

The product must be safe under all conditions of use and potential misuse.
Safe products arise from a combination of careful formulating, good
background data and adequate testing. A review of materials used in products
for similar purposes is an excellent place to start. Most successful commercial
products have been adequately tested and have a history of safe usage. Safety
data for each raw material should be available from its manufacturer and
should be reviewed. In the US, the CTF A has a Cosmetic Ingredient Review,
which evaluates materials and also lists safety data for materials that have
been reviewed. After a thorough background check, finished products should
be tested through a competent third party. Many testing companies not only
do safety testing, but also recommend appropriate testing that should be done
for the class of product that has been developed. It is often useful to solicit
testing protocols from two testing companies, asking them to explain and
justify each test they recommend. It must be remembered, however, that they
can only make enlightened recommendations based on input. Divulging as
much information as possible at this stage, will give better, more appropriate
testing input, and insight into possible untoward reaction.
After adequate clinical testing has been completed, and during all stages
of consumer trial, it is important to check for unexpected reactions or patterns
of misuse, while carefully extending exposure. Careful attention should be
paid to reported reactions from usage or misusage situations. After launch,
there should be a mechanism to check on reported reactions to determine
if, on a broad exposure, these levels are higher than one would expect for the
category. Category adverse response reporting data is available from the US
Food and Drug Administration (FDA), and often from local trade
associa ti ons.
3.4.7 Regulatory and environmental requirements

Regulatory requirements vary greatly from country to country, and can be
ascertained by direct contact with the local regulatory authority. Excellent
advice can frequently be obtained from local trade associations, who have
insight into not only what is required by law or regulation, but also what is
acceptable and expected. Membership of trade associations and participation
in their activities is invaluable.
Environmental restrictions or concerns are often more elusive, or more
difficult to determine. Trade associations, trade publications and local groups
of cosmetic chemists can be of great help. Many companies also seek advice
from consultants who are experts in this area, or, in some cases, have direct
meetings and constructive dialogue with leading environmental groups.
The person responsible for developing a product or formula should accept
total responsibility for the product, and care and diligence should be exercised
throughout every aspect of product development.
3.5 Skin cleansers
Skin cleansers constitute an important segment of the skin-care market.

Cosmetic chemists are usually involved in the formulation of facial cleansers
in forms other than bars. This, however, overlooks a large portion not only
of the overall market, but also of consumers' usage patterns. Most consumers
use bar products, either based on soap or synthetic detergent (syndet), for
skin cleansing. All other cleanser products represent other types of usage
and vary greatly from market to market depending on patterns of make-up
usage, cleansing habits, etc.
In order to properly classify cleansers, it may be helpful to put them on
a grid, roughly related to their physical nature, chemistry and functionality,
and ranging from products that are anhydrous oils, at one end of the
spectrum, to soap and water at the other (Table 3.1). Various product types
have different functions and, while they have advantages for a specific
condition or soil, none is universal. Most consumers use more than one type
of cleanser, so an understanding not only of chemistry and formulation, but
also of consumer usage patterns for their needs in a specific market or market
segment, is key.
When classifying cleansers, the various soils on the skin must be considered.
Soils come from a variety of sources, but can be classified broadly as
oil-soluble, water-soluble and insoluble. Sources for oil-soluble soils can be
sebum, residue from moisturizers, or waterproof make-ups. Water-soluble
materials may also be residue from make-up or moisturizers, soluble skin
Table 3.1 Classification of skin cleansers according to physical nature, chemistry and
functionality
More gentle to skin More harsh to skin
Emollient and moisturizing Foaming and astringent
Oleophilic Hydrophilic
Mineral oil W/O Non-foaming Fatted Fatted Alcohol/ Bar soap

Vegetable oil cream O/W lotion bars bar water Liquid
Petroleum jelly or lotion or cream Mild soap detergent
foaming solution
pastes
Lotion
soils, and soluble grime. Insoluble materials are represented by dead

cellular matter, make-up pigments or, in hard-water areas, precipitated
metallic soaps.
3.5.1 Anhydrous oily cleansers

The first category of cleansers is the most oleophilic group. Mineral oil,
petroleum jelly, vegetable oils and esters are useful as non-drying skin
cleansers for removal of waterproof make-up and oil-soluble soils. The
disadvantage of these cleansers is that they are not readily rinsible and often
have poor cosmetic and esthetic characteristics. More modern versions
incorporate moderate to high levels of esters or gentle oil-soluble surfactant
materials to make the products less greasy, more pleasant and, in some
cases, rinsible. In addition, some formulations are thickened to form gels,
which are easier to spread on to the skin and can be tissued off.
Typical formulation of an anhydrous oily cleanser
Ingredient W t%
Capric/caprylic triglyceride 12.0
PEG-400 dilaurate 6.0
Mineral oil, 70 viscosity 82.0
Procedure: Blend all ingredients at room temperature.
3.5.2 Water-in-oil emulsions: cold creams

The next category of products are water-in-oil (W/O) emulsion cream and
lotion formulas, typified by cold cream [37]. Cold creams are referred to as
W/0 emulsions but, during processing and usage, are more complex water-
in-oil-in-water (W /O/W) emulsions, or mixed emulsions. The partial or mixed
external oil phase of these mineral oil/beeswax/borax systems dissolve
oil-soluble materials and, because of the oily external phase and the beeswax/
borax soap at the interface, they are able to solubilize, wet out and transport
soil and waterproof make-up. Cold creams are generally not rinsible, are
considered greasy and inelegant, and are tissued off the skin. They leave
behind a film that has proven moisturizing characteristics. Classical cold
cream formulas set the standard for mildness to skin and eyes.In recent years,
some rinsible cold creams have emerged. These are cold cream and similar
bases to which non-ionic emulsifiers have been added with an increased water
phase. These rinsible systems then become oil-in-water (O/W) emulsions.
They are not as satisfactory for waterproof make-up removal, but are rinsible
and more cosmetically elegant.
Typicalformulation of cold cream USP XXI
Ingredient Wt%
Cetyl esters wax 12.5
White wax 12.0
Mineral oil 56.0
Sodium borate 0.5
Purified water 19.0
Procedure: Reduce the cetyl esters wax and the white wax to small pieces, melt them on
a steam bath, add the mineral oil, and continue heating until the temperature of the
mixture reaches 70°C. Dissolve the sodium borate in the purified water, warmed to
70°C, and gradually add the warm solution to the melted mixture, stirring rapidly and
continuously until it has. congealed. Pour into jars at 50°C and cool.
3.5.3 Oil-in-water emulsions: cleansing milks

Non-foaming OjW emulsions with greater than 50% water phase typify the
next category of cleansers. These products are typically referred to as cosmetic
milks. The primary cleanser and emulsifier is often a TEA * I fatty acid soap,
or a detergent such as sodium cocoyl isethionate supplemented by anionic
or non-ionic emulsifiers. Cosmetic milks are skin-friendly and have many
similarities with O/W moisturizing lotions. However, they differ from moistur-
izing lotions in that they generally have less water in the water phase, excess
TEA fatty acid, and higher levels of a secondary em ulsifier such as self-emulsi-
fying glycerol monosterate. Significant levels of mineral oils or esters may
also be incorporated to ensure adequate levels of solubilization of oily
materials without reducing rinsibility.
Typical formulation of an 0 /W cleansing lotion

Part Ingredient Wt%
A Deionized water 56.8
Xanthan gum 0.4
Sodium cocoyl isethionate 25.0
Preservative, EDTA * 0.4
B Cocamide MEA * 3.0
POE*-20 sorbitan monostearate 2.0
Ceteareth -20 3.0
Cetyl alcohol 2.0
Ethylene glycol monostearate 2.0
Isopropyl palmitate 2.0
Poloxamer 338 2.0
PEG*-7 glyceryl cocoate 1.0
C Fragrance 0.4
* TEA, triethanolamine; EDTA, ethylene diamine tetra-acetate; MEA, mono ethanolamide;
PEG, polyethylene glycol; POE, polyoxyethylene.
Procedure: Dissolve xanthan gum in water; heat to 65°C. Add sodium cocoyl isethio-
nate, preservative, and EDT A. Premix part B and heat to 65°C. Add B to A with
good mixing; then cool to 45°C. Add fragrance.
3.5.4 Fatted mild syndet foaming bars and cleansers

The next category is differentiated because of a foaming characteristic. This
is the category of fatted syndet bars and gentle fatted foaming pastes and
lotions. These products have good wetting properties but, when used in soap
chamber or flex washing studies, are significantly more gentle than fatted
soaps, detergent solutions or non-fatted soaps. They occur as bars (fatted
sodium coco isethionate [38]), as pastes based on fatted built mono-alkyl-
phosphates [39], and as pastes and lotions based on fatted and built sodium
coco isethionate. Recent additions to this range of gentle foaming cleansers
have been lotions based on sarcosanate surfactants, with high levels of
glycerol, protein, and fatty materials to ensure a mild effect. Due to their
gentle nature on the skin, mild bars, foaming pastes, and lotions are becoming
more important on a worldwide basis.
Typical formulation of a mild syndet bar

Ingredient Wt%
Sodium cocoyl isethionate 50.0
Stearic acid 34.0
Soap chip (80/20 tallow/coco) 10.0
Deionized water 5.0
Fragrance, pigments, etc. 1.0
Procedure: Blend all ingredients in amalgamator. Refine, extrude and stamp bars.
Typical formulation of a mild foaming syndet lotion

Part Ingredient Wt%
Hydroxypropyl methylcellulose 0.5
Triethanolamine 0.1
B Sodium cocoyl isethionate 12.0
Stearic acid 6.0
Preservative, EDT A 0.4
C Mineral oil, 200 viscosity 7.0
Cetyl alcohol 2.0
D Fragrance 0.3
Procedure: Disperse the hydroxypropyl methylcellulose in water. With mixing, add
the triethanolamine to initiate hydration. Begin heating to 65°C. Add the part B in-
gredients. Premix part C; heat to 65°C. Add part C to the batch with good mixing.
Cool to 45°C; add fragrance.
3.5.5 Super fatted bar soaps
Fatted bar soaps have greater cleansing characteristics, with less skin residue
than fatted and built mild detergent pastes and lotions. The formulations
contain varying amounts of fatty acids or other fatty or moisturizing materials
to decrease their aggressive behavior on the skin. This results in a non-taut
skin-feel upon rinsing, and less damage to the skin (see also chapter 9).
Typical formulation of a super fatted bar soap (cold cream)

Ingredient Wt%
Soap chips 65: 35 tallow: coco 97.65
Cold cream fat phase* 0.50
Lanolin 0.50
Antioxidant 0.10
Titanium dioxide 0.25
Fragrance 1.00
*See prior example cold cream USP XXI
Procedure: Blend all ingredients in an amalgamator. Refine, extrude and stamp
bars.
3.5.6 Astringents/toners
Astringents and toners are a class of skin cleansers that have a special use
and very specific formulations. They are hydroalcoholic solutions with an
alcohol content from 20-70%. The products with lower levels of alcohol are
developed for sensitive skins, while those with higher amounts are for oily
skins. Astringents and toners often contain small amounts of emollients or
humectants to decrease their defatting of the skin. They are generally used
by oily-skinned consumers or teenagers as a supplement for cleansing and
acne treatment. They are often the last cleansing step in a ritual to make
the skin very clean in preparation for the use of a moisturizer.
Typical formulation of a hydroalcoholic astringent

Ingredient Wt%
Deionized water 50.90
Ethyl alcohol 40.00
Glycerin 4.00
Sorbitol 70% 2.00
Menthol 0.10
Witch hazel extract 3.00
Fragrance q.s.
Color q.s.
Procedure: Dissolve menthol in alcohol. Add fragrance, water and other ingredients.
Blend at room temperature.
3.5.7 Bar soaps
The final category in Table 3.1 consists of the minimally fatted or non-fatted
bar soaps. These coco/tallow soaps are excellent cleansers, but can, if used
excessively, irritate the skin [40,41]. They enjoy considerable usage among
consumers as part of an everyday cleansing ritual and, on a worldwide basis,
are the most commonly used cleanser product (see also chapter 9).
Typical formulation of a bar soap

Ingredient Wt%
Soap chips 80:20 tallow:coco 97.65
Water 1.0
Antioxidant 0.1
Perfume oil 0.75
Procedure: Blend all ingredients in amalgamator. Refine, extrude and stamp bars.
3.5.8 Particulate scrubs

A specialty category not shown in Table 3.1 is the scrub creams, which contain
particulate materials. These products are often OjW emulsions (if non-foaming)
or gentle pastes (if foaming). They contain particles of polyethylene or other
inert materials such as ground seed-husks. The purpose of these particulate
materials is to remove loose flakes of stratum corneum and to polish the
skin. Interesting research by Loden and Bengtsson [42] indicated that the
effect of scrubbing with a particulate scrub was equal to that of 2.5 to 3 tape
strippings. The use of particulate scrubs can be helpful if there is a need to
remove a layer of stratum corneum. However, excessive use should be
cautioned as, due to their mechanical action, they can be irritating.
Typical formulation of a particulate scrub

Part Ingredient Wt%
A Polyethylene beads 5.0
Octyl decanol 10.0
Ceteareth-12 1.5
Ceteareth-20 1.5
Glyceryl mono oleate 1.0
Propyl p-hydroxybenzoate 0.05
B Deionized water 48.35
Methyl p-hydroxybenzoate 0.1
C Fragrance 8.5
Procedure: Heat A to 70°C. Heat part B to 7SOC. Add part B to part A with agitation
and cool to 40°C. Add part C and mix thoroughly.
The selection of cleansers and their constituents requires extensive testing to

ensure suitability for use. The goal should be to remove soils and make-up
with minimal damage to the skin. An interesting approach to the selection
of surfactant materials and products is outlined by Komp [43], utilizing the
Duhring Chamber Test, as well as the antecubital washing test [33]. As well
as these exaggerated tests, it is very important to follow prototype formulation
with controlled in-use testing for soil and make-up removal, and consumer
evaluation use testing.
3.6 Moisturizers
Moisturizers are products that are usually emulsions, either O/W or W/O.
There are two principal forms of these products: (i) semi-solid emulsions,
known as creams; and (ii) flowable emulsions, known as lotions. Moisturizing
products are differentiated not only by their emulsion type and/or physical
form, but also by their functional use. For the purpose of this discussion,
all-purpose creams, hand and body lotions and creams, facial moisturizing
lotions, and facial 'night' creams, will be considered.
The purpose of moisturizing products is to restore and maintain the skin
in a good-looking, fully moisturized condition. To maintain this condition,
the stratum corneum must be in a fully hydrated condition that allows
flexibility and elasticity. Early work by Middleton and Allen[ 44] and a review
by Idson [45], show the relationship between water content in the skin, as
affected by temperature and humidity. In most products, this moisturization
is accomplished by a combination of hydrating by water followed by the
actions of occlusives and humectants. Emulsion products of either OjW or
W/0 break down when rubbed out on the skin, and add water from their
own composition to the surface layers ofthe stratum corneum. This hydrating
effect by water accounts for the instant appearance benefits, including
reduction of visible dry flakes and chapping (see Blank [8,46]). Less-
immediate effects occur through occlusivity and humectancy.
Occlusivity occurs when the transepidermal water loss is slowed through
reduction of the moisture vapor transmission rate. Many fatty materials
reduce the MVTR. Typical of these materials would be petroleum jelly,
mineral oil, vegetable oil, silicone oils, waxes, fatty acids, alcohols, and esters
of mineral, animal or plant origin, as well as many synthetic oily materials
that are available to the cosmetic chemist.
Humectancy is a separate but related phenomenon, in which materials that
have an affinity for water: (i) help bind water to the skin; (ii) resist evaporation
from the skin; or (iii) under certain circumstances, attract water to the skin.
Typical of these materials are glycerin, sorbitol, sodium lactate and sodium
pyrollidone carboxylate (the skin's naturally occurring humectant [47J). Such
humectants have been shown to be valuable not only in hydrating the stratum
corneum, but also in improving the elastic modulus and stress relaxation
modulus, thus altering the viscoelastic behavior of the stratum corneum [48].
Extensive experimentation with glycerin [49J has shown that it moisturizes
dry skin in a dose-related relationship dependent on the concentration
of glycerin. It was postulated that the water-glycerin mixtures on the skin
also assist in plasticizing the stratum corneum in a less than transient
manner. Middleton [50J found that lactic acid was absorbed by the stratum
corneum and that increased extensibility was retained by the stratum
corneum.
3.6.1 All-purpose creams

All-purpose creams are typified by a W/0 emulsion or by high oil content
OjW emulsions. These products are for general face and body usage and
generally have a heavy consistency and significant drag on rub-out. In
addition, a small amount of product is able to cover a large area. Many
all-purpose creams contain from 30-70% oil phase, resist wash-off, and are
excellent protective as well as treatment products. They represent a very
significant percentage of the European mass moisturizer market, and are often
sold in flat packs (tins) or tubes. Performance characteristics and testing
should focus on tests to maximize a reduction in the MVTR, resistance to
wash-off and a prolonged improvement to the skin, as demonstrated by
regression analysis. Lighter weight, more modern products are, however,
becoming popular.
Typical formulation of a heavy all-purpose cream

Part Ingredient Wt%
A Stearic acid 3.00
Lanolin 7.00
Petrolatum, USP 10.00
Cetyl alcohol 2.00
Microcrystalline wax 2.00
B Magnesium aluminum silicate, 5% dispersion 5.00
Triethanolamine 1.78
Water 29.22
C Fragrance and preservatives q.s.
Procedure: Heat parts A and B to 70°e. Add part B to part A, mixing continuously.
Mix and cool to 35-40°C and add part e. Continue mixing until dispersion is
complete. Adjust evaporation losses with water.
Typical formulation of a modern all-purpose cream
Part Ingredient Wt%

A Stearic acid 4.0
Glyceryl monostearate 1.0
Glyceryl monohydroxystearate 2.0
Cetearyl alcohol 3.0
Cetyl octanoate 10.0
Glycerin 3.0
Carbomer 941 (2% dispersion) 10.0
Triethanolamine 1.5
C Fragrance q.S.
Preservatives q.s.
Procedure: Heat parts A and B separately to 70°C. Add Part A to part B with good
agitation. Mix to 35°C and add part C. Continue mixing until dispersion is complete.
3.6.2 Hand and body lotions

Hand and body lotions are generally O/W emulsions, with typical lotion
products containing 10-15% oil phase, 5-10% humectant, and 75-85% water
phase. They are characterized by easy flow and pumpability, fast rub-in, and
a lack of stickiness after rub-in. Most of these products are sold in bottles
with or without pumps, or in tubes.Their primary performance characteristics
are their ability to instantly hydrate skin and to relieve dry skin symptoms.
In addition, they should have excellent profiles in MVTR reduction and
prolonged improvement to the skin as shown by regression analysis.
Typical formulation of a hand and body lotion

Part Ingredient Wt%
A Stearic acid 2.5
Cetyl alcohol 1.0
Petrolatum USP 1.0
PEG-40 stearate 0.25
B Deionized water no
Glycerin 5.0
Triethanolamine, 99% 1.0
C Preservatives q.s.
Fragrance q.S.
Procedure: Heat parts A and B separately to 70°C. Add part A to part B with good
3.6.3 Hand and body creams

Most modern hand and body creams are OjW emulsions with greater levels of
oil phase and possibly higher humectant levels than lotion products. They
generally contain 15-40% oil phase and from 5-15% humectant phase. These
products are easy to apply, have a reasonably fast rub-in, good esthetics,
and often resist wash-off. They are typically sold in jars or tubes. Their
performance characteristics are similar to hand and body lotions, often with
the added benefit of more resistance to wash-off.
Typical formuldtion of a hand and body cream

Part Ingredient Wt%
A Steareth-21 2.5
Steareth-2 0.75
Cetyl palmitate 1.0
Myristyl myristate 1.0
Dimethicone 50 cSt 2.0
Decyl oleate 4.0
Mineral oil 5.0
Glycerin 10.0
Xanthan gum 0.2
Magnesium aluminum silicate 0.6
C Preservatives q.s.
Color q.s.
Fragrance q.S.
agitation. Mix to 3SOC and add part C. Continue mixing until dispersion is complete.
3.6.4 Facial moisturizer lotions

In terms of esthetics, facial moisturizer lotions are very different from hand
and body lotions. They contain occlusive agents and humectants at the lower
concentration levels of hand and body lotion formulations. Great attention
is paid to quick-breaking, instant-absorbing products with no greasy afterfeel.
These effects are obtained by the use of emulsions that break down quickly,
dry to a matte finish, and utilize light emollients such as esters and fatty
alcohols and, where appropriate, additives such as volatile silicones. Perfor-
mance characteristics are good moisturizing capability, the ability to
reduce MVTR rates, and also an immediate and a short-duration effect on
superficial facial lines. Visual performance effects and esthetics are key factors
in successful products.
Typical formulation of a facial moisturizing lotion

Part Ingredient Wt%
A Deionized Water 63.90
Methylparaben 0.20
Sorbitol, 70% solution 2.00
Propylene glycol 3.00
B Glyceryl monostearate 4.00
Mineral oil 3.00
Caprylic/capric triglycerides 4.00
Hydrogenated vegetable oils 1.50
Stearic acid 2.00
Laureth-23 0.80
C Fragrance and preservatives q.s.
Procedure: Mix all of part A except the triethanolamine. After all of part A is dispersed,
add TEA. Heat parts A and B to 70°C. Add part B to part A with good agitation.
Mix to 35°C and add part C. Continue mixing until dispersion is complete.
3.6.5 Facial moisturizer creams: night creams

Facial moisturizer creams are often sold as night creams or heavier duty
moisturizer products than their lotion counterparts. They generally have
higher levels of occlusive and humectant materials than facial moisturizer
lotions, but are formulated (with esthetics as a principal factor) using lighter
emollients, quick-breaking emulsions, and controlled levels of humectant
materials. Additives such as volatile silicones are often added to improve
rub-in, break and a non-greasy afterfeel which, together with a matte finish,
are key esthetic features. Performance characteristics are excellent
moisturizing capabilities and a good effect on superficial facial lines.
Typical formulation of a night cream

Part Ingredient Wt%
A Ceteareth-20 and cetearyl alcohol 3.0
Stearyl alcohol 2.0
Diisopropyl dime rate 5.0
Octyl palmitate 5.0
Petrolatum USP 3.0
Dimethicone 350cSt 1.0

Hydroxypropyl guar gum OJ
Glycerin 7.0
C Preservative and fragrance q.s.
3.7 Anti-ageing products
The emergence of new technology with proven performance to reverse

damage from photoageing necessitates a separate section on anti-ageing
products. Many such products are sold but, prior to discovery by Kligman
[51] of the effect of retinoic acid on photodamage, and patents issued to
Van Scott and Yu [52] on (X-hydroxy acids, these products had primarily
cosmetic benefits; that is, complete hydration of the skin, a return of
suppleness, the reduction of superficial facial lines and, at times, a masking
effect, giving lines a more youthful, albeit transient, improved appearance.
Ageing is well understood and, although much can be done in the
laboratory to affect cellular vitality, or to affect the overall longevity of
laboratory animals, the human species has not materially advanced in its
maximum age as proposed in the original theories of Hayflick and Moorehead
[53]. A more optimistic review by Pugliese [54], both of ageing and of events
within overall cellular mortality, is of interest and suggests that a proper
understanding of the entire ageing process is the key to effecting changes in
it. This review offers many areas of interest to the cosmetic chemist. Ageing
results in subtle and not so subtle changes in the appearance of the skin. It is
probable that many of the effects seen on the skin with ageing are an indirect
result of the decrease in the blood supply to the dermis [55]. The number of
sebaceous ducts and the level of secretion from them also decreases, however,
many of the remaining ducts increase in size [56]. An excellent review of these
changes in physiology and pathophysiology by Gilchrest [57] is worth
reading in order to understand the substrate in question.
Manifestations of ageing that are of primary concern to the cosmetic
chemist are wrinkles. These lines, which become more pronounced with age,
especially on the face, are caused by a shrinking of the superficial muscles,
which have their points of insertion in the dermis. The facial expression
muscles are the first areas to change with age. They also develop the deepest
wrinkles. As they lose superficial mass, thinning of the epidermis and a loss
of collagen and elastin are apparent. These all contribute to the visible process
called ageing. As yet, it has not been possible to affect this frank, deep cellular
ageing. One reason is that there is nothing histological to differentiate the
cellular structure of a wrinkle from that of a non-wrinkled epidermal area.
An excellent review on this entire subject is provided by Wright and Shellow
[58], who studied the histology of deep wrinkles and adjacent non-wrinkle
areas.
Advances are continually being made to show improvements in ageing of
photo damaged skin, due to retinoid and retinoid-like effects, more recently
demonstrated by a-hydroxy acids and related compounds. Several natural
physiological vitamin A or retinoid effects that are known to be ongoing in
the dermis are dermal development, collagen synthesis, hyaluronic acid
synthesis, DNA content and epidermal protein expression. Since these factors
are, in part, controlled by vitamin A and its derivatives in healthy skin, it
has proven worthwhile to seek profound effects such as those demonstrated
by topical treatment of retinoic acid. Achieving a retinoid effect is not possible
by simply adding vitamin A or another retinoid to a cosmetic formula.
Following topical application, the effective drug must be available to the
dermis and epidermis, without untoward side effects. Recent work [59] with
the hairless mouse model has correlated a dose response to increasing levels
of retinyl palmitate in a suitable cosmetic preparation. This response from
topical treatment resulted in an increase in protein and collagen synthesis,
and in DNA content, together with a thickening of the epidermis. Prior work
with a topically applied retinoid has shown accelerated dermal repair to UV
damaged dermis, due to increasing regeneration of connective tissue [60].
Emerging work has shown quantifiable effects on human photodamaged
skin, and significant biochemical changes in the hairless mouse model, due
to topical application of a common cosmetic retinoid. This, coupled with
the ability to increase cell turnover from use of a cosmetic product, the
reduction of superficial facial lines through new and improved materials and
mechanisms, and the 'plumping' of the epidermis by occlusive or humectant
agents can, in theory, be combined to give excellent visual anti-ageing results.
Both Kligman and Van Scott [51, 52] discuss the effect of both retinoids
and a-hydroxy acids on photodamage. That photodamage has a profound
effect on the appearance of ageing of the skin, is now well understood and
discussed under section 3.8.1 of this chapter. Damage that can manifest itself
as ageing, stems from the effect on the elastic fibers that provide smoothness
and suppleness [61, 62]. Evidence that these changes can be reversed was
demonstrated by Kligman et al. [63].
Recently, a-hydroxy acids, primarily lactic and glycolic, have entered the
marketplace in many skin-care preparations. Smith [64] has demonstrated
various effects of these materials and has compared their efficacy.
Derivatives of a-hydroxy acids have also been marketed [65].
A growing problem is whether or not retinoid-like materials are drugs.
In .the US, and increasingly throughout the world, courts and regulatory
bodies are telling us that if a product contains a 'drug', it clearly is a 'drug'.
Even if it does not contain what has been previously classified as a drug,
but alters the structure or function of the human body, it may well still be
regarded as a drug. In the US, products containing retinoic acid are classified
as drugs and are only available on prescription allowed to be used under
the supervision of a physician. At the present time, such products are cleared
for use only in the treatment of acne, but are being mis-prescribed by many
physicians for treatment of photoageing and its associated dermal
damage. They are not without side effects, including significant levels of
irritation in some patients.
The status of products claimed to possess anti-ageing, and other properties
has recently come under scrutiny by the US FDA. The FDA has issued
several regulatory letters to companies, requesting them to stop making drug
claims, i.e. " ... altering the structure or function of the body." Most of these
regulatory letters have been resolved by the companies modifying their claims
following negotiations with the FDA. One company has, however, initiated
suit over this issue, which will no doubt be decided in the courts. A review
of performance claims for skin-care cosmetics, and the basis of US regulations,
was written by McNamara [66]. In this review, the legal basis for the
distinction between drugs and cosmetics, based on both claims and
ingredients, is discussed.
Anti-ageing products have been marketed by the cosmetic industry for
many years. Successful new products were often launched by interesting
claims such as "penetrates 21 cell layers", "speeds up cell turnover" or
"enhances overnight repair at a cellular level". However, although these
products did have performance characteristics, proven by new biophysical
tests that were optimized in the product, they did not truly change the ageing
process. The proven ability of retinoic acid to reverse photodamage has now
altered this situation, and true pharmacological effect from topically applied
products is now a reality. The successful formulator and marketer will have
to keep up with this rapidly evolving and most exciting area of science.
3.8 Sunscreen products
Sunscreen products form an important subclass of skin-care products. In

order to have a good understanding of these products, the chemist must first
understand the physics and pharmacology of solar radiation, and its effect
on the body.
3.8.1 Solar radiation

Skin damage, and the development of products that help prevent it, require
an understanding ofthe ultraviolet spectrum oflight. The ultraviolet spectrum
of concern is between 200 and 400 nanometers (nm) and, in practice between
280 and 400 nm. The ozone layer around the earth absorbs the shorter
wavelengths [67], therefore the important wavelengths are UV-B
(280-320nm) and UV-A (320-400nm). The penetration of the skin by
ultraviolet radiation depends on wavelength. As the wavelength increases
from 200 to 400 nm, the penetration also increases. Consequently, UV -B
penetrates (depending on the thickness of the skin in the area of the body
irradiated) into the upper layers of the dermis, whereas the longer wavelengths
from UV-A penetrate deeply into the dermis. Due to the variable thickness
of the skin on various areas of the body, some areas are more susceptible
to sunburn and photodamage (ageing) than other areas.
The immediate symptom of excessive UV-B exposure is sunburn. This is
caused by a reaction of UV-B radiation with an absorbing material within
cells. This absorbing material has been shown to be DNA, which is then
depressed prior to cellular propagation [68]. The ability to penetrate varies
greatly according to wavelength [69], with small percentages of UV-B
penetrating to the capillary system in the dermis at lower UV-B wavelengths,
compared to roughly 50% at its greatest wavelength (320nm). UV-B,
however, also stimulates the dermis to form melanin by a complex series of
reactions that stimulate the melanocytes to trigger tyrosine in a multi-step
reaction to form melanin. For this reaction to occur, the skin must be
stimulated by a dose of UV-B, close to the dose that causes redness. On
excessive exposure to UV-B (beyond one minimal erythemal dose (MED)),
the skin becomes pink after a delay of two to four hours. Redness occurs,
which, depending on the severity of the burn, will begin to fade from overnight
to within three to four days. In severe cases, the redness may result in
separation of the stratum corneum by edema and 'blistering'. The wavelength
of maximum redness within the UV-B range is near the peak of UV-B or
305nm [70].
UV -A is not directly associated with erythema, and has a redness-
producing potential compared to UV-B of about 1/1000. However, it has
been shown to damage the skin by penetration to connective tissue, and is
also capable of producing tumors. In addition to damage by the deeper
penetration ofUV-A, photosensitizing or allergic response due to a causative
chemical and UV appears to be primarily caused by UV-A [71]. UV-A is
able to produce melanin, but the tan is more unstable than the melanin
created by UV-B exposure. UV-A is used in tanning salons because of its
lack of erythema, and its relatively quick tanning. It is doubtful, however,
whether tans produced by exposure to UV-A will provide resistance to
significant amounts of UV-B [72]. UV-A exposure in tanning salons is not
without its hazards, especially to the deeper underlying structure of the
dermis.
Due to the damaging potential of UV-B, both near term (sunburn) and
long term (skin damage), and the deeper penetration and potentially greater
damage from UV-A, proper protection from UV-A and UV-B must be
exercised. Exposures to both UV-A and UV-B have been implicated in

increased numbers of skin cancers.
The amount of solar radiation varies depending on the season, the latitude,
the time of day, and the altitude. The closer to the equator, the greater the
total radiation from ultraviolet. The same is true for any location during the
summer, when the sun is at its closest point. From 9 a.m. to 3 p.m. represents
the period of greatest exposure, while increasingly higher altitudes add to
exposure levels. In addition, when directly in the sun, there is from 10 to 100
times more UV-A exposure than UV-B exposure. Consequently, both bands
contribute significantly to harmful effects. An additional concern is that the
vast majority of UV emitted by the sun is absorbed by stratospheric ozone.
There is recent evidence that this ozone layer is decreasing, which will allow
more UV-B to penetrate. A decrease in the ozone layer of 10% is estimated
to increase melanoma by 10-20%, basal cell carcinoma by 25-35%, squamous
cell carcinoma by 50-60%, and cataracts by 6-10% [73].
Sensitivity to UV irradiation depends on the amount of melanin, which
absorbs UV, in the skin. Fitzpatrick and Pathak [74] have developed a
classification for skin types, depending on their response to UV irradiation
(Table 3.2). This response is generally due to the level of melanin pigment
in the skin. It is also typical of various racial or ethnic groups. Those groups
who have a long history of sun exposure, e.g. black Africans, tend to be
classification V or VI, while those with little history of sun exposure, e.g.
people of Irish or Celtic heritage, tend to be category I or II. The normal
reaction following exposure to meaningful amounts of UV is for the skin
not only to produce more melanin, but also to thicken [72]. The most serious
effects are photodamage and cancer. Prolonged exposure can lead to
profound changes in the fibrous component of the dermis, with a decrease
in collagen, alteration in keratinocytes and melanocytes and increased deep
wrinkling and development of age spots. Continuous exposure leads to
development on exposed areas of a wrinkled leather-like appearance or 'red
Table 3.2 Skin classification [74]
Skin type Classification Reaction to sun
Sensitive Burns easily

Never tans
II Sensitive Burns easily
Tans minimally
III Normal Burns moderately
Tans gradually
IV Normal Burns minimally
Always tans well
V Insensitive Rarely burns
Tans profusely
VI Insensitive Never burns
Deeply pigmented
neck'. Skin cancers have been shown to be the direct result of over-
exposure to the sun, and the propensity of the individual to erythema and
damage.
Australia, which has a high concentration of northern Europeans with
Type I or Type II skin, and a location close to the equator giving maximized
ultraviolet radiation exposure, has the highest reported incidence of skin
cancer for a developed population. The most prominent form of skin cancer
is basal cell carcinoma. This cancer is typically preceded by a pre-cancerous
lesion, a solar keratosis. This solar keratosis is easily removed by a
dermatologist. The most serious form of skin cancer is a malignant melanoma,
which usually arises from a mole and, if not treated early, is often fatal. Given
the potential sun-damage to the skin, the need for sunscreen products is
obvious. Some data [75] suggest that 50% of a person's lifetime solar
exposure occurs by the age of 18, therefore early usage is critical.
3.8.2 Sunscreen chemicals

Sunscreen products are simply vehicles for materials that prevent meaningful
amounts of UV radiation from reaching the skin. These materials are usually
classified as chemical absorbers, or physical blockers and scatterers of UV
radiation. In the US, they are recognized by the FDA 'over-the-counter drug
regulations', which list various materials as category I (safe and effective)
sunscreens. In Europe, they form part of the EC and European Federation of
the Perfume, Cosmetics and Toiletries Industry (COLIPA) positive list. An
excellent review concerning the use of UV absorbers in sunscreen products
has been written by Shaath [76]. The materials can be grouped by name,
chemical type, the wavelength at which they have maximum absorbance,
allowed percentage usage in the US and EC, and by EC and COLIPA list
numbers (Table 3.3). The vast majority of the products listed in Table 3.3
are UV-B absorbers. The benzephones and butyl methoxy dibenzoyl
methane are UV -A absorbers. Titanium dioxide is a broad spectrum physical
block.
3.8.3 Testing
Sunscreen products formulated with the sunscreen materials shown in
Table 3.3, at allowed or appropriate amounts, must be tested for performance.
A number of in vitro performance tests have been developed and advocated,
but the only currently accepted tests are in vivo tests. The standard tests vary
from country to country, but are all similar. They are based on exposure to
the sun or, more usually, to lamps that give carefully controlled amounts of
radiation of very specific wavelengths. A useful value has evolved to identify
the efficacy of sunscreens. This is the sun protection factor or SPF, which is
based on production of redness on a test subject with a minimal erythemal
dose (MED), representing the amount of exposure required to produce
Table 3.3 UV absorbers for sunscreen chemicals
Maximum absorbance
(nm) % allowed
CTFA name FDA COLIPA
[Common or chemical name] Chemical type Alcohol Mineral oil Category I FDA EC(max) EC No. No.
Benzophenone-3 Benzophenone 288/325 288/329 Yes 2-6 10 1.4 S38

[Oxybenzone]
Benzophenone-4 Benzophenone 286/324 N/A Yes 5-10 5 2.17 S40
[Sulisobenzone]
Benzophenone-8 Benzophenone 284/327 296/352 Yes 3
[Dioxybenzone]
DEA methoxycinnamate Cinnamate 290 N/A Yes 8-10 8 2.9 S24
[4-Methoxycinnamic acid salts]
Ethyl dihydroxypropyl PABA derivative 312 N/A Yes 1-5 5 2.1 S2
p-Amino benzoic acid (PABA)
[Ethyl-4-bis(hydroxypropyl) amino
benzoate]
Glyceryl PABA PABA derivative 297 N/A Yes 2-3 5 2.4 S6
[Glyceryl 1-(4 amino-benzoate)]
Homosalate Salicylate 306 308 Yes 4-15 10 1.3 S12
[Homomenthyl salicylate]
Menthyl anthranilate Anthranilate 336 334 Yes 3.5-5 N/A N/A N/A
[Menthyl-o-aminobenzoate]
Octo crylene Diphenyl acrylate 303 N/A Yes 7-10 N/A N/A N/A
[2-Ethylhexyl-2-cyano-3, 3-diphenyl
acrylate]
Octyl dimethyl PABA PABA derivative 311 300 Yes 1.4-8 8 2.5 S8
[2-Ethylhexyl 4-dimethyl
amino benzoate ]
Octyl methoxycinnamate Cinnamate 311 289 Yes 2-7.5 10 2.13 S28
[2-Ethylhexyl-p-methoxy
cinnamate]
Octyl salicylate Salicylate 307 310 Yes 3-5 5 2.6 S 13
[2-Ethylhexyl salicylate]
PABA PABA 283 N/A Yes 5-15 5 1.1 SI
[4-amino benzoic acid]
2-Phenyl-benzimidazole-5-sulphonic acid Sui phonic acid Alkaline Solution 310 Yes 2-6 8 1.6 S45
[Novantisol] derivative
TEA-salicylate Salicylate 298 N/A Yes 5-12 2 2.11 S9
3-(4-methylbenzylidene)-camphor Miscellaneous 300 N/A No N/A 6 2.25 S60
4-Isopropyl dibenzoyl methane Miscellaneous 345 N/A No N/A 5 2.28 S64
[1-p-cumenyl-3-phenylpropane-1 ,3-dione]
Butyl methoxydibenzoyl methane Avobenzone 358 N/A No N/A 5 2.31 S66
Titanium dioxide Broad spectrum Yes 2-25
redness. The SPF is then the protection factor achieved with a specified layer
of sunscreen applied to test subjects. For instance, if individuals on average
show a redness (MED) at 20min and, after the application of a fixed amount
of sunscreen product, show redness at 80min, the product would have an
SPF of 4. Much experimentation has been done to evolve alternative testing
methods, and these are discussed in an excellent overall review of the subject
oflight protection by Groves [77].
The thickness of the applied film and lamps specified in sunscreen testing
vary from country to country. The US and Europe differ significantly.
Australia has separate standards and Japan is promulgating guidelines. Since
these methods are under review and change, it is best to seek advice on
acceptable testing from local trade associations, testing companies, sunscreen
suppliers or regulatory bodies.
Another area of testing is that of waterproofness, which also varies from
location to location. For instance, to support claims of waterproofness, the
US FDA requires an in vivo test in which the subject is immersed in water
for 80 min after application of product and then tested using the standard
protocol. The claimed SPF must not be below the value achieved after
immersion. Tests are now evolving and being advocated for testing protection
versus UV -A exposure. At this point in time, no one test is yet accepted as
standard.
3.8.4 Sunscreen formulations

Products that contain active sunscreens must be carefully formulated in order
to ensure that the sunscreen material is in its active form, is available when
used, does not contain materials that adversely shift or diminish its
absorbance, meets the SPF claimed, is waterproof if required, and is
cosmetically elegant. There are many forms available, including the common
lotions (generally O/W emulsions), oils (solutions of sunscreens in mineral
oil, vegetable oil, volatile silicones or esters), gels of a water or water/alcohol
character, sprays, and sticks for special applications. Many modern sun-
screens are formulated with combinations of raw materials that have
absorbance in both the UV-A and UV-B range, as well as physical blocks
to augment protection.
The esthetic properties of products are also important, as the product
must go on easily, spread uniformly and, if necessary, depending upon usage
and claims, establish a waterproof film. In general, there has been a steady
increase in SPF value, the spectrum absorbed and blocked, and the re-
quirement for formulas to be waterproof. The US FDA has established
regulations and, for instance, does not allow products to be marketed as
sunblocks unless they have a proven SPF of not less than 15. It is now
common for products to have SPFs greater than 15, with some having SPFs
approaching 50. Products with high SPFs require considerable formulation
skills to maximize the effect of the sunscreens used, and to make an elegant
and often waterproof product with actives that may be used at levels greater
than 20%. Increasing levels of sunscreen can also lead to problems of product
irritation.
Due to the variation in sunscreen formulations, and the multitude of active
ingredients and product forms, a careful study of available literature and
the marketplace is essential before meaningful exploratory work with formu-
lation can be initiated. Although there are relatively few manufacturers of
sunscreen chemicals, their help can be invaluable.
3.8.4.1 Suntan lotions These are generally O(W emulsions containing

levels of UV absorber or physical blocks to give a desired SPF. Their
formulation may differ from that of conventional moisturizing lotions, in
that significant amounts of oil phase are replaced by oil-based UV absorbers.
In addition, if suntan lotions are required to be waterproof, they require
addition of a water-repellent film former or some other means of ensuring
adherence of the active to the skin. The following formula is that of a low
SPF non-waterproof suntan lotion.
Typical formulation of an SP F 4 non-waterproof suntan lotion

Part Ingredient Wt%
A Ethylhexyl p-methoxycinnamate 2.0
Oxybenzone 1.0
Stearic acid 3.0
Cetyl alcohol 1.0
Glycerol monostearate 1.0
Sorbitol 3.0
C Fragrance and preservative q.s.
3.8.4.2 Waterproof sunblock creams These formulas incorporate signifi-

cantly higher levels of sunscreens, and also contain waterproofing agents.
The following formula is for an SPF 15 waterproof O(W lotion.
Typical formulation of a waterproof sunblock cream SPF 34 (US)

Part Ingredient Wt%
A Stearic acid 4.0
Cetyl alcohol 1.0
DEA cetyl phosphate 2.0
PVP eiocosene copolymer 3.0
Dimethicone 0.5
Ethylhexyl p-methoxycinnamate 7.5
Oxybenzone 6.0
Octyl salicylate 5.0
Octyldodecyl neopentanoate 10.0
Glycerin 5.0
Carbopol 940 0.1
C Deionized water 0.9
D Fragrance and preservative q.s.
Procedure: Add part C to part B and mix until uniform. Add ingredients of part A
and mix to dissolve evenly. Hold at 85°C. To form the emulsion, add part A to the
mixed parts of Band C at 85°C. Mix and cool to 35°C. Add part D.
3.8.4.3 Suntan oils Suntan oils are typically used by individuals who are
seeking a tan, rather than by individuals who are seeking protection. They
usually have a low SPF and are used not only to afford some protection for
a longer exposure, but also to give a glistening appearance to pigmented
skins. They are seldom waterproof and incorporate oil-soluble sunscreens
into mineral oil, vegetable oils and derivatives, fatty esters, and comb-
inations of the above, at times with volatile silicone added to decrease
oiliness. Products should be formulated to give hedonistic values upon
application.
Typicalformulation ofa suntan oil

Ingredient W t%
Cyciomethicone 64.9
Capric/caprylic triglyceride 5.0
Fragrance 0.1
Procedure: Blend all ingredients at room temperature.
3.8.4.4 Sun gels These products are often alcoholic/water solutions of

alcohol-soluble sunscreens, thickened with gums or polymers. They are cool
to apply and represent a small but loyal sub-segment of the category.
Typical formulation of a sunblock gel SP F 15

Ingredient W t%
Alcohol, 190 proof 75.0
Water 10.4
Oxybenzone 2.0
PPG-15 stearyl ether 1.0
Carbomer 940 0.6
Fragrance q.s.
Procedure: Blend in order at room temperature. Ensure thorough dispersion of

carbomer before adding triethanolamine.
3.8.4.5 Sprays Most sprays are solutions of sunscreens in alcohol with or

without volatile silicone, or alcohol-soluble emollients. They can either be
pump sprays or aerosol sprays, usually propelled by hydrocarbon propellants.
Such products are, by nature, light and easily spread on the skin. Since they
are in volatile bases, they tend to leave mainly sunscreen actives on the skin.
Great care must be taken to ensure spreadability, and enough dispersion to
ensure performance as well as maintenance of good esthetics.
Typicalformulation of a spray-pump SPF 15

Ingredient Wt%
Cyclomethicone 20.0
Ethyl alcohol, 200 proof 25.0
Oxybenzone 6.0
PVP/hexadecene copolymer 3.0
Fragrance q.s.
Procedure: Blend in order at room temperature. Ensure solution before addition of
the next ingredient. Filter well before packaging.
Typical formulation of an aerosol-spray SP F 15

Part Ingredient Wt%
A Cyclomethicone 20
Ethyl alcohol, 200 proof 25
Diisopropyl adipate 20
Oxybenzone 6.0
PVP/hexadecene copolymer 3.0
Fragrance q.s.
B Propellant 20
Procedure: Blend in order at room temperature. Ensure solution before addition of

the next ingredient. Filter well before packaging. Part A is a 100% formula for the
concentrate. Fill into an aerosol container and charge with a suitable propellant.
3.8.4.6 Sticks Sticks are usually for special application. They are of two
general types: (i) for lips; and (ii) for areas that burn easily, such as the nose,
ears and cheekbones. The formulas for lips are similar in nature to lip balm
or lip-stick formulas, and must be made of cosmetic raw materials that are
edible. The products for areas that burn easily are often formulated with
pigments that can act as total blocks. Zinc oxide, titanium dioxide, and talc
are frequently used in a waxy matrix, not altogether different from the
lip-balm products.
Typical formulation of a lip-balm stick SP F 15

Ingredient W t%
Petrolatum USP 72.5
Paraffin wax 17.0
Oxybenzone 3.0
Color q.s.
Fragrance q.s.
Procedure: Melt petrolatum and paraffin wax. Add other materials. Pour into molds
or swivel sticks.
Typical formulation of a burn-block pigmented stick

Ingredient Wt%
Titanium dioxide (oil dispersible) 10.0
Petrolatum USP 74
Paraffin wax 16
Color q.s.
Fragrance q.s.
Procedure: Melt petrolatum and paraffin wax. Add other materials. Pour into molds
or swivel sticks.
3.8.4.7 Everyday cosmetics with UV screens Many everyday cosmetic

products, including color cosmetics, are now being marketed with sunscreen
actives in their formulation. Recently, protective UV variants of the most
common hand and body moisturizer, as well as the most common facial
moisturizer, were launched. These are products that contain sunscreens with
an SPF of 4 and 15, respectively. It appears that many skin-care products
for everyday usage will contain UV screens. It is critical for these products
that the formulator takes extra care to ensure that esthetics do not suffer, that
the active is stable, and that the products do not cause irritations with the
mass of consumers who may be exposed to them on an everyday basis.
3.9 Acne
Acne vulgaris is a disease that can range from occasional blemishes to a

devastating, continuing episode leading to permanent scarring and much
anguish. This section will discuss the various forms of acne and their
treatment, except the treatment of cystic acne, which should only be treated
professionally.
There are many misconceptions about acne. It is not caused by diet, lack
of cleansing, sleep or social habits [78], but by hormonal control. Both males
and females secrete the male sex hormone testosterone. These secretions
stimulate the sebaceous glands to secrete sebum [3]. Acne is a disease that
often develops due to genetic predisposition during puberty, and typically
decreases during adulthood. The years of greatest severity are from 16 to 18
for women and from 18 to 19 for men. In white women, the incidence of
clinical acne during the years of greatest severity is 40%; in men, the incidence
is 35%. By the age of 40, 1% of men and 5% of women have lesions. The
incidence among orientals and blacks is lower [79]. The location of acne
lesions is generally on the face, neck, back and chest.
As discussed previously (section 3.2.2.4), the pilosebaceous system contains
sebaceous glands, and their associated hair follicles, both of which secrete
sebum. Acne generally occurs in sebaceous glands that are either associated
with fine or vellous hairs, or not associated with any hair. Humans are the
only mammals that routinely develop acne; this is because they have lost
their need for a hairy coating over the body, but still have many sebaceous
glands without terminal hairs. In the presence of a coat, these glands would
serve to wick sebum out on to the hair for the purpose of lubricating and
waterproofing terminal hairs, or for the purpose of providing an identifying
odor.
3.9.1 Sebaceous gland

As indicated previously (section 3.2.2), the sebaceous gland, with or without
a hair, has its origin within the dermis. The follicle is, however, lined with
stratum corneum, creating the follicle wall. This stratum corneum sheds
flattened dead cells into the follicle channel. This, combined with sebum,
produces a mixture which, if it does not flow freely to the skin's surface, has
the opportunity to plug, get infected and, through the enzymatic action of
bacteria, break down certain components of sebum. There are between 400
and 800 sebaceous glands per square centimeter, and it takes only one to
become inflamed to cause an acne lesion. All of these are factors in the disease
called acne, but none alone is the direct, single cause. All individuals have
sebaceous glands, containing sebum and bacteria. Some individuals have
severe acne, while others have little or no acne, sometimes only during
adolescence. Individuals who develop severe acne are differentiated by the
speed at which the epidermis lining the sebaceous gland produces and sheds
cells. This is called retention hyperkeratosis. The increase of cells into an
area rich with bacteria and lipid materials, including fatty acids, can cause
an acne lesion. The acne lesion can be classified, and the acne graded by
severity.
3.9.2 Acne nomenclature

Closed comedones or whiteheads are impactions of cellular debris, sebum,
etc., that build up under the skin in the shape of an inverted 'U' with a nearly
closed opening. The development of a comedone takes weeks and can lead
to other stages, some of which are more serious. If the comedone matures
without irritation, it becomes an open comedone or blackhead. The dark
color is due to the accumulation of dead cells and oxidized sebum, or collected
melanin, not to dirt. If the comedone, with its rich supply of cellular debris,
sebum and bacteria, becomes inflamed it is then a closed, red lump called a
papule (commonly a pimple, a spot, or a zit). As the process of inflammation
continues, the papule can build up white blood cells or pus, which arise from
the body's attempt to fight the irritation. This is known as a pustule, or
fluid-filled pimple. If the inflammation continues, the follicle wall ruptures,
and the inflammation spreads under the epidermal surface and into the
dermis, creating a nodule which is firm, red, but much larger and deeper
than a pimple. In severe acne, several follicles become inflamed in an area
and form a very large, merged, multiple pustule known as a cyst. Cystic acne
is deep and can lead to much loss of tissue and scarring. The entire process,
starting from an impacted sebaceous gland, and leading to cystic formation,
can take months from start to finish. In severe cystic acne, there is overlap
of one episode to another.
3.9.3 Acne grades

Acne is identified by four severity grades.
Grade I is a mild acne, which has both open and closed comedones, or
whiteheads and blackheads. This level is without redness, and does not spread
to adjacent tissue, or form pus. It is the first stage of the disease. Depending
on the individual, it may develop into more severe acne, remain at this stage
because of treatment, or may actually recede because of treatment or the
natural course of the disease.
Grade I I consists of closed comedones or whiteheads that are present in
a large number. They cause a bumpy surface and do not develop into open
comedones or blackheads. This bumpy surface is generally without
inflammation but, if left untreated, can lead to papules and pustules.
Grade I I I consists of both open and closed comedones, as well as
comedones that have become inflamed and have progressed to papules and
pustules. This grade of acne is severe, involves regions of redness, and can
lead to light scarring.
Grade IV, or cystic acne, is most severe. Individuals in Grade IV not only
have open and closed comedones, but papules and pustules that have merged
together with much irritation, inflammation and eventual loss of tissue with
scarring.
3.9.4 Treatment
Acne of all but the most mild and transient forms should be treated
professionally. Treatment can be either topical or systemic. Various treat-
ments are available, either at retail or on a prescription from a physician,
depending on their nature. Topical treatments sold at retail consist of benzoyl
peroxide, salicylic acid, sulfur, resorcinol, and a combination of ethyl lactate
and lactic acid. Topical preparations available on prescription are retinoic
acid, and various antibiotics such as clindamycin and tetracycline. Oral
therapy consists of antibiotic therapy with tetracycline or erythromycin and
13-cis-retinoic acid. The retinoids have revolutionized the treatment of severe
acne. Topical retinoic acid [80] decreases the cohesiveness of the pre-acne
follicular epithelium, which leads to decreased microcomedo formation. In
addition, it stimulates mitotic activity and causes extrusion of existing
comedones. Systemic or oral administration of isotretinoin is used for severe
or cystic acne. It has been shown to affect sebum secretion, to have an
inflammatory action, and to stimulate the immune system. Its primary
function is to reduce over-active sebaceous glands to epithelial buds. It often
results in a complete and prolonged remission of cystic acne [81]. This oral
therapy has severe side effects, including fetal abnormalities, extreme dry
skin, and peeling, especially of the lips. Consequently, it must be carefully
controlled and monitored, and is contra-indicated in female patients of
child-bearing age, unless adequate steps to prevent pregnancy are taken.
Treatment for Grades I, II or III acne is often a combination of oral and
topical treatment. Isotretinoin is reserved for Grade IV acne that has been
shown to be unresponsive to other treatments.
A wide variety of cleansing products are sold to acne-prone individuals.
This includes astringents, exfoliating scrubs, and buffing pads that are used
to get the face very clean and to remove surface sebum. The products sold
are satisfactory as cleansers, but do not provide adequate therapy for acne.
This is because acne is caused by a combination of factors, all of which are
operating in the sebaceous gland below the surface of the epidermis and, are
not therefore, vulnerable to topical or surface cleansers, be they solvents
(alcohol), exfoliants (polyethylene beads) or scrubbing pads of rough synthetic
material.
As already stated, acne is a disease that can have devastating results on

the appearance and psyche of individuals affected. In all but the most mild
and transient cases, it is advisable to seek competent professional advice.
3.10 Liposomes
The use ofliposomes in cosmetic products has increased during the 1980s and
1990s. The attractiveness of liposomes to both the cosmetic chemist and
marketeer comes from several factors. Liposomes are very small spheres
consisting of a lipid bilayer. It is interesting to note that the skin's lipids are
also organized into a similar bilayer structure [82]. Liposomes range from
25-500 nm and vary with the lipids used and method of preparation.
Liposomes are often formed with phospholipids, from lecithin of either
vegetable (soybean) or animal (egg yolk) source [83]. However, liposomes
can also be formed with non-ionic surfactant vesicles and other materials
[84]. Liposomes have been shown to be effective carriers for a wide variety
of materials, both active and cosmetic.
Liposomes formed from phospholipids are notoriously unstable in
finished formulations and may be stabilized by the addition of cholesterol to
increase bilayer viscosity. The liposome may also be given a positive or
negative charge by the addition of dicetyl phosphate or stearylamine [85].
Liposomes have been shown to be capable of carrying drug materials within
the sphere. Many drugs are made more available to the body by the use of
liposomes [86]. Ghyczy et al. [87] have shown that even so-called empty
liposomes formed from vegetable source phospholipids are able to increase
the moisture content of the skin and improve roughness in comparison with
a typical O/W emulsion.
Formulating with liposomes requires care in order to maintain the stability
of the liposome. Rules advanced by Brooks and McManus [83] are:
• Avoid surfactants or materials that can act as a co-solvent for the
phospholipid.
• Avoid materials with high ionic strength such as salts.
• Avoid solvents such as alcohol that can remove the water that stabilizes
the surface of the bilayer.
• Avoid excessive shear or temperature when adding the liposome to your
final formula.
Typical formulation of a liposome-containing facial lotion
Part Ingredient Wt%
Magnesium aluminium silicate 0.3
Tetrasodium EDTA 0.1
Glycerin 3.0
B Ceteryl alcohol and ceteareth-20 0.8
Sorbitan stearate 0.5
Stearic acid 0.5
Cetyl alcohol and acetylated
lanolin alcohol 0.5
C 12-15 alcohols benzoate 0.4
Dimethicone 0.2
Mineral oil 70 vis 3.0
C Potassium hydroxide (10% soln) 1.5
D Soy lecithin and tissue
respiratory factors 10.0
E Preservatives q.s.
Fragrance q.s.
Procedure: Heat parts A aItd B separately to 75°C. Add part A to part B with good
agitation and mix until uniform and creamy. Add part C and begin cooling with
mixing. Add part E, then part D (liposome) and mix gently to 30°C.
References
1. Marzalli, F.N. and Maibach, H.I. (1984) Permeability and reactivity of skin as related to
age. J. Soc. Cosrnet. Chern. 35 95-102.
2. Montagna, W. and Parakkal, P.F. (1974) The Structure and Function of Skin, 3rd edn.
Academic Press, New York.
3. Hamilton, J.B. (1941) Male hormone substance: a prime factor in acne. J. Clin. Endocrinol
1570-592.
4. Kligman, A.M. and Shelley (1958) An investigation of the biology of the human sebaceous
gland. J. Invest. Derrnato!' 30 99-125.
5. Strauss, J.S. and Kligman, A.M. (1958) Pathologic patterns of the sebaceous glands. J.
Invest. Derrnato!' 30 51-61.
6. Utlley, M. (1972) Measurement and control of perspiration. J. Soc. Cosrnet. Chern. 2323-43.
7. Froebe, et al. (1990) Auxiliary malodor production: A new mechanism. J. Soc. Cosrnet. Chern.
41 173-185.
8. Blank, I.H. (1952) Factors which influence the water content of the stratum corneum. J.
Invest. Derrnatol. 18 433-440.
9. Kligman, A.M. (1978) Regression method for assessing the efficacy of moisturizing. Cosrnet.
Toilet. 93 27-35.
10. Boisits, E.K. et al. (1989) The refined regression method. J. Cutaneous Aging and Cosmetic.
Derrnat.l 155-163.
11. Packman, E.W. and Gans, E.H. (1978) Topical moisturizers: quantification of their effect on
superficial facial lines. J. Soc. Cosrnet. Chern. 29 79-90.
12. Packman, E.W. and Gans, E.H. (1978) The panel study as a scientifically controlled
investigation: moisturizers and superficial facial lines. J. Soc. Cosrnet. Chern. 29 91-98.
13. Jansen, L.H. et al. (1974) Improved fluoresence staining technique for estimating turnover of
the human stratum corneum. Brit. J. Derrnatol. 90 9-12.
14. Cook, T.H. (1980) Profilometry of skin: a useful tool for the substantiation of cosmetic
efficacy. J. Soc. Cosrnet. Chern. 31 339-359.
15. Dorogi, P.L. and Zielinski, M. (1989) Assessment of skin conditions using profilometry.
Cosmet. Toilet. 10439-44.
16. Hargens, e.W. (1981) The gas-bearing electro dynamometer (GBE) applied to measuring
mechanical changes in skin and other tissues. Bioeng. Skin 1 133-122.
17. Christensen, M.S. et al. (1977) Viscoelastic properties of intact skin: instrumentation,
hydration effects and the contribution of stratum corneum. J. Invest. Dermatol. 69 282-286.
18. Nucci, J. (1989) Measurement of skin surface viscoelasticity for claim support and product
development. Cosmet. Toilet. 10447-51.
19. Aubert, L. et al. (1985) An in vivo assessment of the biomechanical properties of human skin
modifications under the influence of cosmetic products. Int. J. Cosmet. Sci. 7 51-59.
20. Berube, G.R. et al. (1971) Measurement in vivo of transepidermal moisture loss. J. Soc.
Cosmet. Chem. 22 361-368.
21. Berube, G.R. and Berdick, M. (1974) Transepidermal moisture loss II. The significance of
the use thickness of topical substances. J. Soc. Cosmet. Chem. 25 397-406.
22. Berube, G.R. and Tranner, F. (1979) Transepidermal moisture loss III. An in vitro approach.
J. Soc. Cosmet. Chem. 30181-190.
23. Steitz, J.e. and Spencer, T.S. (1982) The use of capacitative evaporimetry to measure
effects of topical ingredients and transepidermal water loss (TEWL). J. Invest. Dermatol. 78
351-356.
24. Potts, R.O. (1985) In vivo measurement of water content of the stratum corneum using
infrared spectroscopy: a review. Cosmet. Toilet. 100 (10) 27-31.
25. Salter, D.C. (1987) Instrumental methods of assessing skin moisturization. Cosmet. Toilet.
102 103-109.
26. Rieger, M.M. and Deem, D.E. (1974) Skin moisturizers, methods for measuring water
regain, mechanical properties, and transepidermal moisture loss of stratum corneum. J. Soc.
Cosmet. Chem. 25 239-252.
27. Nishiyama, S. et al. (1983) A study on skin hydration with cream, influence of its components
on skin hydration. J. Soc. Cosmet. Chem. Japan 16(2) 136-143.
28. Nishiyama, S. et al. (1983) A study on skin hydration with WIO type cream. J. Soc. Cosmet.
Chem. Japan 17(2) 116-120.
29. Quattrone, AJ. and Laden, K. (1976) Physical techniques for assessing skin moisturization.
J. Soc. Cosmet. Chem. 27 607-623.
30. Kligman, A.M. et al. (1986) Sebutape: A device for visualizing and measuring human
sebaceous secretion. J. Soc. Cosmet. Chem. 37 369-374.
31. Frosch, P.J. and Kligman, A.M. (1979) The soap chamber test: A new method for assessing
the irritancy of soaps. J. Am. Acad. Dermatol. 1 35-41.
32. Murahata, R.I. et al. (1986) The use of transepidermal water loss to measure and predict
the irritation response to surfactants. Int. J. Cosmet. Sci. 5 225-232.
33. Lukacovic, M.F. et al. (1988) Forearm wash test to evaluate the clinical mildness of cleansing
products. J. Soc. Cosmet. Chem. 39 355-366.
34. Strube, D.O. et. al. (1989) The flex wash test: A method for evaluating the mildness of
personal wash products. J. Soc. Cosmet. Chem. 40 297-306.
35. Frosch, P.J. (1982) Irritancy of soaps and detergent bars. In Principles of Cosmetics for the
Dermatologist Frosch, P. and Horowitz, S.N. (Eds). Mosby, St. Louis, pp. 5-12.
36. CTF A (1991) International Cosmetic Ingredient Dictionary, 4th Edn. CTFA Inc., Washington,
D.e.
37. US Phamacopea XXI (1970) Mack Publishing Co., Easton, PA, p. 143.
38. US Patents 2, 894, 912; 3, 376, 229; 3, 394, 155; 3,420,858.
39. US Patents 4, 132,679; 4, 139,485; 4, 369, 134; 4, 536, 519; 4, 758, 376.
40. Bettley, F.R. (1960) Some effects of soap on the skin. Brit. Med. J. 5187 1675-1679.
41. Prottey, e. et al. (1972) The effect of soap upon certain aspects of skin biochemistry. J.
Soc. Cosmet. Chem. 24 472-492.
42. Loden, M. and Bengtsson, A. (1990) Mechanical removal of the superficial portion of the
stratum corneum by a scrub cream: methods for the objective assessment ofthe effects. J. Soc.
Cosmet. Chem. 41111-/21.
43. Komp, B. (1987) Skin compatibility tests-Importance in skin cleansing product
development. Cosmet. Toilet. 102 89-98.
44. Middleton, J.D. and Allen, B.M. (1973) The influence of temperature and humidity on
stratum corneum and its relation to skin chapping. J. Soc. Cosmet. Chem. 24 239-243.
45. Idson, B. (1973) Water and skin. J. Soc. Cosmet. Chem. 24 197-212.
46. Blank, I.H. (1953) Further observation on factors which influence the water content of the
stratum corneum. J. Invest. DermatoI. 21 259-271.
47. Laden, K. and Spitzer, R. (1967) Identification of a natural moisturizing agent. J. Soc.
Cosmet. Chern. 18351-360.
48. Rieger, M.M. and Deem, D.E. (1974) Skin moisturizers II. The effects of cosmetic ingredients
on human stratum corneum. J. Soc. Cosmet. Chem. 25 253-262.
49. Bissett, D.L. and McBride, J.F. (1984) Skin conditioning with glycerol. J. Soc. Cosmet. Chern.
35345-350.
50. Middleton, J.D. (1974) Development of a skin cream designed to reduce dry and flaky skin.
J. Soc. Cosmet. Chem. 25 519-534.
51. US Patents 4, 603, 146, and 4, 888, 342.
52. US Patents 3,879,537; 3, 920, 835; 4,105,783; 4, 234, 599; 4,363,815;4,380,549; 4, 518, 789;
5,091,171;5,093,360;5,258,391;5,385,938.
53. Hayflick, L. and Moorehead, P.S. (1961) The serial cultivation of human diploid cell strains.
ExptI. Cell Res. 25 585-621.
54. Pugliese, P.T. (1987) Concepts in aging and the skin. Cosmet. Toilet. 102 19-44.
55. Ryan, J.C. (1966) The microcirculation of the skin in old age. Gerontol. Clin. 8 327-337.
56. Plewig, G. and Kligman, A.M. (1972) Follikulare pusteln im kaliumjodid-epicutantest.
Arch. Dermatol. Forsch.242137-152.
57. Gilchrest, B.A. (1991) Physiology and Pathophysiology of Ageing Skin in Physiology,
Biochemistry and Molecular Biology of the Skin. Goldsmith, L.A. (Ed.). Oxford University
Press, pp. 1425-1444.
58. Wright, E.T. and Shellow, W.V. (1973) The histopathology of wrinkles. J. Soc. Cosmet.
Chem. 24 81-85.
59. Counts, D.F. et al. (1988) The effect of retinyl palmitate on skin composition and
morphometry. J. Soc. Cosmet. Chem. 39 235-240.
60. Kligman, L. (1986) Effects of all trans-retinoic acid on the dermis of hairless mice. J. Am.
Acad. Dermatol.15 779-785.
61. Braverman, I.M. and Fonferko, E. (1982) Studies in cutaneous ageing I: the elastic fiber
network. J. Invest. Dermatol. 78 434--443.
62. Smith, J. G. et al. (1962) Alterations in human dermal connective tissue with age and chronic
sun damage. J. Invest. DermatoI. 39 347-350.
63. Kligman, L.H. et al. (1983) Sunscreens promote repair of UV radiation induced dermal
damage. J. Invest. Dermatol.8194--102.
64. Smith, W.P. (1994) Hydroxy acids and skin aging. Cosmet. Toilet. 109 41-48.
65. Abamba, G. (1993) Skin preparation of Poucher's Perfumery, Cosmetics and Soaps.
Volume 3, Poucher, W.A. and Butler, H. (Eds). pp. 335-392.
66. McNamara, S.H. (1987) Performance claims for skin care cosmetics. Cosmet. Toilet. 102
81-88.
67. Koller, L.R. (1965) Ultraviolet Radiation, 2nd edn. John Wiley and Sons Inc., New York,
p.107.
68. Wier, K.A. et. al. (1971) Nuclear changes during ultraviolet light-induced depression of
ribonucleic acid and protein synthesis in human epidermis. Lab. Invest. 25451-456.
69. Everett, M.A. et al. (1966) Penetration of epidermis by ultraviolet rays. Photochem. Photobiol.
5533-542.
70. Olson, R.L. et aI. (1966) Effect of anatomic location and time on ultraviolet erythema. Arch.
Derm. 93 211-215.
71. Ibson, A. and Blank, H. (1967) Testing drug phototoxicity in mice. J. Invest. DermatoI. 49
508-511.
72. Kaidby, K.H. and Kligman, A.M. (1978) Sunburn protection by longwave ultraviolet
radiation induced pigmentation. Arch. Derm. 114 46-48.
73. Editorial (1991) Protecting man from UV exposure. The Lancet 3371258-1259.
74. Fitzpatrick, T.B. and Pathak, M.A. (Ed.) (1974) In Sunlight and Man. University of Tokyo
Press, Tokyo.
75. National Institutes of Health (1989) Sunlight, Ultraviolet Radiation and the Skin. NIH
Consensus Development Conference Statement 7, No.8, pp 1-10. NIH, Bethesda, MD.
76. Shaath, N.A. (1987) Encyclopedia of UV absorbers for sunscreen products. Cosmet. Toilet.
10221-39.
77. Groves, G.A. (1980) Sunburn and its prevention. Aust. J. Dermatol. 21 115-14l.
78. Fulton, J.E. and Black, E. (1983) Dr. Fulton's Step-By-Step Program for Clearing Acne.
Harper and Row, New York.
79. Rook, A. et al. (1986) Textbook of Dermatology. Blackwell Scientific, Oxford, England.
80. Frank, S.B. (1971) Acne Vulgaris. c.B. Thomas, Springfield, II\.
81. Physicians Desk Reference (1986) Medical Economics, Oradell, N.J.
82. Elias, P.M. (1991) Epidermal barrier function: intercellular lamellar lipid structures, origin,
composition and metabolism. J. Contr. Release 15 199-208.
83. Brooks, G.l. and McManus, R.C. (1990) Finding new uses for liposomes in cosmetics.
InformI891-896.
84. Abate, K. (1993) Non-phospholipid liposomes in cosmetics. Soap/Cosmet/Chem Specialities
69 (S) 37-40.
85. Perrier, P. and Redziniak, G. (1989) Liposomes in cosmetics. Soap, Perfumery Cosmet. 62 (2)
29-30.
86. Talsma, H. and Crommelin, D.l.A. (1992) Liposomes as drug delivery systems, part I:
preparation. Pharm. Tech. 1696-106.
87. Ghyczy, M. et al. (1992) Effect and production ofliposomes from vegetable phosphatidyl-
choline (lecithin) in cosmetics. Society of Cosmetic Chemists Annual Meeting, Dec. 3-4, New
York.
4 Color cosmetics
J. CUNNINGHAM
4.1 Introduction
The primary reason a pigmented product is purchased is for the color it

imparts. Other beneficial characteristics will be appreciated by the consumer,
but short of total discomfort, these will be sacrificed if the color is 'just right'.
This color selection will be based on the purchaser's general complexion,
and on what he or she perceives as making him or her look attractive, much
the same criteria that dictate the purchase of clothing and other fashion
accessories. In a nutshell, then, when speaking of colored cosmetics, it is
fashion first and science second.
The role of cosmetic formulators is important. Product safety must be
ensured, and creative work on the secondary benefits such as application
and texture can often mean the difference between the success or failure of
the product in a competitive environment. For this reason, each product
category treated in this chapter is prefaced with a list of consumer wishes
after the shade has been chosen.
4.2 Lip color
Lip products fall into three main categories; (i) lipsticks; (ii) glosses; and (iii)
liners. Lipsticks, as the name suggests, are molded in the form of a crayon
and are dispersed from a swivel-up case (Figure 4.1). Lip glosses, too, can be
marketed in stick form, but the majority of products in this category are
semi-solid and dispensed from a tube with a sponge-type applicator. The
majority of liners are sold in pencil form. The share of lip make-up (US
dollars) is shown in Figure 4.2. Total sales in the US and Europe are estimated
to be around 1.5 billion dollars per year.
4.2.1 Lipsticks
4.2.1.1 Consumer expectations A lipstick should apply easily, give good

color coverage, yet look natural. It should feel moist, not dry, and should
not bleed (flow) into the lines around the mouth. It should not change color
1
I
t
Figure 4.1 Standard lipstick case.
Glosses
14%
Liners
13%
Figure 4.2 Share of lip make-up sales (dollars) in the US and Europe during 1990.
during wear and should have an acceptable flavor fragrance. It should keep
lips from cracking and peeling, and last a minimum of three to four hours.
A wide range of colors, in both cream and frost (or pearl), with varied shine
levels from matte (dull) to cream (soft shine) to glossy (high shine) is essential.
4.2.1.2 Formulation Lipsticks are mixtures of waxes, oils and pigments.

Varying the ratio of these ingredients determines the final product
COLOR COSMETICS 151
characteristics. In the case of lipstick, a high wax, low oil, high pigment
formulation generally results in a long-wearing product that sacrifices a
varying degree of gloss and texture. Meanwhile a lower wax, higher oil base
will apply more smoothly, have greater shine, but will not wear as long. More
recently several lipsticks have been introduced which incorporate a volatile
silicone or hydrocarbon. These formulations apply smoothly but soon dry
down to leave a matte and rather dry film on the lip. These newer products,
wear longer and are more resistant to the common bane of the lipstick
consumer 'transfer of the lipstick to the coffee cup'. Consequently, the claims
that are to be made for a product must be known before embarking on the
formulation process. In addition, if it is decided to incorporate a volatile into
the lipstick it is important that an airtight package be sourced, and it is just as
critical that the packaging materials be occlusive to the passage of the chosen
solvent. The following is an example of a basic lipstick formulation. Other
examples are shown in Table 4.1.
Trade name Manufacturer: Wt%
Indopol H-lOO Amono Chemical 6.00
Eutanol G Henkel, Inc. 7.50
Candelilla wax Strahl & Pitsch 9.00
Multiwax ML-445 Sonneborn 3.00
Satulan Croda 7.50
Pigments phase (iron oxides and lakes) 8.00
Pearlescent pigments 6.00
Castor oil 52.00
Fragrance (if desired)
Preservatives and antioxidants 1.00
Table 4.2 gives examples of formulations which incorporate volatile

solvents. Recent estimates suggest that the market share of such formu-
lations exceeds 10% in the US.
Candelilla wax Candelilla serves two purposes in this formulation.
Primarily, it is a hard wax which gives the stick rigidity. Its high melting
point aids the overall high temperature stability of the finished stick. In most
formulations, carnauba wax can be used either as a substitute, or in
combination with candelilla.
Multiwax ML455 (microcrystalline wax) Microcrystalline wax is used to
give the stick structural integrity. Like candelilla, it has a high melting point
(approx. 80°C), but is softer and less brittle. This improves the overall tensile
strength of the stick. Ozokerite and cerasynt waxes are often used to achieve
the same end.
Indopol H-lOO (polybutene) Indopol is a viscous semi-solid and is pri-
marily used to increase the gloss of the stick and the lay down (imparting
the color film). It also serves to increase the viscosity of the oil phase, which
Table 4.1 Lipstick formulas (wt%) by Mearl Corporation
Soft Medium Firm
A B A B A B
Carnauba wax 12.0 11.6 13.7 13.3

Candelilla wax 11.5 11.5
Beeswax 8.5 8.5 15.0 15.0
Hydrogenated lanolin 13.0 13.0
(Lipolan)
Pur-cellin wax 15.0 15.0
Isopropyl lanolate 15.0 15.0
(Amerlate P)
Castor oil 32.8 10.7 16.0
Isostearyl alcohol 14.0 14.0
(AdoI66)
Laury I lacta te 16.0 8.0
(Ceraphyl 31)
Diisopropyl adipate 13.5 7.0
(Ceraphyl 230)
Decyl oleate 15.0 7.5
(Ceraphyl 140-T)
Butyl stearate 14.0 7.4
Isopropyl myristate 30.0 30.0
Flamenco Superpearl 100a 15.0 15.0 15.0
Flamenco Superpearl cca 37.5 37.5 37.5
Antioxidant q.s. q.s. q.s. q.s. q.s. q.s.
Antimicrobial q.s. q.s. q.s. q.s. q.s. q.s.
Perfume/flavor q.s. q.s. q.s. q.s. q.s. q.s.
aMearl Corporation
Table 4.2 Long wearing lipstick formulas (wt%)
Trade name Manufacturer A B
Liponate TDTM Lipo 12.4 13.0
Synthetic Wax Dura 12.3 13.0
Paraffin Ross 6.5 6.5
Ozokerite Strahl & Pitsch 5.0 5.0
Emerest 2452 Henkel 4.7 5.0
Silicone Fluid G.E. 6.7 5.0
Abil Wax 9800 Goldschmidt 5.3 5.0
PEG-4 Lipo 1.4 2.0
Indopol H -100 Chern Central 4.6
MasilSFVV Mazer 30.0 20.0
Permethyl99A Presperse 10.0
Pigments 10.0 12.0

Preservatives and
fragrance q.s. q.s.
in turn reduces the potential of color bleeding into the fine lines around the
mouth.
Eutanol and satulan (octyldodecanol and hydrogenated lanolin) Both these
items are used to increase the slip and moisturizing feel on the lips. They
COLOR COSMETICS 153
can be replaced by a myriad of similar emollients, such as mineral oil,
isopropyl myristate, etc.
Castor oil Castor oil is the backbone of most lipstick formulations. It
is an excellent pigment dispersing aid and imparts a superb creamy,
moisturizing feel on the lips.
Pigments In lipsticks, color concentrations range between 2 and 10%.

Bismuth oxychloride and titanium-coated micas are used to impart a
pearlescent look (frost).
Fragrance Fragrance/flavor is often added, usually at less than 1%, to
improve the taste of the product on the lips.
4.2.1.3 Manufacture Lipsticks are generally manufactured in four stages:

(i) Pigment milling
(ii) Combination of pigment phase into the base
(iii) Molding
(iv) Flaming
Milling Milling is required to break up pigment agglomeration rather
than to reduce particle size. There are no hard and fast rules on how this
can be accomplished, but today most people opt for the three-roll mill.
Carborundum and colloid mills are also used. The pigment must first be
wetted with one of the liquid constituents of the base. It is wise, therefore,
to incorporate a good milling media into the formula recipe. The majority
offormulations on the market today use castor or lanolin oils for this purpose.
To determine the pigment/oil ratio best for milling, a good rule of thumb is
to use two parts of oil for one part of pigment, but a formulation particularly
high in organic pigments may necessitate an increase in the oil level. The
pigment/oil mixture is usually blended together in a Cowles Dissolver or
any high-shear mixer that can handle high viscosity materials. The resultant
paste can then be passed through the mill. The blend is milled until it reaches a
satisfactory particle size (usually 20.um) on a standard paint gauge. Often
two passes through the roller mill are enough to accomplish this but,
depending on the shade, three passes are sometimes required.
Combination of pigment phase into the base The batching of the lipstick
itself is a simple procedure. The wax and oil phase are usually melted in a
steam-jacketed kettle equipped with a single propeller agitator. Following
this, the milled pigment phase is added.
Two points should be considered during manufacturing. The first is that
a conscious effort should be made to minimize the incorporation of air into
the mass. Air in the bulk is difficult to remove and will lead to unsightly
pinholes in the stick during molding, resulting in slow production and increase
rejection rate. The second point is that it is often wise to complete a small
trial batch (as little as a 100 g) on the laboratory bench using the pigment
shade phase before preparing the wax/oil/pigment blend on full scale. The
reason for this is that color mismatch will show up on the laboratory trial
batch and, if major color adjustments are needed, it is better to make the
changes to the pigment/oil shade blend rather than the finished batch.
It should be noted that in the case of the formulations containing cyclo-
methicone (Masil SFVV) or Permethyl 99A (Isododecane) several modifica-
tions to this procedure will be necessary. First of all, because of the fugitive
nature of the volatiles it is best to add these materials at the last possible
moment. Some manufacturers will add the volatiles just before the finished
batch is dropped into storage, while others delay the addition until the
molding process itself. Then again, and of course, this will vary with the
specific formulation, since owing to the lack of a sufficient quantity of a good
milling media, it probably will be necessary to mill the pigment into the total
base (minus the volatiles). Ultimately manufacturers prefer to fill these
formulations directly into the case rather than going through the inter-
mediate block molding routine.
Molding The most common method for molding lipsticks is by use of
verticle split molds. The split itself runs down the center of each row of sticks
(Figure 4.3). Most lipstick formulations mold well between 75 and 85°C.
Pre-heating the mold to around 35°C avoids the formation of 'cold marks'
on the stick, and holding the mold at a slight angle to the verticle is a
technique often used to avoid air entrapment. The mass should not be poured
directly into the cavities for the same reason. Rapid cooling after the mass
is poured into the mold is important since it leads to a smaller, more uniform
crystalline structure, which, in turn, leads to better stability and gloss. Once
cooled, the molds can be split open and the sticks ejected on to trays or
some other suitable storage container until they are ready for flaming.
Flaming Flaming is a procedure for passing the molded stick through
the flame of a gas burner, or series of burners, to increase the surface gloss.
Highly polished cavities
I I I I I I I
I I I II I
I I I I I I
I I I I I I
\ I \
- - -
1\ 1\ I \
Figure 4.3 Lipstick split mold.

COLOR COSMETICS 155
Flamed finished
sticks ready for
Flame jets capping
Lipsticks from mold ('bullets')

inserted into case bottoms
(mechanism)
Shield for
gas flames
Conveyor belt
Figure 4.4 Lipstick flame line.
The flames are adjusted to a level just hot enough to just melt the surface
of the stick (Figure 4.4).
Although only one method of lipstick manufacture has been described
here, several high-speed, automatic molding machines, which produce high
quality lipsticks are available. For more information, the reader is referred
to the manufacturers.
4.2.1.4 Blooming Under certain conditions, particularly high ambient

temperatures, certain liquid fractions in the formulation, including the
higher melting point portions in solution, can migrate through the lipstick
manifesting as unsightly oil droplets on the surface. This phenomenon is
known as 'blooming' or 'syneresis'.
What happens next depends on the subsequent environmental conditions
in which the lipstick is stored. Under some conditions the oil can be
reabsorbed into the stick leaving the product with an unesthetic blotchy
appearance, while on other occasions the oil exudate and its solute can
recrystallize giving the composition a mottled salty look. These problems
are shared with the manufacturers of chocolate, and the confectionery
industry has contributed much research into the cause of this manifestation.
One result of this research indicates that the root cause of bloom can be
traced to an incompatibility between individual ingredients in the formula-
tion. The studies also show that bloom can be exacerbated by processing
and, ultimately, the storage conditions of the finished product. Although
these statements may seem to be stating the obvious, the real story is
extremely complex. For example, many waxes, oils and fatty acids commonly
used in lipsticks are completely miscible in the liquid phase, tolerate each
other in the solid phase, but are incompatible in the eutectic state. In
chocolates, this phenomena leads to a lauric acid-triglyceride migration

which subsequently recrystallizes on the surface. The parallel with lipsticks
containing castor oil and fatty acids is clear.
Another common form of bloom can be created by a tempering mechanism
during molding. Shock cooling can impress a needle shaped crystal in the
stick, and these needles are, by nature, more soluble than the competing
platelet and intermediate malcrystalline types. As time passes, the needle
crystals dissolve and other more stable, but less soluble forms dominate.
The transition from needle to other crystal types leaves behind the excess
solvent (oil) that the needles once contained. Subsequently, an excess of oil
develops, which then migrates to the surface of the stick.
The results of the research into the mechanism leading to bloom suggest
several solutions to the problem. Perhaps the most important of these is the
recommendation that all ingredients used in a specific formulation are
compatible at the ratios in which they are incorporated. It is suggested that
no assumptions be made in this regard. Most formulations are developed by
trial and error with aesthetic considerations being the primary goal and
stability being considered only after this has been achieved. The rules can be
ignored if required and sometimes the aesthetic qualities might be worth a
minor stability problem. However, it is better that this be a choice rather than
an accident.
Another way to minimize the bloom is to incorporate anti-blooming
agents into the formulation. The chocolate industry has found that sorbitan
tristearate, at levels up to 2.5% has yielded excellent results. Lactic acid esters
of monoglycerides have also shown promise. These compounds have also
been employed successfully in cosmetics. Meanwhile, ascorbic palmitate, at
levels of around I % and octyldodecanol, at 5% and above, have also been
found to reduce the propensity to bloom.
This discussion on blooming only touches upon some of the more
important issues involved in this most complex subject. As mentioned, most
of the research work on this area has taken place in the confectionery
industry, and although parallels can be made with cosmetics, it should be
pointed out that chocolate formulations are far simpler than the multi-waxed
lipstick formulation. In addition, no attempt has been made here to discuss
'super cooling', which maintains waxes in liquid form well below their normal
solidification point, thus creating the eutectic effect mentioned earlier.
Finally, literature is available on the intercompatibility of wax systems and
can be obtained from the raw material suppliers or from several publications
on industrial waxes [1-3].
4.2.2 Lip glosses
4.2.2.1 Consumer expectations A lip gloss should apply easily and provide
a wet, shiny look. It should have a transparent color coverage (sheer) and
COLOR COSMETICS 157
feel very moist, never dry, on the lips. The fragrance/flavor may be higher
than in lipstick. As with lipstick, lip gloss should come in a wide variety of
colors, both cream and frost (pearl).
4.2.2.2 Formulation Like lipstick, lip gloss consists of a mixture of waxes,

oils and pigments. The major difference is that gloss and transparent coverage
are the key properties required and, consequently, the oil to wax ratio is
higher and the pigment level is lower. A typical lip gloss formulation is shown
below.
Deodorized lanolin Amerchol 44.40
Indopo! H-lOO Amoco 32.00
Beeswax Strahl & Pitsch 6.00
Amerlate P Amerchol 23.00
D&C Red #7 W,C,D 3.00
D&C Red #27 Sun Chemical 1.50
Yellow iron oxides W,C,D 0.10
Fragrance (to taste)
Preservatives
Deodorized lanolin Lanolin, like castor oil, is an excellent pigment
dispersant. It also has an excellent feel on the lips, and imparts an excellent
gloss.
Indopol H-JOO Details of this are given in section 4.2.1.2.
Beeswax Beeswax is used to build viscosity and lengthen the wear.
Amerlate P (lanolin oil) Imparts excellent slip and moisturizing feel to
the lips.
Pigments Pigments range from 0 to 5% in most lip glosses. As there is
desire for transparency, inorganic pigments are usually used at low levels.
4.2.2.3 Manufacture Lip gloss manufacture is identical to that of lipsticks,

but, if the product is not in stick form, the molding and flaming steps are
omitted.
4.2.3 Lip liners
4.2.3.1 Consumer expectations Liners should have high pigment coverage

to accent the line of the lip, and should be firm enough not to run into the
lines around the lip. A wide range of colors is desirable, and the products
must be suitable for drawing a thin, clearly defined line around the periphery
of the lips.
4.2.3.2 Formulation As with the other lip products, lipliners are mixtures
of waxes, oils, and pigments. Emolliency is not the necessity it is with lipsticks
and lip glosses, but pigment cover is essential. For this reason, the wax/
pigment level is elevated and the oil level lowered.
4.2.3.3 Manufacture Although a small segment of the lip liner market uses
small diameter molded crayons, the majority of products sold are in the form
of woodcased pencils, most of which have extruded 'leads.' Bulk manufac-
turing usually takes place in a steam-jacketed kettle, but, due to the heavier
pigment/wax concentration the bulk is more pasty and requires a
kneading-type action to ensure proper mixing. Due to the high pigment
concentration, pre-milling of pigment is often impractical and it is best to
roller mill the whole batch as the final step. Roller milling helps to remove
any entrapped air.
Examples of extruded bulk lip liner formulations

Japan wax Robeco Chemical 43.41
S70-XXH Durkee Foods 7.66
EE hard fat flakes Swift & Company 3.91
Lanolin, anhydrous Croda 8.81
Bentone 34 N.L. Industries 8.26
D&C Red #27 W,C,D 8.00
D&C Red #6 W,C,D 5.81
D&C Red #7 W,C,D 3.07
Titanium dioxide W,C,D 10.63
Preservatives 0.44
Paramount X Durkee 46.46
EE hard fat flakes Swift & Company 2.70
Japan wax Robeco 14.70
'B' wax Int'I Wax Refining 7.70
Bentone 34 N.L. Industries 2.80
D&C Red #7 Sun Chemical 2.22
Flamenco Superpearl 100 Mearl Corporation 21.16
D&C Yellow #6 W,C,D 1.69
Cosmetic brown C33-115 Sun Chemical 0.11
Manganese violet 7101 W,C,D 0.02
Preservatives 0.44
Extrusion The liner bulk is loaded into a cylinder and forced by a piston
through a narrow opening of desired shape and size of the crayon (usually
round). At this point, the crayon is generally soft and flexible, and must
undergo a tempering phase of up to five days before it will reach its optimum
crystalline form. The sticks are then placed in wooden slats, and shaped,
pointed, painted and sharpened.
COLOR COSMETICS 159
4.3 Nail polish
4.3.1 Consumer expectations

Nail polish should be easy to apply, giving a good cover of the nail with
two coats, and should not streak or apply unevenly. The polish should dry
quickly to the touch and leave a high-shine finish film that will not stain the
nail when removed. The film should be sufficiently hard so it will not mar
easily and, during the wear cycle should not chip or peel. Durability and
wear should last for 4 to 5 days. It is particularly important that nail polish
is available in a wide range of colors, cream and frost (pearl), transparent
and opaque. The polish is mostly dispensed from a bottle with a brush
applicator (Figure 4.5).
Sales of nail polish in 1990 were approximately $660 million in the US
and $365 million in Europe.
Figure 4.5 Nail polish bottle.
4.3.2 Formulation
Nail polish, simply stated, consists of pigments suspended in a volatile solvent
in which a film former or film formers have been dissolved. On application,
the solvent evaporates leaving the color and film former on the nail. A
standard nail polish formulation is as follows:
Wt%
Nitrocellulose 112 sec 15.00
IPA 4.50
Polyester resin 8.00
Ethyl acetate 28.00
Butyl acetate 40.00
Bentone 1.00
Camphor 3.00
Color 0.50
Nitrocellulose Although the choice of film former is not absolutely

universal, the vast majority of formulations use nitrocellulose. This is not
accidental for, although it is not perfect, nitrocellulose has a blend of all the
qualities necessary to make a successful product: (i) nitrocellulose films are
quite hard yet remain flexible for a reasonable amount of time; (ii) the films
adhere well to the nail surface, which reduces the occurrence of chipping and
peeling; (iii) nitrocellulose has excellent gloss, which is extremely important
to the consumer; and (iv) nitrocellulose is not totally occlusive to the passage
of water and air, which, according to some sources, eliminates the possibility
of fungal infections in the nail bed. Nitrocellulose is usually supplied as a
solution (lacquer). This limits the high flammability risk of the so-called
dampened material supplied for other purposes. Other polymeric materials,
of which many have been tried, may be superior in one specific attribute of
nitrocellulose but fail badly in some other way. Listed below are some of
the materials that have been tried over the last 60 years. Despite optimistic
claims made for these materials, nitrocellulose remains supreme.
• Cellulose acetate isobutyrate

• Methacrylate and nitrocellulose
• Ethylcellulose and nitrocellulose
• Nitrostarch and polyvinyl acetate
• Polyvinyl acetate and nitrocellulose
• Alkyl vinyl ether-maleic anhydride copolymer
• Methyl or ethyl methacrylate and propyl or butyl methacrylate
• Acrylamide-butyl methacrylate-ethyl acrylate copolymer
• Polyvinyl butyral
• cis-4 Cyclobexane, 1,2 anhydrodicarboxylic acid-2,2 dimethyl 1-3
propane diol copolymer
• Siloxanylalkyl ester-acrylate-methacrylate copolymer
• Polyacrylic and polyethyleneimine crosslinked with polyepoxide
• Cellulose acetate
• Cellulose acetate propionate
COLOR COSMETICS 161
I sop ropy I alcohol ( I P A) Nitrocellulose is generally shipped 70% active in
IPA, therefore IPA is present incidently.
Butyl and ethyl acetate Butyl and ethyl acetates are solubilizers for the
nitrocellulose. By modifying the ratio of the two solvents, the drying time
of the film on the nail can also be modified. Since ethyl acetate is approximately
four times more volatile than butyl, the higher the level of ethyl, the faster
the film will dry. This is often a delicate balance in nail polish formulations- if
the film dries too fast it can cause streaky application and low gloss on the
nail, while ifit dries too slowly it is an obvious inconvenience to the consumer.
Camphor Camphor is a plasticizer for nitrocellulose. Its inclusion
increases the flexibility of the film, reducing brittleness, thus reducing the
potential for film chipping. Dibutyl phthalate is also commonly used as a
plasticizer.
Bentone (Quaternium-18 bentonite) Bentone is used in modern formu-
lations as a suspending agent. Being thixotropic, its 'at rest' viscosity is
relatively high, making it ideal for suspending the pigments. On application,
through the action of a brush or when the bottle is shaken, the viscosity drops,
allowing the user to apply an even film to the nail.
Polyester resin Polyester resin is used as an auxiliary resin to nitro-
cellulose. Its addition improves hardness and increases the gloss of the film.
The following resins have also been used as adjuncts to nitrocellulose.
• Santo lite MHP
• Dammar
• Sandarac
• Pontianac
• Resin and esters
• Ester gum
• Resin and esters
• Ester gum
• Hexyl methacrylate-methylmethacrylate copolymer
• Acrylic ester oligomers
• Alkyd resin
• Polytetrahydrofuran
• Polyamides
• Laurolactam-caprolactam- hexamethylene diamine adipate terpolymer
• Helamine resin
4.3.3 M anu{acture
The manufacture of nail polish involves the high-shear mixing of highly
flammable and volatile materials and, because of this, involves high risk.
Precautions must be taken to ensure that the equipment and premises used
are adequately protected. Both buildings and manufacturing equipment must

be flame-proof and carefully monitored for harmful vapours.
As with all color cosmetic manufacture, pigment preparation is the most
important step. This is particularly true of nail polish since the finer the
pigment is ground, the higher the gloss that will be achieved, and the more
stable the finished product. Pigments for nail polish are usually prepared in
'chip' form. The required pigment is blended with nitrocellulose in a mix of
bent one solution and plasticizer. The resultant mixture is then ground
through a triple roll mill, dried and 'chipped' (i.e. split up into solid fragments).
Although the final product is stable, the process involved is very hazardous,
and explosions are not unknown. As a result, most nail polish manufacturers
prefer to buy the 'chips' already made.
The color chips are blended in the desired shades and dissolved in the
nitrocellulose solution (lacquer) using a high-shear mixing blade (Cowles)
under flame-proof conditions. The temperature must be carefully monitored
to avoid a large increase. The other solvents and additives are added when
a uniform color has been achieved. Following this, the bentone is added
and the viscosity adjusted by addition oflacquer or thinners. Special viscosity
modifying additives are also required. For this mixing, a normal propeller-type
blade may be used.
For convenience, all the materials used may be obtained as solutions in
the mixed solvent base. The operation consequently becomes a single liquid-
blending operation to obtain the correct shade, with appropriate viscosity
adjustment as required. To ensure that the correct shades are achieved and
that the product will remain stable on-shelf, careful control over the
thixotropy and viscosity of the finished product is essential. The quality of
the incoming raw materials must also be carefully controlled. The viscosity
of nail polish is '>ometimes adjusted by adding small quantities of phosphoric
acid or organic acids to modify the gelling system. This is a delicate operation,
which requires very careful monitoring and control shade-by-shade to avoid
unwanted overgelling or loss of viscosity with time.
4.4 Face make-up
Face make-up can be divided into three segments: (i) face powders; (ii) liquid
foundation, and (iii) blushers. In 1990, total sales in the US and Europe were
estimated to be in the area of 3.5 billion dollars. Of this, 46% was for liquid
foundation, 29% was for blush and, 25% was for face powder (Figure 4.6).
4.4.1 Consumer expectations

Face make-up should apply easily to give smooth, even coverage, but a
natural look. The product should blend easily and not settle into the lines
and pores on the face. The shades for foundation and powders should be
COLOR COSMETICS 163
Powder
25%
Foundation
46%
Figure 4.6 Share of face make·up sales (dollars) in the US and Europe during 1990.
plain flesh tone or lightly pearlized for a moist look, while the blush should
be available in a wide range of translucent reds. Changes in fashion and
location will determine different requirements in degree of translucence,
depth, and type of color, and other appearance characteristics.
4.4.2 F ace powders
4.4.2.1 Formulation Face powders are available in loose and pressed

forms-applied with either a brush or puff. A typical loose formulation is
as follows:
Wt%
Talc 80.50
Zinc stearate 3.60
Kaolin 8.80
Magnesium carbonate 2.40
Cosmetic oxide 2.50
Octyldodecanol 2.00
Fragrance 0.20
Preservatives
Talc As in all colored cosmetic formulation bases, face powder is a vehicle

to apply color and, in most formulations today, talc is the major ingredient.
Talc is chosen because of its excellent slip, its transparency, and its light feel
on the skin. Its drawbacks are that it is not very water-repellent, it does not
adhere well to the skin, and is somewhat too shiny.
Zinc stearate Zinc stearate adds the water repellancy to the formulation
and adheres well to the skin. It improves the wear and has a creamy, almost
unctuous feel, which aids the consumer in gaining an even aoolication. Other
metallic stearates, particularly magnesium and lithium, are used to impart

these same qualities. Generally, zinc stearate is added below 10%, since at
higher levels it can cause caking.
Kaolin Kaolin is added to reduce the shine and add a more natural look
to the product lay-down (layer left on the skin).
Magnesium carbonate Magnesium carbonate serves two purposes in the
standard face powder formulation: (i) it has a tremendous capacity to absorb
oil, which helps prevent the formulation from forming lumps; and (ii) it has the
reputation for extending the fragrance topnote-for this reason the fragrance
is often added to the magnesium carbonate as a separate step before its
incorporation into the batch.
Octyldodecanol The octyldodecanol is used to add lubricity to the
formulation and to reduce the possibility of dusting. Since this applies to
the feeling of the powder on the skin, the addition of such an ingredient
depends purely on esthetic considerations. Acetylated lanolin alcohols,
mineral oil, lanolin oil, dimethicone, and a multitude of esters are also used
for this purpose.
Formulations for loose pearlescent face powders can be designed to give
a moist look to the skin. This is generally obtained by incorporating a
nacreous material (e.g. Mibiron N-50). A typical formulation is as follows:
Loose pearlescent
Wt%
Talc to 100
Magnesium carbonate 1.S0
Iron oxide pigments q.s.
Zinc stearate S.OO
Mibiron N-SO* 2S.00
Preservatives
*Rona Pearl
It is generally not necessary to incorporate an emollient since the pearles-
cent pigment itself is a lubricant, and usually a heavy material that dampens
the potential for dusting. It should be noted that the opacity of pearlescent
materials varies considerably and, since most applications require a natural,
moist look, the pearls with the most translucency should be chosen.
When formulating pressed compact powders, the best results are generally
obtained by using low-micron talcs, which compress more easily. In addition,
a compact powder needs to be 'wetter', therefore requires increased levels of
emollient (mineral oil). The disadvantage of zinc stearate in loose powders
(i.e. caking) now becomes an advantage, and its use in pressed powders
improves the ability to press. A typical formulation for a pressed face powder
is shown below.
COLOR COSMETICS 165
Wt%
Lo-micron talc 79.00
Zinc stearate 5.00
Magnesium carbonate 2.50
Kaolin 6.00
Pigments 2.50
Mineral oil 5.00
Preservatives
More recently, several speciality items have become available and have gained
popularity in these types of formulations. Sericite is a special grade of mica
that has replaced talc in some loose and pressed formulations. For the most
part, however, it is used as an adjunct to talc. Sericite repels water better
than talc, and has less slip but a more emollient feel. The use of spherical
silica imparts tremendous slip to any formulation. Its incorporation in pressed
powders also reduces the possibility of 'glazing' - the development of an oily
crust on the surface of the pan. The following formulation illustrates a typical
example of the use of sericite and spherical silicas.
Wt%
Lo-micron talc 76.50
Sericite 14.00
Spherical silica 2.00
Zinc stearate 5.00
Hydrogenated polyisobutene 2.50
Pigment 2.50
Pigments Since the desired effect of a face powder is a natural looking

flesh tone, the chosen pigments are usually inorganic colors. Titanium dioxide
or zinc oxide are used to provide coverage, while iron oxides and ultramarine
blue are used to provide the flesh tones.
4.4.2.2 Manufacture The preferred method of manufacturing a face

powder is by using a PK blender or Gemco-type mixer, although a standard
ribbon blender will suffice. The advantage of a PK or Gemco-type mixer is
that the equipment is designed to lessen the possibility of dead space.
The first step is to mill the pigments. This is usually done by combining
the pigment blend with an equal portion of the talc and pulverizing it through
a hammer mill equipped with a low micron screen. All the other ingredients,
with the exception of the pearls and the liquid phase, are then filled in the
main mixer. When a uniform dispersion has been achieved, the oil phase can
be added. With the PK and Gemco mixers this is done through the central
mixing bar, which sprays the liquid phase on to the powder and reduces the
chances of clumping. With ribbon blenders, the oil phase is often sprayed in
with a nozzle and pump arrangement. Uniform blending is followed by the
addition of the nacreous materials, if required. If pearlescent pigments are

added, the amount of energy required to finish the blending should be as
low as possible since there is a danger of breaking the platelets or at least
coating them with other ingredients, which will reduce their lustre. If it should
be necessary (which can be so when using a ribbon blender) to obtain better
dispersion by passing the batch through a pulverizer, this should be done
through a jump gap or high micron screen. For the same reason, when using
PK and Gemco mixers, the high intensity bars should be avoided as much
as possible.
4.4.2.3 Special considerations During the filling process most powders,

whether loose or pressed, are volumetrically dispensed into their container
from cone-shaped hoppers. Considering this, it is easy to see that control of
the flow and the density of the product are vital to the ultimate cost effective-
ness. This control is not easily quantified, and is usually attained through trial
and error by a team of experienced and skilled operators. Nevertheless, there
Figure 4.7 Scott volumeter. The powder is sifted through the cone. It then falls over a series of
oblique glass plates which serves to randomize the packing into the unit cube receptacle. The
weight of the powder is determined by difference. Bulk density is determined by the formula: bulk
density = weight/unit volume.
COLOR COSMETICS 167
are two evaluations, specifically the bulk and the apparent densities, which
are useful aids to predicting the suitability of a powder to be filled.
Bulk density, measures the weight per unit volume of the loose fluffy bulk.
In practical terms, this test will predict the powders predisposition, in loose
form, to fit into its container. The apparent density is the evaluation of the
propensity of a powder to compress under its own weight. It is really a
measure of the change in bulk density over time or after undergoing a
variable amount of stress. Almost universally, it is an increase in the bulk
density that is being measured. The apparent density is important because it
will give an indication to the manufacturer of how the volume of the loose
powder will change during shipping. Obviously, even though a product may
meet its legal weight, an unesthetic fill height is not recommended.
Meanwhile, both the bulk and apparent densities can be used to predict if a
specific pressed powder bulk will easily compress into its pan and meet its'
legal weight. However, skillful pressing machine manipulation can compen-
sate for some deviation from the standard.
For more detailed information on bulk density the reader is referred to the
'Scott Volumeter Method' ASTM B 329-6 (Figure 4.7) or CTFA Method
C-7-1, and for the apparent density, CTFA Method C-8-2 (Figure 4.8).
Figure 4.8 Bulk and apparent density. The powder is poured loosely into a volumetric cylinder.
The height is noted. The cylinder is then raised manually or mechanically to a fixed height and
then allowed to fall freely. The volume of the powder will decrease as it packs. This process is
repeated until there is no significant change in the volume. The change in volume is noted. The
apparent density is usually written as the percentage of change in the volume.
4.4.3 Liquid foundations

To some degree, liquid foundations could be described as powder base
suspended in liquid emulsion or gel base. They are the most popular type
of face make-up, probably because they are easy to spread, therefore the
coverage can be controlled, and any existent skin blemishes hidden more
easily. They are often sold to suit particular skin types-gels and oil-in-water
emulsions for dry skin, and water-in-oil emulsions for oily skin.
4.4.3.1 Formulation and manufacture The formulations given in this section

illustrate the variability of liquid foundations, and may be used as intro-
ductory formulations that can be worked on to achieve the qualities required.
(i) Henkel formulation: water-in-oil cream, recommended for dry skin

Part Ingredient Wt%
A Glyceryl oleate (Monomuls 90-018) 2.00
Polyglyceryl-3 diisostearate 4.00
(Lameform TGI)
Dioctylcyclohexane (Cetiol S) 10.00
Cetearyl alcohol (Lanette 0) 1.00
Mineral oil 10.00
Pigment colors q.s.
Talc 0.90
B Glycerine 3.00
Magnesium sulfate 0.70
Water to 100.00
C Preservatives, fragrances q.s.
Procedure: Melt part A to 75-80°C. Heat part B to the same temperature and stir
it into the fat phase. After the water has been added, homogenization takes place.
Cool down and stir continuously. Add part C below 40°C and homogenize.
(ii) Goldschmidt formulation: oil-in-water emulsion, good for oily skin

Part Ingredient Wt%
A Steareth-7 (and) stearyl alcohol (and) 9.00
steareth-tO (Emulgator 2155)
Isooctadecyl isononanoate 2.00
(Tegosoft 189)
Isopropyl myristate 9.00
Mineral oil 8.00
Stearyl dimethicone (Abil Wax 9800) 2.50
Dimethicone (Abil tOO) 0.50
COLOR COSMETICS 169
B Water 10.00
Glycerine 2.00
Talc, USP 4.00
Iron oxides 3.40
Ultramarine blue O.1S
C Water 43.45
Preservatives, fragrances q.s.
Procedure: Heat part A to 70°C with mixing. Heat the water and glycerine of part B
to SO°C and grind in talc, titanium dioxide and pigments. Heat the water of part C to
70°C; add to part A. Begin cooling while homogenizing. When homogenized, stir in
part B. With a slow sweep agitation, cool to 30-3S°e. Add fragrance and preservatives.
Slow sweep until cool.
(iii) M earl Corporation pearly foundation: helps produce a natural lustre on

the skin
Part Ingredient Wt%
A Laneth-l0 acetate (Solulan 98) 3.00
Isopropyl lanolate (Amerlate P) 5.50
Acetylated lanolin alchohol (Acetulan) 5.30
Glyceryl stearate SE (Tegin) 3.S0
Stearic acid 2.70
B Propylene glycol 5.00
Water 64.00
C Titanium dioxide coated mica 10.00
(Flamenco Satina)
Procedure: Separately heat parts A and B to 80°e. Stir part B into part A until
homogeneous. Cool to 40°C with slow stirring. Disperse part C into warm base.
(i v) National Lead Industries formulation

Part Ingredient Wt%
A Talc 1621 (W,C,D) 5.00
B Titanox 1020 (TGA)-328 5.00
C Pure oxy yellow 3170 (W, C, D) 0040
D Pure oxy umber 3315 (W, C, D) 0.20
E Lo-micron pink 2511 (W, C, D) 0040
F Water (deionized) 79.95
G Methylparaben (Goldschmidt) 0.25
H Propylene glycol USP 5.00
J Cerasynt 840 (PEG-20 stearate) 2.00
K Bentone LT 1.50
L Fragrance 0.30
Procedure: Blend the powder phase (parts A to F) and pass through a micro-pulverizer.
Heat the water phase (parts G to J) to 6SOC in a stainless steel vessel equipped with
a homogenizer. Adjust the homogenizer to a medium speed and add the powder
phase. Add the bent one and allow to mix for 30 min. Cool the batch before adding
the perfume.
This formulation uses Bentone L T (as an organically modified clay) as its
gelling agent. PEG-20 stearate is added as an emollient. The thixotropic
qualities of bentone allow for excellent pigment-suspending characteristics
and smooth, even application.
Modern formulations often contain volatile silicone oils to improve feel
and application, and sunscreen to protect the skin against ageing effects of
sunlight.
4.4.4 Blushers
Most blushers are currently sold in the pressed powder form, although cream
versions also constitute a significant segment. Liquid blush is very like its
counterpart liquid foundation. The difference is primarily in the choice of
pigments. The goal of blusher is to impart a healthy glow to the skin, therefore
the major difference compared with regular pressed powder is the choice of
pigments.
4.4.4.1 Formulation and manufacture
Pressed powder 1.' Nikko formulation

Wt%
Talc 38.90
Sericite (Nikkol Sericite J) 30.00
Mica (Nikkol Mica G) 5.00
Nylon-12 5.00
Mica (Flamenco pearl) 10.00
Magnesium stearate 3.00
Cetyl octanoate (Nikkol CIO) 3.00
Dimethicone 2.00
Mineral oil 2.00
Propylparaben 0.05
Butylparaben 0.05
Fragrance q.s.
Procedure: Mix all ingredients, except liquid oils and fragrance, in a blender. Spray
or add liquid oils and perfume. Mix and pulverize. Press into pans. (Any blender
suggested for face powder could be satisfactory.)
Pressed powder #2 Wt%

Kaolin 1.21
Lithium stearate 1.94
COLOR COSMETICS 171
Zinc stearate 3.65
Talc 40.09
Magnesium carbonate 1. 70
Iron oxides 12.82
D&C Red #30 lake 4.09
Mineral oil 2.11
Octyl palmitate 1.76
Timica golden bronze (Mead) 15.00
Gemtone amber (Mead) 15.00
Preservatives q.s.
4.5 Eye make-up
Eye make-up consists of three major categories: (i) eyeshadow; (ii) mascara;
and (iii) liners. Total US and Europe sales for 1991 are estimated to be in the
region of2.5 billion dollars (Figure 4.9).
Eyelfner
12%
Other
Eyebrow 3%
6%
Eyeshadow Single pan PWD (b)

(a) 48%
39%
Figure 4.9 (a) Share of eye make-up sales (dollars) in the US and Europe during 1990;
(b) share of eyeshadow sales by form.
4.5.1 Eyeshadow
4.5.1.1 Consumer expectations Eyeshadow should blend easily, give good

coverage, yet look natural. It should be available in a wide range of colors,
matte and frost (pearl), and should not crease when worn.
4.5.1.2 Formulation and manufacture The most popular form of the

eyeshadow is the pressed powder cake, but pigmented creams also constitute
a significant market share.
Pressed powder cakes The formulation will not differ greatly from a
standard compacted pressed face powder, but the range of shades is far more
extensive and frost/pearlescent colors are more popular. A standard
formulation for a pink pearlescent eyeshadow is as follows:
Wt%
Talc 141 17.30
Zinc stearate 7.00
Duocrome RY 40.10
Ultramarine pink 4.40
Ultramarine blue 0.60
Flamenco Superpearl 100 3.00
Timica brilliant gold 19.00
Mineral oil 8.00
Preservatives (q.s.) 0.60
Due to its superior compressibility, a low-micron talc is chosen but, due to

the difficulty in compacting the peariescent materials, the zinc stearate and
mineral oil are present in larger percentages. The following formulation uses
spherical silica for slip, and sericite to improve emolliency and waterproofness.
Part A Wt%
141 talc' 34.676
Sericite S-lOOb 8.00
Press-aid XF b 5.625
Spheron P-1500 b 3.00
Sericite SI-Sb 6.50
PTFE-19 b 1.875
Violet 12b 5.04
Carmine 224b 4.536
Ultra blue 104b 3.312
Ultra pink 113 b 4.536
Methylparaben 0.30
Propylparaben 0.10
Germall 115 C 0.25
Part B
Pearl Ib 18.00
Part C
Permethyl 102A/I04A (50%/50%)b 4.25
Suppliers:
aWhittaker, Clark & Daniels
bpresperse, Inc.
CSutton
Procedure: Combine ingredients of part A and mix well, then pass through micro-
pulverizer. Place back into ribbon-type blender and spray in binder, part C. Pass
entire batch through pulverizer, mix well again while adding pearl, part B. This
can also be pulverized one final pass to keep a smooth consistency and a matte
finish.
Cream eyeshadows Although not the most popular form, these are often
chosen when long wear is desired. The following Sutton formulation
COLOR COSMETICS 173
incorporates a wax-resin base dispersed in a volatile hydrocarbon solvent.
When the solvent evaporates, a relatively water-impervious film will be left
on the eyeshadow lid.
Part A Wt%
Cetyl lactate (Ceraphyl 28) 2.0
Octyldodecyl stearoyl stearate (Ceraphyl 847) 2.0
Beeswax, white 7.8
PVP, eicosene copolymer (Ganex V-220) 6.5
Trihydroxystearin (Thixcin R) 3.5
Petroleum distillate (Shell Sol 71) 33.0
Part B
Petroleum distillate (and) Quaternium-18 14.7
hectorite (and) propylene carbonate
(Bentone gel SS-71)
Zinc stearate 2.0
Magnesium stearate 1.0
328 titanium dioxide 6.0
Talc 141 14.5
Mica (and) bismuth oxychloride (and) ferric 6.0
ammonium ferro cyanide (Chroma-lite blue)
Part C
Germaben II 1.0
Procedure: Combine and mix part A with propeller stirrer while heating to 70°C or
until melted. Add part B ingredients and mix, with homo-mixer at medium speed.
Stir with propeller stirrer while cooling and add part C at 60°C. Cool to just above
congealing point and pack.
The following highly frosted pearlised formulation (Mearl Corporation)
achieves the same effects using a volatile silicone fluid in place of the
hydrocarbon.
Part A Wt%
Acetulana 11.05
Syncrowax HRC b 4.60
Schercemol ICS e 3.00
Part B
Silicon fluid 344d 17.00
Part C
Flamenco Superpearle 21.00
Cloisonne or Gemtone colore 18.00
Part D
Methylparaben 0.20
Propylparaben 0.10
Butylated hydroxy anisol (BHA) 0.05
Part E
Bentone gel SS-71 f 14.00
Part F
Silicon fluid 345 d 11.00
Suppliers:
aAmerchol Div. CPC International, Inc.
bCroda, Inc.
cScher Chemicals, Inc.
d Dow Corning
eMearl Corporation
fNL Industries
Procedure: Heat ingredients of part A to 70°C with gentle stirring until all ingredients
are melted. Remove from the heat and add part B with stirring; then mix in the
pre-blended part C. When all the pigments are thoroughly dispersed, add preservatives
and part D. While stirring, blend in the gel, part E, and, finally part F.
4.5.2 Mascara
4.5.2.1 Consumer expectations A mascara is designed to make the

eyelashes look thicker and longer. Coverage should be good, but the mascara
should not clump on the lashes, flake during wear, or feel brittle after drying.
In addition, the mascara should be tear-resistant, waterproof or water-
resistant, and must not smear or smudge. The most popular color is black
but other dark shades (e.g. blue, green and brown) are also sold.
Mascara is available in two basic categories: (i) water-resistant; and
(ii) waterproof. Total sales in the US and Europe during 1991 were estimated
to be in the range of one billion dollars and over 75% of these sales fall into
the water-resistant category.
Mascaras are now almost universally applied from a tube with a specially
designed applicator (see Figure 4.10). Cake mascaras are now virtually
obsolete.
4.5.2.2 Formulation and Manufacture

Waterproof mascaras Waterproof mascara formulations have changed
very little for many years. For the most part they consist of a blend of waxes
and pigments in a volatile hydrocarbon solvent. The choice of waxes
determines the final characteristics of the formulation. A typical formulation
is as follows:
Wt%
Pigments 5.0-10.0
Beeswax 26.00
Ozokerite 4.00
Lanolin 0.50
Preservative 0.25
Aluminum stearate 2.50
Hydrocarbon solvent to 100.00
COLOR COSMETICS 175
Cap
Stem
Brush
~
U Wiper insert
and seal
Bottle
Figure 4.10 Mascara bottle.
Procedure: Add the aluminum stearate to the solvent with stirring while the mixture
is heated to approximately 90°C. Maintain at that temperature until solution and
gelation are evident. Melt the waxes together and add to the solvent. Grind the
pigments in a portion of the solvent-wax mixture and add to the remainder of the
batch. To avoid settling of pigments while the mixture is still warm and fluid, continue
stirring until the mixture is cool.
Although mascaras of this type are extremely waterproof, they also tend to
be very difficult to remove. This is probably why they are less popular than
the water-resistant types. The following Tevco formulation attempts to
ease removal by combining a mascara solvent in a beeswax borax emulsion.
Part A Wt%
Petroleum distillate to 100.00
Beeswax 18.00
PEG-6 sorbitan beeswax 6.00
Ozokerite 170-D 4.00
Carnauba wax 6.00
Propylparaben 0.10
Glyceryoleate (and) propylene glycol 1.50
Part B
Iron oxides 15.00
Part C
Petroleum distillate (and) Quaternium-18 hectorite
(and) propylene carbonate 12.50
Part D
Methylparaben 0.30
Sodium borate 0.60
Quaternium-15 0.10
Procedure: Mill pigment, part B, into part A, which has been heated to 90°e. After
part C has been added slowly and heated with part A, emulsify by adding part D
at 90°C to the mixture of parts A, Band e. Continue mixing until cool.
Emulsion formulations using morpho line to neutralize a fatty acid oil phase
are also used and are quite waterproof, although they are generally becoming
less popular. The Amerchol formulation shown below is an example.
Part A Wt%
Carnauba wax 1.00
Lanolin acid (Amerlate LF A) 4.00
Isopropyl palmitate and lanolin oil (isopropylan 33) 2.00
Beeswax USP 8.00
Ozokerite 6.00
Part B
Water 37.20
Magnesium aluminum silicate, 4% aqueous 12.50
Cellulose gum 0.70
Part C
Iron oxide pigments lO.OO
Part D
Morpholine 1.60
Water 5.00
Part E
Methacrylol ethyl betainejmethacrylates copolymer 12.00
(Amersette)
Preservatives q.s.
Water-resistant mascaras By far the most popular form of mascaras today

are formulations based on a triethanolamine stearate, or oleate, soap system.
These formulations can be quite water-resistant, feel soft on the lashes, and
are relatively easy to remove. Just as importantly, they also have less potential
to cause eye irritation. The following Tevco formulation illustrates this
approach. The inclusion of hydroxyethyl cellulose in the water phase reduces
the potential to smudge.
Part A Wt%
COLOR COSMETICS 177
Methylparaben 0.30
Ammonium hydroxide, 28% 0.50
Preservative 2.00
Part B
Iron oxides 10.00
Part C
Isostearic acid 2.00
Stearic acid 2.00
Beeswax 9.00
Carnauba wax 6.00
Propylparaben 0.10
Part D
Quaternium-15 0.10
Part E
30% Acrylic/acrylate copolymer 20.00
solution in ammonium hydroxide
Procedure: Mill the pigments of part B in the water phase, part A. Heat to SO°c.
Heat the oil phase, part C, to 82°C. Emulsify. Cool to 50°C. Add part D, then part E.
Cool to 30°C.
4.5.3 Eyeliners
4.5.3.1 Consumer expectations On application, eyeliners should 'glide on'

without tugging or pulling on the eyelid. The color coverage should be good
and should blend easily. The formulations should be such that the depth of
color can be controlled during application. The line should last all day
without smudging or smearing. The color range can be limited to the basic
black, black-blues, greens, and violet.
4.5.3.2 Formulation and manufacture

Wax-based crayons The majority of eyeliner formulations are sold in
woodcased pencil form, although a significantly smaller, but growing segment
of the market is dispensed in the form of a mechanical pencil (Figure 4.11).
Most products are extruded like lip pencils, therefore the manufacturing
process is the same (see section 4.2.3.3). However, as the eye is a more sensitive
area than the lip, the formulations tend to be softer. Typical examples are
as follows:
Ingredient Mit%
Myverol IS-50 (Eastman Chemical) 14.35
Stearic acid 13.86
n
n
:!
, I
!!
Figure 4.11 Mechanical pencil.
Japan wax 13.50

Paramount XX (Durkee) 7.95
Cutina HR (Henkel) 7.44
Softisan 100 (Kay Fries) 4.51
Cutina CP (Henkel) 4.27
Mineral oil 1.59
Miglyol 812 (Kay Fries) 1.29
Talc 141 (W,C,D) 1.17
Neobee 62 (PVO) 1.05
Crodamol W (Croda) 0.82
Veba wax (Dura Commodities) 0.82
Black iron oxides 16.94
Titanium dioxide 3328 (W,C,D) 7.77
Ferric ammonium ferrocyanide 0.89
Mica 1.05
Preservatives to 100.00
Ingredient Wt%
Lipocire CM (Gattefosse) 49.69
Eutanol G (Henkel) 3.91
Polyethylene 6 (Allied) 12.56
COLOR COSMETICS 179
Carnauba (Strahl & Pitsch) 1.66
Japan wax 5.25
Ferric ammonium ferrocyanide 7.00
Titanium dioxide 3328 1.05
Black iron oxides 3.44
Chromium hydroxide green 7.00
Preservatives to 100.00
Liquid eyeliners Liquid eyeliners have recently become more popular due
to the introduction of pen liners. In this package, a wick is soaked with a
liner formulation containing an ultra-fine pigment. This solution is fed by
capilliary action to an applicator nib. The major disadvantage of this system
is that, due to the pigment size necessary to feed the tip, a true black is
difficult to obtain. The system is, however, very convenient to use. The more
traditional liquid formulations remain popular with consumers who like a
darker more defined iine. These formulations are dispensed from a tube by
means of the thin brush. A typical example is shown below.
Part A Wt%
Magnesium aluminum silicate (Veegum) 2.50
Part B
PVP (PVP K-30) 2.00
Part C
Iron oxides 10.00
Part D
Preservative q.s.
Procedure: Slowly add magnesium aluminum silicate to part A water while agitating
with maximum available shear. Continue mixing until smooth and free of visible
particles. Dissolve the PVP in part B water with mild heating. Add part B to part A
and mix until uniform. Add parts C and D in order, and mix until fully dispersed
and uniform.
Very recently, new pen devices using a cartridge system and conventional
pigment technology have been introduced. In these units the formulation is
dispensed to the tip using a shaking motion. For further details of pen devices,
the manufacturers should be consulted.
4.6 Preservation
It is important that cosmetics are adequately preserved, the degree of

preservation being dependent on several variables, which include the nutrient
composition of the formulation, the part of the body to which the cosmetic is
to be applied and the nature of its intended use. For example, a formulator
may wish to be more discriminating in developing a preservative system for
mascara, than say, a face powder. The rationale here is that a mascara is
probably water based, is used around the eye and by the very method of its
use, is subject to repeated insults. By 'repeated insults', it is meant that the
applicator, after use, is returned into the product. Face powders, meanwhile,
although they share this same bane, are anhydrous and are used on a less
sensitive part of the body.
The type of preservative that is to be used is also important. Again, the
composition of the formulation is integral to making this decision as well as
other factors such as the pH of the product, and last, but not least, where the
product is to be distributed and sold. This last point is particularly important
because there is a lack of consensus both regionally and around the world as
to which preservative agents are preferred.
In summation, preservation is a complex issue and certainly cannot be
covered in great detail here. Fortunately, there is aid for the formulator
which comes in the form of supplier's literature and several excellent
reference books. The reader is also recommended to review the October '93
edition of 'Cosmetics and Toiletries', [4] wherein several distinguished
writers cover the topics mentioned here, and several others which are not, in
some detail.
4.7 Color coating
One problem that has always been present in the formulation of cosmetic
products, particularly items which have high solid levels (e.g. pressed
eyeshadow), is the variability of texture from shade to shade. For instance,
a shade containing a high level of pearlescent pigment would feel different
from a product containing an elevated level of, say, iron blue. Consequently,
it is becoming increasingly popular to pre-coat solid materials, particularly
pigments, with a common film. Experience has shown this wili lead to a
more uniform texture across the total shade line. The choice of coating will
also have a profound effect on the final attributes of the product and can,
when skillfully chosen, help the formulator achieve the pre-set performance
characteristics of the finished product more easily. Some of the more common
coatings available are silicone, polyethylene, lecithin, teflon, metal soap, and
dimethicone copolymer. Several of these processes are patented. Details of
available alternatives in this rapidly developing technological area, and ways
of using the materials in formulations can be obtained from pigment and
color manufacturers.
COLOR COSMETICS 181
4.8 General considerations
All cosmetic color products depend on a thorough knowledge of the colors

and pigments used. This is true no matter what product form is being worked
on. The safety, general stability and physical form of the ingredients is of
paramount significance and there is a wealth of detail available from
regulatory offices, suppliers, and trade literature.
The handling of colors and pigments, particularly when producing pres-
sed powders, is of fundamental importance, and the setting of machinery to
obtain the correct product flow and pressure for a stable pressed cake is a
skilled operation. A great deal of attention to trial and error may be necessary
to achieve the correct balance of pigment load and binder for the system
under study. Pilot work is essential in cost-effective development.
Finally, the essence of good formulation is the precise handling of the
colors and color matching. Color matching is a skilled technique only learned
with experience, and a good color matching technician can save a great deal
of time and money in adjustments to products in manufacture. Close attention
must be paid to the consistency of the color shade of the incoming raw
materials; observance of quality control is essential to ensure consistency in
final product.
References
1. Talbot, G. (1990) Fat migration in biscuits and confectionery systems. Confectionery

Production (April) 56 (Issue 4), 255.
2. Laustsen, K. (1991)Thenature offat bloomin molded compound coatings. The Manufacturing
COIifectionery (May) 71 (Issue 5), 137.
3. Bennett, H. (1975) Industrial Waxes. Chemical Publishing Company, New York.
4. (1993) Preservation. Cosmet. Toilet. 108(10) 10.
Further reading
Belgian Patent 892, 174. Anhydrous nail polish containing styrene or unsaturated amide and
acrylic polymers. Assigned to L'Oreal SA (August 17, 1982).
Make-up documentary formulary (1981) Cosmet. Toilet. 96(4).
Make-up documentary (1986) Cosmet. Toilet. 101(4).
Make-up documentary (1989) Cosmet. Toilet. 104 (7).
Gels and sticks documentary (1989) Cosmet. Toilet. 102(10).
de Navarre, M.G. (1975) (Ed.) The Chemistry and Manufacture of Cosmetics, 2nd edn., vol. IV.
Continental Press, Orlando, Florida.
Dweck, A.C. and Burnham C. (1981) Lipstick moulding techniques-comparison and statistical
analysis. Cosmet. Toilet. 96(4).
European Patent Application 199,325 A2. Silyl-containing nail enamel. Schnetzinger, R.W.,
assignor to Revlon, Inc. (October 29, 1986).
Frost and Sullivan (1989) Marketing Strategies in the US Beauty Products Industry. Winter 1989.
Frost and Sullivan (1990) The European Marketfor Make-up Products. Spring, 1990.
German Offen 76,076. Fingernail polish. Kabs, u., Ruehle, R. and Petzoid, 8. (September 12,
1970).
German Offen 2,830,958. Nail polish. Masters, E.l., assignor to Mallinckrodt, Inc. (J uly 15, 1977).
German Offen 2,721,456. Nail polish containing hexyl methacrylate-methyl acrylate copolymers.
Boulogne, J. and Papantoniou, c., assignors to L'Oreal SA (November 24, 1977).
Goldner, T. (1986) Principles of pigment dispersion in color cosmetics. Cosmet. Toilet. 101(4).
Harry, R.J. (1973) Harry's Cosmeticology, 6th edn., vol. I. Chemical Publishing Company, New
York.
Japan Patent 3800. Nail enamel. Uekl, K. (September 19, 1952).
Japan Patent 71,43,400. Nail polish containing acryl ester oligomers. Sugiyama, I. and
Tomozuka, H., assignorS' to Matsumoto Selyaku Kogyo, Co., Ltd., (December 22, 1971).
Japan Patent 79,129,137. Nail polish composition. Assigned to Kanebo KK (October 6,1979).
Japan Patent 80,57,512. Stable nail lacquer compositions. Assigned to Kanebo, Ltd (April 28,
1980).
Japan Patent 81,25,107. Linear polyester oligomer resin as nail polish. Assigned to Asunuma
Sogyo K.K.; Riken Selyu KK (March 10, 1981).
Japan Patent 86,246,113. Nail lacquer containing nitrocellulose, an alkyd resin, sucrose benzoate,
and triethyl acetylcitrate. Yamazkl, K., Soyama, Y., Kotamura, C. and Tanaka, M., assignors
to Shiseido Co., Ltd. (November 1, 1986).
Remz, H.M. (1988) Polymers and thickeners in nail-care products. Cosmet. Toilet. 103.
UK Patent 724,041. Nail polish. Assigned to Cosmetic Laboratories, Inc. (February 16, 1955).
US Patent 2,i73,755. Nail enamel. Fuller, H.C. (September 19, 1939).
US Patent 2,195,971. Fingernail enamel composition. Peter, R.C., assignor to E.1. Du Pont de
Demours & Company (April 2, 1940).
US Patent 2,215,898. Nail polish. Anderson, R.J., assignor to the Vorac Company (September
24, 1940).
US Patent 2,279,439. Lacquer composition. Bowlby, W.8., assignor to Trojan Powder Company
(April 14, 1942).
US Patent, 3,483,285. Human nail coating compositions. Michaelson, J.B. and Criswell, A.F.
(December 9, 1969).
US Patent 3,786,113. Composition containing an acrylic resin, a polyethylenealmine, and a
polyopoxide. Vasslleff, N.I., assignor to National Patent Development Corporation (January
15, 1974).
US Patent 4,097,589. Nail polish. Shansky, A., assignor to Del Laboratories, Inc. (June 27,1978).
US patent 4,283,324. Nail enamel composition. Duffy, J.A., assignor to Avon Products, Inc.
(August 11, 1981).
US Patent 4,545,98. Nail enamel containing polytetrahydroturan as a resin. Jacquet, 8.,
Papantoniou, C and Goetani, Q., assigned to L'Oreal (October 8, 1985).
Wing, H.J. (1975) Nail preparations. In Chemistry and Manufacture of Cosmetics. deNavarre,
M.G. (Ed.) Continental Press, Orlando, Florida, chapter 49.
5 Baby care
1.L. KNOWLTON
5.1 Introduction
Baby cosmetics and toiletries, intended for use on new-born babies and
children of up to five years old, represent a very special category indeed.
They are invariably functional, rather than decorative, mainly concerned
with keeping the baby or child clean, comfortable and healthy. Since babies
and young children are somewhat more vulnerable than their adult counter-
parts, baby products must be carefully formulated to be extremely mild and
gentle to skin and hair. These considerations impose a number of require-
ments and constraints for the design, evaluation and manufacture of baby-
care products. Any person working in the area of baby care must understand
these issues and adhere to them accordingly.
Finally, it is important to recognise that baby products have a significant
part to play in giving an emotive benefit to the user, that is the parent. It is
essential that products used on the young are safe, but the ability to leave the
hair and skin feeling soft and clean, and with a pleasant smell is equally
important in providing emotional support for protective parental instincts.
5.2 Specific basic requirements for baby products
The basic requirements for baby products are very similar to those for
products aimed at the adult sector. However, additional factors, over and
above those normally encountered, must be adhered to and, in the opinion
of the author, the following list indicates the minimum requirements for any
product to be sold in this market sector.
(i) Products should be functional, efficacious and demonstrably capable
of delivering the benefits for which they are purchased. Functionality
should not sacrifice aesthetics, and pleasantness of use is a mandatory
req uiremen t.
(ii) Products should comply with the most stringent standards of safety,
such that they can be used with absolute confidence on even the
youngest skin.
(iii) Products should contain the purest grades of materials available and
the microbiological purity of the finished product should be tightly
controlled to eliminate the risk of infection.
(iv) The levels of dyestuffs and fragrances should be kept as low as possible
so as to reduce the risk of adverse skin reactions. At the present time
an increasing number of fragrance-free products are appearing in the
market.
(v) Preservative levels in baby products should be kept to a minimum,
whilst ensuring adequate preservation to negate the risk of contami-
nation or infection of the user.
(vi) Product packaging should be carefully designed to minimise the risk
of product ingestion or other form of misuse. A number of tamper-
proof or childproof enclosures and containers are available, and
should be used where possible.
(vii) The platform on which the product is marketed should communicate
a high degree of honesty and trust, with emphasis on the benefits of
product purity and performance, rather than ephemeral marketing
claims.
5.3 Product types and their presentation
5.3.1 Baby powders

Powders are amongst the earliest and best known of all baby products, with
a very high level of penetration into the target market. The primary function
of a baby powder is to absorb residual moisture on the skin and to provide
a degree of mild lubrication, thus reducing the possibility of post-cleansing
chaffing and soreness.
The main ingredient in baby powder is normally talc, known chemically
as hydrated magnesium silicate. It is chosen for its unique ability to provide
a high degree of silkiness and lubricity on the skin, due to its unusual morpho-
logy. This property is conferred by the flat, hexagonal, platelet structure of
the talc crystals, which exhibit a low coefficient of inter-particulate friction,
producing a high degree of 'slip'. Raw talc is mined from the earth, therefore
must be purified before it can be safely used. A natural contaminant of talc
from some sources is asbestos, a fibrous material that can produce a fatal
lung disease, known as asbestosis, in humans. Obviously, talc of this type
should not be used. Bacteria, natural contaminants in talc, must be controlled.
Clostridium tetani is the causative organism of tetanus, so the importance of
an effective sterilisation process cannot be over-emphasised. Many methods
of sterilisation have been tried over the years, but that utilising gamma
irradiation is still amongst the most popular [1]. A second method, now
becoming far more widespread in use, is steam sterilisation. This involves
heating the raw talc, under pressure, with super-heated steam at temper-
atures exceeding 120°C for periods of 30 min or more. Whilst this method is
BABY CARE 185
very effective, it is essential to remove any residual moisture from the raw talc
after the sterilisation process, otherwise the likelihood of contamination by
adventitious micro-organisms will be significantly increased.
Some powder products are composed simply of talc and a low level of
fragrance. Many contain other additives, claimed to give the product addi-
tional benefits. Additives that possess a higher degree of moisture absorbency
than talc may be included, making the baby powder more effective. Such
materials include kaolin, magnesium and calcium silicates, and starch-based
products. However, whilst these materials achieve extra absorbency, they
compromise the lubricious feel of talc itself, impairing the feel of the finished
product. This disadvantage can be minimised by careful selection of the
physical form of the absorbent material used. Generally fine particle sizes
with uniform spherical shape should be selected. The inclusion oflow levels
of mild bactericides can improve performance in terms of the prevention of
nappy rash. Powdered zinc oxide, with mild bactericidal properties, is often
incorporated at levels between 1 and 5% for this purpose. A typical form-
ulation for an absorbent baby powder designed to help prevent the formation
ofnappy rash is illustrated below.
Wt%
Talc 77.90
Starch 20.00
Zinc Oxide 2.00
Perfume 0.1 0
Perhaps the best known baby powder on the market today is that from
Johnson & Johnson, which is a high purity talc-based product.
A more recent innovation in this product sector is liquid talc. Typically
between 5 and 15% of talc is suspended in an oil-in-water emulsion, yielding
a product which provides a convenient method of applying talc to a baby's
skin. Apart from the pleasant cooling effect of the product in use, the
elimination of dusting and avoidance of unintentional inhalation of airborne
particles confers additional advantages. A typical formulation for a baby
liquid talc, based on an oil-in-water emulsion, is illustrated below [2].
Wt%
Cyc1omethicone (and) dimethicone 1.00
PolawaxNF* 2.50
Carbomer 980 0.20
PEG-7 glyceryl cocoate 0.50
Talc 12.00
Triethanolamine topH7.0
Water to 100.00
Perfume, preservative, etc. q.s.
* Polawax NF* is a registered trade name of Croda
Chemicals Limited
When formulating a product of this type it is important to ensure that good

application characteristics are combined with sufficiently high viscosity so
that the talc remains homogeneously dispersed within the product, even after
storage at elevated temperatures for extended periods of time.
5.3.2 Lotions and creams

It is impossible to cover every aspect of baby lotions and creams in this
chapter, but the products normally possess one of two primary functions,
cleansing and/or protection. Products designed for cleansing are more
commonly lower viscosity lotions, while those intended to give a protection
benefit are generally higher viscosity creams. Traditional baby-cream products
were heavy water-in-oil emulsions. Their modern day counterparts are more
commonly oil-in-water. Lotions, on the other hand, are nearly always oil-
in-water emulsions, which are more favourable for producing the required
aesthetics and cleansing function.
Classic formulations for protective baby creams were based on mineral
oil or petrolatum, emulsified with an anionic emulsifier such as triethanol-
amine stearate. Such products generally possess a relatively high oil:water
ratio, making them ideal for use in the nappy area after cleansing during
nappy changes. These creams leave a protective film of oil on the surface of
the baby's skin, thus reducing the chances of chaffing and soreness, and
leaving the skin soft and smooth. In addition, water-in-oil creams leave no
sensation of coldness on a baby's skin, as the evaporation of the internal
water phase is retarded by the presence of the external oil phase. A traditional
protective baby cream, based on mineral oil and incorporating an anionic
emulsification system, is illustrated below.
Wt%
Mineral Oil 30.00
Petrolatum 2.00
Stearic acid 1.20
Stearyl alcohol 1.00
Cetyl alcohol 0.70
Water 63.45
Perfume, preservatives, etc. q.s.
Modern baby creams are frequently based on non-ionic emulsifier systems,
and offer protective benefits combined with a high degree of emolliency and
much improved aesthetics. A typical formulation is illustrated below.
Wt%
Mineral oil 15.00
Propylene dicapratejdicaprylate 5.00
BABY CARE 187
Cyclomethicone 100
POE sorbitan monostearate 1.50
Sorbitan monostearate 1.00
Glycerine 2.00
Water 72.50
Perfume, preservatives, etc. q.s.
A special type of protective baby cream, yet one that nevertheless consti-
tutes a very important market sector, is that designed to help the prevention
of nappy rash. Nappy rash is a painful inflammatory condition, normally
found in the anogenital area of the baby's anatomy. The aetiology ofnappy
rash is subject to debate but the main causative factor is widely accepted as
the microbiological breakdown of urine and faecal constituents into irritant
materials, principally ammonia, which are subsequently held in close contact
with the baby's skin by the nappy itself. An effective nappy rash cream must
therefore be formulated to provide good barrier properties and to inhibit the
proliferation of bacteria and fungal micro-organisms in the occlusive nappy
area. Products of this type are typically water-in-oil emulsions that are able to
provide an effective barrier against moisture and chemical attack, with the
inclusion of actives such as zinc oxide, hexamidine and benzalkonium
chloride to reduce the levels of micro-organisms present. A typical water-in-
oil nappy rash cream, containing zinc oxide, is illustrated below [2].
Wt%
Petrolatum 13.00
Mineral oil 15.00
Sorbitan isostearate 2.00
Glycerine 4.50
Zinc oxide 7.00
cx- Bisabolol 0.20
Magnesium sulphate 0.70
Lactic acid/ sodium lactate buffer topR 5.5
Water to 100.00
Perfume, preservative, etc. q.s.
Baby lotions are invariably lower viscosity oil-in-water emulsions, with
the internal oil phase of the product providing the cleansing property. Mineral
oil, with the ability to cleanse by solubilising fats and other lipophilic sub-
stances found on the skin, is the most favoured base. Most cleansing lotions
also contain emollients to leave the skin feeling soft and smooth after use.
Water, present in the product as the external phase of the emulsion, provides
a fresh, cooling sensation during use, due to the rapid evaporation of water
vapour from the skin's surface. Mixed non-ionic surfactants, frequently used
for emulsification of lotion pr9ducts, offer maximum degree of flexibility in
formulation design. A typical formulation for a baby lotion cleanser is
illustrated below.
Wt%
Mineral Oil 12.00
Dimethicone 2.00
POE sorbitan monooleate 1.20
Sorbitan monooleate 0.70
Water 81.60
Perfumes, preservatives, etc. q.s.
5.3.3 Soaps
Soap, one of the earliest methods of cleansing the body, is normally a mixture
of alkali metal salts of long-chain fatty acids. Triglycerides, for example
tallow, palm oil and coconut oil, provide the basic 'fats' from which the fatty
acid mixtures used for soap are derived. The finished soap properties are
primarily dependent on the mixture and ratio of triglycerides used. Tallow,
for example, gives a much harder soap than coconut oil. Potassium soaps
are much softer than their sodium-based counterparts, although, in practice,
they are rarely used. The finished soap bar can be modified by the addition
of other ingredients, such as emollients, opacifiers and chelating agents.
Although there is no evidence to suggest that soap is harmful to a baby's
skin, its very alkaline pH (typically 9-10) is a disadvantage, and is implicit
in the drying effect that soap is considered to have on skin. Consequently,
baby soaps often contain emollients or superfatting ingredients (to help
minimise the drying effect), white colour and low fragrance levels.
This disadvantage of soap led to the development of a new type of cleansing
bar, with mild properties and superior skin-feel, ideally suited for babies and
young children. Such products, commonly known as 'syndet' bars, are made
from synthetic detergents, most of which are based on isothionate or sulpho-
succinate systems. Various additives, including plasticisers, binders and lather
enhancers, can be added to the product to modify the properties of the
finished bar.
The mildness of the syndet bar is largely attributable to its 'neutral' pH
(5-7). To date, syndet bars have not widely penetrated the market, particularly
the baby-care market, for two main reasons: (i) they are much more difficult
to manufacture than their soap-based equivalents; and (ii) the production
costs are between three and five times that of soap. Syndet bars marketed
as baby products should be white in colour, not discolouring with age, and
should contain minimum practical levels offragrance, thus ensuring maximal
consumer perception of mildness in use.
5.3.4 Hair products

In the context of baby use, hair products can be strictly limited to shampoos
BABY CARE 189
and conditioners, the former being far more important than the latter. The
most important requirements are mildness and low eye-sting potential. The
latter is particularly relevant since the blink response of babies and young
children is not fully developed and gives no protection to the cornea against
contact with external substances. The low activity of a baby's sebaceous
glands means that the potential for soiling of the hair is not particularly
high, therefore the cleansing requirements for an effective product are not
too severe.
Mildness is normally achieved through the use of non-irritating surfactant
systems, all of which have limited detergency properties. One of the earliest,
and perhaps still the best known baby shampoo, is that from Johnson &
Johnson. This product was the first to make extensive use of amphoteric
imidazolines, blended in specific ratios with milder types of alkyl ether sulphate.
This combination was used in conjunction with selected non-ionic surfactants
to give the now famous 'no more tears' claim.
In more recent years, many new amphoteric surfactants have been developed,
allowing much greater flexibility in the formulation of mild baby shampoos.
Amphoteric betaines and anionic sulphosuccinates, in combination with alkyl
ether sulphates (3 or 4 moles ethylene oxide) produce detergent systems for
mild shampoos. Much attention has also been given to effective irritation
mitigants which, when added to already mild surfactant systems, further
ameliorate the potential for adverse reactions in the eye. Classically, both
sorbitan and sucrose fatty acid esters have been used for this purpose. A
typical formulation for a mild baby shampoo is illustrated below.
Wt%
Sodium lauryl ether (3.0) sulphate, 70% 6.00
Cocamidopropyl betaine, 30% 12.00
Polyoxyethylene (80) sorbitan monolaurate 6.00
Polyethylene glycol distearate 1.50
Water 74.50
Perfumes, preservative, colour, etc. q.s.
In recent years there has been increasing concern over the potential toxicity
of I,3-dioxane, an impurity found in most ethoxylated surfactants. Con-
sequently, baby shampoos based on detergent systems containing only
amphoteric surfactants have been developed. The perceived need for this
change is largely unfounded however, as levels of dioxane found in modern
ethoxylated surfactants materials are very low indeed.
With respect to hair conditioners, it must be recognised that the primary
function for baby use is detangling, rather than conditioning per se. A baby's
hair does not require conditioning in the same way as that of an adult as it
has not been subjected to regular combing and styling treatments. The
detangling attributes are, however, extremely important, as even gentle
combing after washing can result in knotting and breaking, causing dis-
comfort and distress for the child. As a result, conditioning agents in baby
conditioners are chosen for their ability to impart good wet-combing and
slip characteristics, rather than to improve dry hair properties~the main
aim of adult products. Relatively low levels of quaternary ammonium salts,
such as distearyl dimethyl ammonium chloride are used to achieve this
objective. A typical formulation for a baby hair conditioner is illustrated
below.
Wt%
Distearyl dimethyl ammonium chloride 2.00
Ethoxylated stearylamine 0.30
Cetyl alcohol 1.50
Water 95.40
Whilst the potential for eye sting from a conditioner is significantly less
than that for a shampoo, mildness should still be paramount in the formula-
tors mind. Typically, quaternary ammonium salts with higher molecular
weight hydrophobic chains offer the best potential for mildness on the eye,
due to their increased molecular size and distribution of the cationic charge.
A material of this type which has more recently become popular is
behentrimonium (C 22 ) chloride.
5.3.5 Bath products

Baby bath products must provide both gentle cleansing action, and pleasant
aesthetics for mother and baby during the bathing process. Like baby shampoos,
baby bath products need not possess high activity, as the extent of soiling
of a baby's skin will be low by comparison with that of an adult.
The primary requirement of a baby bath is that it should be functional,
yet mild on the skin, and be as non-drying as possible. When diluted in bath
water, the product is often used to shampoo a baby's hair, therefore low eye
irritancy is essential. For this reason, baby bath formulations generally
contain low active detergent systems composed of mild alkyl ether sulphates
(3 or 4 moles ethylene oxide) combined with a relatively high ratio of imidazo-
line or betaine foam boosters. In this way, sufficient quantities of light, open
foam for the cleansing process, with no significant drying of the skin at the
in-use dilution, is obtained. The viscosity of the product should be such that
easy and rapid dispersion in the bath water is possible with minimum agitation.
A perfume level as low as possible, but sufficient to generate a pleasant odour
in use is desirable. Additional ingredients may be used to minimise any drying
effect and enhance the softness and feel of the skin after use. Many materials
are claimed to be beneficial. Care must be taken when selecting hydrophobic
oils for this purpose, so as not to impair foaming characteristics. A popular
means of enhancing moisturising properties is to include low levels of polyol
BABY CARE 191
fatty acid esters, with which a minimal effect on the foaming capability of
detergent systems, and considerable enhancement of pleasant skin-feel may
be achieved. The formulation shown below illustrates this.
Wt%
Sodium lauryl ether (3.0) sulphate, 70% 5.00
Lauryl betaine, 30% 8.00
PEG-7 glyceryl cocoate 2.00
Water 84.50
Electrolyte (viscosity builder) 0.50
A second, although much less important category of bath product, is baby
bath oil. Here the emphasis is on mildness rather than cleansing, although the
use of such products does provide a pleasant means of removing superficial
soil from the baby's skin in a bath environment. A simple baby bath oil
formulation is illustrated below [2].
Wt%
Caprylic/ capric triglyceride 80.00
Polysorbate 85 20.00
Perfume, preservative, colour, etc. q.s.
5.3.6 M oussed products

The term 'mousse' normally refers to a product that is filled into a sealed
container, which is press uri sed with a propellant that serves both to 'mousse'
the product, and to expel it from its pressurised container. Mousses offer
novel ways of improving the convenience of baby products, particularly in
view of their suitability for single-handed operation. They also offer the
advantage of being 'pre-foamed' at the time of dispensing, providing significant
in-use benefits for baby shampoos and body cleansing products. However,
at the present time, there are very few moussed baby products on the market.
The reason is unclear, but the additional cost, the historical connection with
adult hair-care products, and the potential danger of pressurised containers
if misused, may be significant factors. An early product was 'Care For Kids'
baby shampoo mousse, launched in the US by the Revlon Group in the mid
to late 1980s. Despite views that this would lead to an increased demand
for similar products, the market remains largely undeveloped.
Products available in the market today are principally skin care mousses,
where the functional benefit is moisturisation rather than cleansing. These
formulations are normally based on low viscosity oil-in-water emulsions,
utilising an oil-soluble propellant system, which provides an instantaneous
creamy foam when the product is dispensed.
When formulating baby mousses, the safety considerations normally
associated with baby products are paramount. In particular, the propellant
system chosen must present no hazard to a baby's skin or respiratory system,

even under conditions of predictable misuse.
5.3.7 Wipes and tissues

Baby wipes and tissues represent one of the fastest growing sectors of the
baby products market. There are essentially two types of baby wipe, categorised
by function of either 'cleansing plus freshening' or 'cleansing plus moisturising'.
The first type are normally 'aqueous' wipes, while the latter are referred to
as 'lotion' wipes, depending on the nature of the wipe impregnant. The wipe
itself is normally made from paper or fabric, the latter offering improved
strength and aesthetics over the former, at higher cost. Paper substrates may
be either 'wet-laid' or 'air-laid' and are manufactured in different weights,
depending on the properties required. Fabric substrates come in a variety
of different materials, including viscose-rayon, cotton, or various combinations
of the two.
Aqueous wipe impregnants are composed largely of water, with the addition
of solubilisers to improve cleansing properties and assist in the stabilisation
of low levels of fragrance. Lotion wipes, normally much more effective in
cleansing than their aqueous-based counterparts, are generally stable, low
viscosity oil-in-water emulsions, the internal phase of which provides the
cleansing and moisturising properties. Emollient esters and silicones are
often added to enhance post-use skin feel. A more recent innovation is the
antibacterial or 'total care' lotion wipe. These formulations contain low
levels of bactericidal agents which are included to help in the prevention of
nappy rash. Additionally, water-repellent materials may be added to help
protect the skin in the advent of nappy soilage. The production of a safe and
effective wipe product, with adequate preservation throughout the expected
shelf-life, is a problem. A wipe with a high water content provides an ideal
environment to support microbial growth, if contaminated with adventitious
micro-organisms. This is discussed more fully in section 5.8.
5.3.8 Oils
Traditional oils, offering gentle and effective cleansing, particularly in the
nappy area, are one of the oldest forms of baby product. The oil itself has a
softening and moisturising effect on the skin, the residual layer affording
some barrier protection against subsequent nappy soilage.
Historically, product design has been simple and straightforward with high
purity, low viscosity mineral oil enjoying almost universal use. Additional
ingredients are usually restricted to fragrance and a small quantity of solubiliser.
A major disadvantage is the inevitable greasiness in use. Overcoming this
problem by the use of 'degreasing' additives, for example low levels of fumed
silica, have not been successful.
BABY CARE 193
Recently the design approach to baby oils, motivated by the requirement
to deliver an effective cleanser with improved aesthetics and lower greasiness,
has changed. Many methods have been tried, one of which is the extensive
use of vegetable-based oils such as soya-bean oil, jojoba oil or palm kernel
oil. Although these are not such effective cleansers, they are often perceived as
being less greasy. They are, however, more readily oxidised, leading to
rancidity and malodour.
Contemporary baby oils use another approach to improve product aesthe-
tics. High purity mineral oil is mixed with light esters, volatile silicone oils
or mixtures of the two. Esters, for example isopropyl myristate, 'dilute' the
greasy effects of the mineral oil, while volatile silicones, such as cyclo-
methicone, evaporate rapidly from the skin's surface after application,
leaving behind a thinner oil layer. A light, non-greasy baby oil may be
obtained using the following formulation.
Wt%
Mineral oil 70.00
Octyl palmitate 5.00
Isopropyl myristate 10.00
Cyclomethicone 15.00
Perfumes, solubilisers, antioxidants, etc. q.s.
5.3.9 Perfumes and colognes

The popularity of perfumes and colognes for baby use varies in different
parts of the world, more so than with any other product. The prime function
of a perfume is to leave a pleasant odour on the baby's skin. A cologne
achieves a lesser but similar effect, while simultaneously cooling the skin.
Not surprisingly, colognes are particularly popular in hot countries,
especially parts of southern Europe around the Mediterranean, where they
are often applied several times a day to cool the skin and alleviate discomfort
caused by heat. Most baby colognes are water-based products, containing
low levels of fragrance and a solubiliser to assist with fragrance dispersion.
Other additives include plant extracts, said to impart soothing benefits to
the skin. Microbiological contamination from these materials may be a
hazard. The cooling effect of the cologne can be greatly enhanced by the
addition of relatively low levels of ethyl alcohol. This is rarely done because
of the adverse drying effects of alcohol on the skin.
When formulating baby perfumes and colognes, product safety must be
the prime concern. Of all cosmetic ingredients, fragrances are most
commonly associated with skin allergies and sensitisation reactions. It
follows therefore, that any fragrance compound selected for use in this type
of baby product should be subjected to the most rigorous safety assessment,
before commercialisation is contemplated.
Perfumes for babies are controversial, as the 'image-led' marketing strategy
for perfumes and fine fragrances has little relevance for babies, whose social
interaction is confined primarily to that of the parent-child relationship.
Nevertheless, perfumes and fine fragrances for babies are currently very
popular in some parts of Europe, notably in France. Obviously, babies and
young children are not sufficiently developed to determine their own social
image through the fragrances they wear. Perhaps the perceived need for this
type of product is driven largely by the parents' desire to extend their own
social values to their offspring.
5.4 Raw materials for baby products
The prime requirement for any baby product is absolute safety. Great care
should be taken that raw materials used are not only efficacious but also
innocuous, with no incidence of irregularity in their toxicological profile.
Only the purest grades of material should be selected, and careful attention
paid to the types and levels of any impurities that may be present. This is
increasingly important with the current use of pesticides, antioxidants and
preservatives, with which even low levels of contamination in the raw material
may be potentially harmful to a baby's delicate skin. If any doubt is
encountered over raw material selection, significant confidence can be gained
by the use of materials which conform to the requirements of the British
Pharmacopoeia (BP), European Pharmacopoeia (EP) or the United States
Pharmacopoeia (USP). Specifications must encourage tight control over the
quality of materials used, such that confidence in the batch-to-batch
consistency is high. The concentrations of raw materials must be carefully
chosen to eliminate all risks, even of minor skin reactions. The comedogenic
nature of any material destined for use in baby products must also be
considered. The 'comedogenicity' of a material describes its potential to form
comedones, or 'spots', on the skin. Use of comedogenic materials should be
avoided.
Particular diligence is required in the selection of raw materials for deter-
gent-based products, which, by their very nature, exhibit a higher propensity
for irritation of the skin. Even the so-called 'mild' detergents will extract
natural lipids from the skin's surface layers. The formulator's skill in selecting
a synergistic blend of detergent materials that exhibits lower irritancy than
its component parts is particularly valuable. Materials used should exhibit
very low microbial counts, and the absence of any micro-organism that can
be classified as pathogenic is mandatory. This is particularly relevant in the
case of talc, starches, natural gums and plant extracts, where high levels of
contamination by micro-organisms, sometimes pathogenic, are known to
occur.
Of particular importance is the quality of water used. The purity of this
ingredient, a major component in the vast majority of products, often over-
BABY CARE 195
looked, is one of the most common causes of problems in the finished product,
particularly those of a microbiological nature.
5.5 Developmental pathways
5.5.1 Formulation development

Formulation starts with an evaluation of the marketing concept and accom-
panying brief, clearly identifying the product de9-ign. Early developmental
work will focus on establishing a 'base formulation', which can be progressively
modified to satisfy the product brief. This base technology can be derived
from many sources, including the formulator's personal knowledge, prior
technology of a similar type, or the vast quantity of guideline formulations
available in raw material suppliers' literature. Product prototypes, satisfying
as closely as possible the performance requirements of the original brief are
then submitted for initial evaluation of product efficacy, preservative
efficacy, product stability and product safety. At this stage, the manufac-
turing process should be studied (see section 5.10). Optimisation of the
product, and subsequent full evaluation, aids the decision as to whether or
not to launch the product.
5.5.2 Practical requirements

Although developmental pathways can be precisely defined, practical require-
ments for any new product development must be observed. Aspects of safety
have already been highlighted as mandatory. In addition the formulation
must support the marketing concept, allow easy and convenient use of the
finished product, and be compatible with the chosen packaging presentation.
The product should meet the defined cost targets, allowing effective marketing
of the finished product, while offering the purchaser a high quality product
at a realistic price.
5.6 Product evaluation
Product evaluation is an integral step in any new product development

exercise. Three main techniques are used to ensure that the product meets the
defined performance criteria.
5.6.1 Laboratory evaluation

Laboratory techniques are used to evaluate early development prototypes
and, by screening formulations, to assist in the development process before
progressing into more sophisticated and expensive evaluation exercises. The

many established laboratory techniques available may be modified to suit
the formulator, and to extend the range of possibilities. Viscosity, density
and pH are readily determined using simple instrumental techniques, and
can help to identify correct product design rapidly. In the development of
detergent products, the Ross-Miles test is a useful means of determining the
quantity and quality of foam generated by products in-use. Skin absorption
characteristics for emulsion-based products can be predicted through careful
selection of raw materials, combined with rheological evaluation in the labor-
atory. In baby products co'ntaining active ingredients, for example nappy-rash
creams, the active material can often be measured spectrophotometrically to
determine its availability in the product base.
5.6.2 Mother and baby panels

While useful data on product performance may be obtained with laboratory
techniques, the most meaningful tests are in-use studies. Classical in-use
evaluation techniques involve either panel or consumer testing, but assessment
of baby products presents a special problem in that the end-user, the baby
or child, is frequently unable to express an opinion. For this reason, a common
technique for evaluating the performance of baby products is to use mother
and baby panels. These panels may be conducted with the assistance of the
local health clinic. The mother uses the test product on her child for a fixed
period of time and subsequently acts as the respondent for the research
exercise. The mother may also use the product on herself, yielding valuable
information regarding the performance of the product on adults, and
providing an opinion of the suitability for the baby. This format is one
of the most valuable ways of assessing product performance since it is the
mother, and not the child, who will ultimately buy the product.
Clinical trials use the same methodology as mother and baby panels but
are carried out with a higher degree of medical supervision, monitoring the
possibility of adverse skin reactions. Such trials, which normally utilise 50
to 100 respondents, are particularly useful when assessing the performance
of 'active' products, such as nappy-rash creams.
Finally, it is essential to note that adequate product safety must be obtained
for the product under test before any evaluation using mother and baby
panels is undertaken.
5.6.3 Consumer research

For the reasons outlined earlier consumer research, the final evaluation step
prior to launch of the product, is not always used for baby products. It can,
however, provide certain information that the mother and baby panel cannot.
BABY CARE 197
The most valuable data is information about the acceptability of branding
for the product. In all human evaluation trials, informed consent must be
sought before starting the test, and requirements for product safety must not
be compromised in any way.
5.7 Product safety requirement
The need for the highest standards of product safety for baby-care products
has been emphasised throughout this chapter. Notwithstanding, there are
legal requirements for any toiletry product to be safe, for use as intended,
throughout its shelf-life. There is, however, no defined evaluation programme
for determining the safety of a product, and this decision is therefore left to
the individual. The legal aspects must, of course, be observed but with baby
products there is also a high degree of emotive importance in ensuring product
safety. This must always be remembered. The perception of vulnerability of
babies or young children, and the need to protect them from anything harmful
is very strong.
A testing programme, ensuring that the product meets these high standards
of safety, is not easy. Historically, such programmes may have included a wide
variety of safety tests, culminating with evaluation using animal studies. This
apprdach is expensive and time-consuming, and intense concern has been
expressed over the unnecessary use of animals in safety evaluation. Con-
sequently, it has become increasingly feasible to devise a testing programme
that avoids animal testing altogether, yet provides a high degree of confidence
in product safety. When adopting this approach, careful selection of raw
materials and close examination of their toxicological profiles is essential.
Fragrances used must conform, as a minimum requirement, to the guidelines
laid down by IFRA (International Fragrance Research Association) and
RIFM (Research Institute for Fragrance Materials). If sufficient toxicity data
is lacking, an increasing number of in vitro tests are available to determine
product safety. For example, cytotoxicology, using various cell cultures, has
already been successfully employed to determine the irritation potential for
detergent-based products such as baby shampoos.
When reasonably satisfied with toxicological safety data, studies on human
volunteers are normally conducted using adults, not babies. Occlusive patch
testing and arm immersion studies are often used to gain more knowledge
about the safety profile of a product. Should circumstances demand, a number
of more sophisticated methods are available. Human volunteer programmes
should reflect the in-use situation, and be carried out over minimum period
of two weeks. Testing on babies or young children may then be considered,
but must only be carried out under strictly monitored conditions, such as
the mother and baby panels referred to in section 5.6.2.
5.S Product preservation
Product preservation is necessary for two reasons: (i) to prevent the product
becoming contaminated during use; and (ii) to protect the user from the
possibility of harmful infection. Preservation is particularly relevant in baby-
care products often used around the nappy area, where there is normally a
high incidence of faecal micro-organisms such as Escherichia coli. The
potential for contamination of the product and reinfection of the user at a later
date is high.
By definition, all preservatives are harmful to living organisms, therefore
should be used with extreme caution. A full review of available toxicological
data on any preservative used in baby products is mandatory. The preservative
level should be kept as low as possible, consistent with adequate activity.
Higher preservative efficacy can often be obtained by utilizing the broad
spectrum and synergistic activity of preservative blends. In order to minimise
total preservative addition levels in a product, it is essential that the raw
materials used are microbiologically as clean as possible. A minimum micro-
biological specification of less than 100 colony forming units (cfu) per gram
is recommended and absence of pathogens is essential. The practice of
over-preservation of a product to compensate for poor manufacturing
practice must be avoided, particularly in the case of baby-care products.
Preservative efficacy testing is essential. The microbiological quality of
toiletry and personal-care products is covered by recommendations and
guidelines issued by the CTPA (Cosmetics, Toiletries and Perfumes Association)
in 1975 [1]. The reference to baby products specifies less than 100 cfu per
gram of product, and absence of pathogenic organisms.
Finally, the media often confounds the issue of product preservation. A
particular preservative can become 'unfashionable' overnight, sometimes
causing irreparable commercial damage to any products containing it.
However, the temptation to produce 'preservative-free' products should
be avoided, as the potential for harm to the user, through product contami-
nation, far outweighs the risk of adverse skin reactions to the preservative
system.
5.9 Product stability
Before a product can be launched, the producer must ensure that it will remain
in good condition, be safe to use, and fulfil its intended function throughout
its envisaged shelf-life. In terms of safety, this shelf-life may be defined as
three years. Consequently, product stability is an essential consideration when
any new product is developed. Clearly, since it is not practical to wait three
years before launching a product, it is necessary, as far as is reasonably
practical, to predict the product stability. The most common technique is
BABY CARE 199
an accelerated ageing study, which is similar for baby and adult products.
Product parameters, such as appearance, odour, viscosity, density and active
matter, are measured and the product is then stored under a wide variety of
conditions, for a period of time. The minimum recommended number of
storage conditions are listed below.
(i) Freeze thaw cycling (- 30°C to room temperature; six cycles)
(ii) Storage at 5°C
(iii) Storage at room temperature in darkness
(iv) Storage at room temperature in the presence of UV light
(v) Storage at 40°C
Periodically, for example one month intervals, products stored under
these conditions are reassessed and changes in measured or sensory attributes
checked. During this exercise, microbiological challenge tests are carried out
on product stored under various conditions, to see if preservative efficacy
has been affected. The decision determining suitability for launch is largely
arbitrary; the longer the test duration, the lower the risk in the marketplace.
For baby products, maximum levels of caution are advised, and successful
completion of ageing studies of not less than three months, and preferably
six months, should be considered mandatory.
5.10 Manufacture and quality control

5.10.1 Manufacture
The production of baby products, or indeed any cosmetic or toiletry, is
normally a simple process. It involves the mixing of the required raw
materials, perhaps with heating and cooling, in a variety of ways. Of
paramount importance for baby products are the procedures used, general
cleanliness in the production area and compliance with GMP (good
manufacturing practice) guidelines.
Mixing vessels used for manufacturing baby products should conform to a
number of fundamental requirements. Fabrication should be of high quality
stainless steel, at least grade 304 and ideally grade 316, and should have the
optimum configuration for producing a wide variety of products. Steam-
jacketed vessels, with a simple impeller and some form of high-shear mixing
device to produce emulsions, are a good starting point. Vessels should be
maintained in a clean condition and should be sanitised regularly, according
to defined procedures. Associated pipework should not contain any 'deadlegs'
and must be continually cleaned and sanitised. Scoops and stirring paddles
used fur mixing should also be fabricated from stainless steel and should be
kept clean and dry at all times. Control of raw materials and manufacturing
processes must be specified according to GMP requirements, and all
personnel should be adequately trained.
Finally, the quality of water used for the manufacture of baby products
should be of the highest order. Water should be chemically purified using a
two-stage deionisation plant, and microbiological integrity may be obtained
through the use of ultra filtration and UV irradiation treatment.
Water for the manufacture of baby products should be used immediately
after purification, ideally on demand and should on no account be stored in
static containers prior to use. Finished bulk product should be filled immedi-
ately into the primary packaging in order to preserve product integrity. If
finished bulk has to be stored for any length of time prior to filling, purpose-
designed hygienic storage containers should be used.
5.l0.2 Quality control

Quality control, the final, extremely important process before a product
is released for general sale, must ensure that all product leaving the factory
meets the required specification. There is currently an increasing emphasis on
quality assurance rather than quality control, the essential difference being
to monitor the entire manufacturing process rather than to measure the
product it produces. This is the approach of total quality management, and is
nowhere more relevant than in the production of baby products (see
chapter 10).
References
1. CTPA (197 5) Cosmetics, Toiletries and Perfumes Association.

2. Croda Formulary I (1994) Baby Care. Croda Chemicals Ltd.
Further reading
Harry, R.1. (1982) Harry's Cosmeticology. 7th edn. Longmans, London.

Love, P.M. (1989) What Makes Baby Different? Unpublished presentation to the Society
of Cosmetic Scientists of Great Britain.
6 Afro products
1.F.L. CHESTER
6.1 Introduction
This chapter deals specifically with cosmetic products designed for use by
people of African origin. Intensive research and development of products in
this field during the 1980s has resulted in the acceptance and recognition of
this class of product as a legitimate, and now established part of the general
skin, and in particular hair care market. The development of such products is
therefore a relatively recent consideration. It must above all take into
account fashion and the different characteristics of the skin and hair of this
ethnic group.
6.2 Hair structures
The fundamental properties and chemistry of hair are outlined in chapter 2.

The purpose of the present chapter is to point out important differences
that have a bearing on the approach to formulating Afro products.
First impressions suggest that Caucasian and Afro hair are structured very
differently, Caucasian being straight and Afro tightly curled. Under the
microscope, however, the two hair types appear similar, except that Afro hair
is somewhat elliptical in transverse section whereas Caucasian hair is
circular. Chemical analysis reveals that the amino acid contents are very
much the same. The distribution of sulphur-containing amino acids,
however, is different and accounts for the structural variations that give rise
to the quite different appearance. In wavy, tightly curled hair there is a non-
uniform distribution in that the disulphide bridges are more prevalent on one
side of the hair fibre.
The principal reason why specific products are required for treatment
of Afro hair lies in the widespread use of chemical treatments to
restyle or straighten it. These treatments rupture the bonds that link
protein fibres, and thus weaken the structure of the hair. Indeed, the more
drastic treatments, which cleave peptide bonds, can cause the destruction
of the fibres themselves. Consequently, formulations must be chosen with
specific recognition of these facts. Products in this range can be divided into
three categories: (i) products for preconditioning, which ensure well-
conditioned hair prior to subsequent chemical treatments; (ii) less-aggressive

chemical treatments than those normally designed for the straightening
process; and (iii) products that will restore lustre, body and moisture content
to chemically treated hair.
6.3 Skin characteristics
In contrast to the relatively subtle chemical differences between Caucasian

and Afro hair, there are more fundamental differences in the skin types.
These must be considered when designing products for the care and
decoration of the skin.
Colour is the most obvious difference and is due to the variation of
pigments-haemoglobin, carotene and melanin-in the epidermis. The level
of melanin is the crucial factor in determining the colour of skin. The greater
quantity of melanin in black skin is due to the greater activity of the melano-
cytes that produce the grains of melanosomes. These 'mature' into melanin
in the epidermis, developing from colourless to black and moving closer to
the skin surface. In white skin the maturing process occurs only to a limited
extent, and smaller, round melanosomes tend to clump together in bundles.
In black skin the larger, oval, mature melanosomes are singly dispersed and
evenly distributed throughout the epidermis giving it its characteristic colour.
There is considerable variation in the quantity of melanin present in 'black'
skin, and this gives rise to a much wider range of skin tones. Consequently,
in order to represent the full range of skin tones found in dark-skinned
people, some 35 shades are required.
Black skin characteristically possesses a tough outer layer of the epidermis.
This is prone to scarring, which can result in serious disfigurement (see below).
Black skin also contains a greater number of sebaceous glands than white
skin (40-60% more). This does not, however, automatically result in more
oiliness, although it often produces a shiny surface. All basic skin types (dry,
sensitive, normal, oily and combination) are observed for black skin just as
they are for white.
Many problems associated with black skin arise from changes in pigmentation.
For example, loss of colour (hypopigmentation) is common to all races and
occurs in disorders such as the little-understood vitiligo (leucoderma). This
effect, unsightly in white skins, can be devastating in black skins. Darkening
of the skin or hyperpigmentation, again occurring in all races, can be a
particular problem for black women as a result of hormonal changes during
pregnancy, or the use of the contraceptive pill. Both darkening and lightening
ofthe skin (due to local increased pigmentation or destruction ofmelanocytes)
can occur as the horny layer of the skin heals after damage caused, for
example, by spots and rashes. Common skin conditions such as acne can
lead to serious disfigurement for those with black skin. When formulating
AFRO PRODUCTS 203
facial care products for black skin it is therefore especially important to
select raw materials shown to possess low comedogenicity so as to avoid
irritation or the initiation of comedones 'acne'.
Ashy skin (xerosin) is a particular problem resulting from excessive drying
of the skin. This can be caused by harsh detergents or environmental effects
such as extreme cold spells or excessive dry heat. The condition manifests
itself as dry white patches, commonly on elbows, knees and backs of hands.
In areas where conditions are extremely dry, occlusive preparations inhibiting
water loss are particularly valuable, although they would be entirely inap-
propriate for areas of high humidity. For these conditions, light moisturising
non-occlusive preparations, allowing passage of moisture to and from the
skin, are required.
6.4 Hair products
The formulations described in the following sections are examples designed

to offer products suitable for restyling Afro hair using treatments which take
account of the need to condition and remoisturise before, during, and after
treatment. Where applicable, suppliers of formulation ingredients are given.
Full details of these, and other suppliers, can be found in Appendix I.
6.4.1 Relaxing and restyling products

Hair-straightening treatment using caustic alkaline chemicals has a severely
detrimental effect on the hair shaft. Such treatment should never be used on
hair in poor condition. The treatment procedure therefore comprises three
stages:
(i) a preconditioning programme;
(ii) a relaxer treatment (sodium, potassium or guanidine hydroxide); and
(iii) a post-conditioning treatment.
6.4.1.1 Preconditioning programme A conditioning programme prior to

the relaxing treatment is necessary to improve the physical state of the hair.
Ideally, this should be started two weeks previously to allow build-up of
sebum and protective oils on both hair and scalp. The oily build-up slows
the relaxation process and lessens damage to the hair. A three-stage process
is recommended:
(i) initial shampoo with protective conditioning shampoo;
(ii) moisturising with hot oil treatment; and
(iii) deep conditioning using rinse-off conditioners containing substantive
actives.
Table 6.1 Protective shampoo CI454
wt%
Empicol AL30T (ammonium lauryl sulphate, 28%)' 30.00

Crotein Q or Crodacel QM (steartrimonium hydrolysed animal protein) or 0.50
(cocodimonium hydroxy ethyl cellulose)b
Crodafos SG or N3N (PPG-5 ceteth-lO phosphate) or(DEA 0leth-3 phosphate)b 3.00
Incronam 30 (cocoamidopropyl betaine)b 10.00
Perfume, preservatives, colour q.s.
aAlbright & Wilson; bCroda Chemicals Ltd

Method of manufacture: dissolve Crotein or Crodacel in water along with the Crodafos and
triethanolamine; add Empicol followed by Incronam 30. Make final adjustment to pH 5.0-5.5.
Table6.2 Conditioning shampoo CI219
wt%
D-Panthenol 0.50
Crodasinic LS30 (sodium lauroyl sarcosinate)a 20.00
Incronam 30 (cocoamidopropyl betaine)' 10.00
Empilan CDE (cocoamide DEA)b 5.00
Incroquat SDQ25 (stearalkonium chloride, 25%), 0.20
Croquat L (Iauryldimonium hydroxypropyl hydrolysed animal protein)' 1.00
EDTA 0.10
Lactic acid q.s. to pH 6.7
'Croda Chemicals Ltd; bAlbright & Wilson

Method of manufacture: warm together all components to 60-65°C. When homogeneous,
stir to cool.
Table 6.3 Conditioning shampoo C1343 (high concentration)
wt%
Incronam 30 (cocoamidopropyl betaine), 13.00

Empicol ESB3 (sodium laureth sulphate, 28%)b 46.00
Crodalan AWS (polysorbate (80) (and) cetyl acetate (and) acetylated 1.00
lanolin alcohol)'
Crotein Q (steartrimonium hydrolysed animal protein)' 1.00
Empilan CDE (cocamide DEA)b 1.00
Lactic acid topH 6.00
'Croda Chemicals Ltd; bAlbright & Wilson

Method of manufacture: simple blend, with warming and mechanical agitation as
necessary. Note this is a high concentrate shampoo; if desired, the detergent content
may be reduced to make a cheaper milder product.
AFRO PRODUCTS 205
Conditioning shampoo Conditioning shampoos (see Tables 6.1 to 6.5)
contain a protective protein and are designed to clean, increase the strength
of the hair and reduce the porosity of the hair fibre. They may also be used
as post-relaxing conditioners.
Table 6.4 Conditioning shampoo CI571M3
wt%
Empicol AL30T (ammonium lauryl sulphate, 28%)" 40.00

Incromate SDL (stearamidopropyl dimethylamine lactate)b 2.00
Empilan CDE (cocamide DEA)" 2.25
Dow Corning 193 surfactant (dimethicone copolyol)' 2.25
EGMS PE3127 (glycol stearate)b 1.00
Croquat L (lauryldimonium hydroxypropyl hydrolysed animal protein)b 0.50
Crodacol CSjBP (cetostearyl alcohol)b 0.50
Deionised water to lOa
Lactic acid/sodium lactate buffer to pH 5.50-6.00
(approx. 1.0%)
"Albright & Wilson; bCroda Chemicals Ltd; 'Dow Corning Ltd

Method of manufacture: combine all ingredients with half of the quantity of water and heat to
approximately 70°C. With stirring, add remaining cold water. Stir to cool.
Table6.5 Pearlised conditioning shampoo CI571M3
wt%
Empicol AL30T (ammonium lauryl sulphate, 28%)" 40.00

Empilan CDE (cocamide DEA)" 2.25
Dow Corning 193 surfactant (dimethicone copolyol)' 0.50
EGMS PE3127 (glycol stearate)b 1.00
Croquat L (Iauryldimonium hydroxypropyl hydrolysed animal protein)b 0.50
Crodacol CS (cetostearyl alcohol)b 0.50
Lactic acid/sodium lactate buffer to pH 5.00-6.00
aAlbright & Wilson; bCroda Chemicals Ltd; 'Dow Corning Ltd

Method of manufacture: combine all ingredients (excluding the buffer) with half the quantity
of water and heat to approximately 70°C. With stirring, add remaining cold water. Stir to cool.
In addition to pretreatment, this shampoo represents an excellent conditioner shampoo for
post-treatment cleansing of the hair.
Hot oil treatment This treatment (Table 6.6) can use either a traditional
oil-based product, a light mineral oil alone, or an aqueous-based product,
which relies on the substantive effects of a cationic material (i.e. coco-
trimonium chloride and quaternary proteins or gums) combined with the
moisturising effects of a humectant.
Table 6.6 Hot oil treatment C1463MI
wt%
White mineral oil (25 cSt at 25°C) to 100

Crodamol ICS (isocetyl stearate)" 15.00
Crodamol PMP (PPG-2 myristyl ether propionate)" 5.00
Incroquat SDQ-95 (stearalkonium chloride)' 0.20
Novol (oleyl alcohol)' 2.50
Isopropyl alcohol 1.00
Perfume, preservative, colour q.s.
'Croda Chemicals Ltd

Method of manufacture: simple mlxmg with gentle heat to
dissolve the solid material. Cool. Add perfume.
Table 6.7 Deep pre-conditioner C5004
wt%
Lanolic acid (lanolin acid)" 2.00

Polawax NF (non-ionic emulsifying wax)' 3.00
Novol (oleyl alcohol)" 1.00
White petroleum jelly 4.00
Crodacol S95 (stearyl alcohol)' 4.00
Incroquat SDQ-25 (stearalkonium chloride, 25% active)' 10.00
Crotein 0 (hydrolysed animal protein)" 1.00
Crotein HKP/SF (hydrolysed keratin)" 0.50
Croderol GA 7000 (glycerine)" 3.50
Perfume, preservative q.s.
"Croda Chemicals Ltd

Method of manufacture: melt oils and waxes together and heat to
70°e. Dissolve the protein and amino acids in water. Heat to 70°C
and add oil phase. Cool with stirring.
Table 6.8 High activity deep pre-conditioner C50 19
wt%
Novol (oleyl alcohol)' 1.00

Crodacol C90 (cetyl alcohol)" 2.50
Incroquat SDQ-25 (stearalkonium chloride)" 1.80
Croquat L (lauryldimonium hydroxypropyl hydrolysed animal protein)' 1.00
GMS AjS ES0743 (glyceryl stearate (and) PEG-IOO stearate)' 3.00
White mineral oil (25 cSt at 25°C) 4.00
Perfume, preservative q.s.

Method of manufacture: heat oil phase at 75°e. Heat the aqueous phase to 80°e.
Add the water to oil phase slowly with stirring. Stir to cool. Fill off at 30°e.
Deep conditioning Deep conditioning treatments use creams containing a

high level of quaternary (cationic) product (e.g. stearalkonium chloride),
humecant, fats and oily material (Tables 6.7 and 6.8). The conditioner should
be applied for 10-20 min and then rinsed off.
AFRO PRODUCTS 207
6.4.1.2 Relaxer treatments These consist of two types: (i) sodium/
potassium hydroxide or guanidine hydroxide hair-straightening formula-
tions; and (ii) thioglycollate-based chemical relaxation treatment.
Sodium/potassium hydroxide or guanidine hydroxide hair-straightening
formulations These formulations are effective but aggressive. In addition to
the ameliorating preconditioning programme outlined in section 6.4.1.1,
damage to the hair is lessened by the inclusion of emollient oils in the
products.
Sodium/potassium hydroxide based relaxers (see Table 6.9) are formu-
lated as viscous creams. The emulsification systems are often based on non-
ionic, self-bodying emulsifying waxes, together with auxiliary emulsifiers
Table 6.9 Hair relaxer creams
wt%
CM5042MI CI624 C834MI BW29
Polawax NF (non-ionic emulsifying wax)" 7.50
Crodacol C90 (cetyl alcohol)a 1.00
White petroleum jelly BP 20.00 20.00 20.00 21.00
White mineral oil (25 cSt at 25°C) 10.00 10.00 10.00 15.00
Crodafos NION (DEA oleth-lO phosphate)" 1.50
Crodafos CES (cetearyl alcohol (and) cetearyl 7.00
phosphate)"
Crodacol S70 (stearyl alcohol)" 2.00
Volpo SlO (steareth-lO)" 2.50
Solan E (PEG-75 lanolin)" 0.50 0.50
Polawax A31 (non-ionic emulsifying wax)" 11.00
Volpo CSI5 (ceteareth_15)" 1.00
Liquid base CB3929 (mineral oil (and) lanolin
alcohol)" 5.00
Polawax GP200 (non-ionic emulsifying wax)" 15.00
Crodacol S95 (stearyl alcohol)" 1.00
Volpo NI5 (0Ieth-15)" 2.00
Polychol 5 (laneth-5)" 1.00
Solan 50 (PEG60 lanolin)" 0.50
Propylene glycol 2.00 5.00 2.00 2.00
Deionised water to 100 to 100 to 100 to 100
Croquat M (cocodimonium hydroxypropyl 1.00
hydrolysed animal protein)"
Sodium hydroxide, 25% aqueous solution 6.80 8.00 8.50 8.40
Perfume, preservatives, colour q.s. q.s. q.s. q.s.
aCroda Chemicals Ltd
Note: (I) For mild strength product, 7.0-7.5% of a 25% solution of sodium hydroxide is
suggested.
(2) For medium strength product, 8.0-8.5% of a 25% solution of sodium hydroxide is
suggested.
(3) For high strength product, 9.0-9.5% of a 25% solution of sodium hydroxide is
suggested.
Method of manufacture: heat oil and water phases separately to 65°C. Add water to oils with
stirring. Add sodium hydroxide solution at 45°C; add perfume. Continue stirring and cool to
30-35°C, homogenise by milling, cool and fill into containers.
such as ethoxylated alcohols. A sodium hydroxide level of 1.9-2.4% is used

in the formulation depending on the strength required. C5042MI contains a
protein derivative, for its excellent conditioning effects. High levels (25-30%)
of protective emollients, i.e. hydrocarbon oils and waxes, must be included in
these formulations to slow down the reaction of the caustic on the hair, and to
reduce burning or irritation of the scalp. It is also important that only
materials chemically stable at the high pH resulting from the NaOH are
employed in this class of product.
Because of the difficulty in formulating products of this class, which are
effective, safe and both chemically and physically stable, various raw
material suppliers now offer pre-compounded emulsifying bases. To these
bases the appropriate (prescribed) levels of protective emollients, active
ingredient (Na or KOH), conditioner and water are added. The manufac-
turing technique involved in the preparation of these products is essentially
the same as that described for the formulations illustrated in Table 6.9.
Alternative alkaline relaxer treatments use guanidine hydroxide in place
of sodium hydroxide. Guanidine hydroxide is created in situ from guanidine
carbonate and calcium hydroxide, necessitating a two-component system in
which the active chemicals are kept separate until required (Tables 6.10 and
6.11). The guanidine relaxer is prepared by mixing four parts of the cream
base (Table 6.10) with one part of the liquid activator (Table 6.11). This causes
release of guanidine hydroxide to relax the hair.
Relaxation treatment using either sodium hydroxide or guanidine hydroxide
systems requires application of the cream relaxers to the hair for approxi-
mately 20 min, after which it is removed by rinsing and shampooing.
Extreme caution should always be exercised both in the development of and
use of these products. Appropriate trials and tests must be performed in order
Table 6.10 Guanidine hydroxide hair relaxer C5002:

cream base
wt%
Polawax (non-ionic emulsifying wax)' 15.00

Crodacol CSjBP (cetostearyl alcohol)' 1.00
Volpo NlO (0Ieth-l0)" 2.00
Calcium hydroxide 5.00
Perfume, preservatives q.s.

Method of manufacture: heat the oil phase and water
separately to 60°C. Add water to the oils with efficient
agitation. Continue to stir until the cream starts to
thicken (around 45°C). Add calcium hydroxide and
stir with scraping to disperse.
AFRO PRODUCTS 209
Table 6.11 Guanidine hydroxide hair relaxer CS002:
liquid activator
wt%
Guanidine carbonate 25.00

Keltrol F (xanthan gum)" 0.20
Preservatives q.s.
"Ke\cojAIL Ltd
Method of manufacture: dissolve the Keltrol and
preservatives in the water with stirring and heat to
70°C. Cool to 45°C and add the guanidine carbonate.
Table 6.12 Neutralising shampoo C5003
wt%
Empicol AL30T (ammonium lauryl sulphate, 28~{»' 20.00-40.00

Incromine Oxide C (cocoamidopropyl amine oxide)b 3.00
Crodafos SG (PPG-5 ceteth-20 phosphate)b 3.00
Crotein HKP SjF (hydrolysed keratin)b 1.00
Citric acid 1.00
'Albright & Wilson; bCroda Chemicals Ltd

Method of manufacture: add the Empicol Al30T to water at 65 C. Add
C
the Incronam 30 and the Incromine Oxide C; mix until uniform. Add
the Crodafos SG. Cool to 50 C and add the Crotein HKP SjF and
u
citric acid. Cool to room temperature and fill off.
to ensure the product is not over-aggressive, thus being destructive to the hair
or irritating to the scalp. Following this, residual alkaline material on the hair
must be completely neutralised. This is accomplished by washing the hair
with an acid-based shampoo (Table 6.12). In order to ensure stability of the
detergent base in the acidic environment, ammonium salts (e.g. ammonium
lauryl sulphate) and amphoteric products (e.g. cocamidopropyl betaine) are
incorporated into the shampoo. The use of an acid-base indicator will give a
change of colour in the lather when all the residual alkali has been
neutralised.
Thioglycollate-based chemical relaxation treatment An alternative chemical
treatment giving a waved, less curly appearance to the hair, instead of the
aggressive straightening achieved with sodium hydroxide relaxer products,
is based on sulphur-containing reducing agents, principally thioglycollates.
Thioglycollates disrupt sulphur-sulphur bonds in the hair protein by their
reducing action; subsequent application of an oxidising agent (neutraliser)
results in reformation of the protein sulphur-sulphur linkages. During the
reforming of these bonds, the hair fibre is styled into a new, relaxed structure,
Table 6.13 Ammonium thioglycollate hair·relaxer cream C5001
wt%

Crodafos NION (DEA 0leth-l0 phosphate)a 1.50
Volpo S2 (steareth-2)" 0.50
White petroleum jelly BP 11.50
Crosterene SA4310 (stearic acid)a 8.00
Volpo S 10 (steareth-IO)" 2.50
EDTA 0.50
Croquat M (cocodimonium hydrolysed animal protein)a 1.00
Ammonium thioglycollate, 60% 9.00
Ammonium hydroxide 88 4.63

Method of manufacture: heat oil and water phases separately to
65-70°C. Add water phase to oils under stirrer. Add ammonium
hydroxide to ammonium thioglycollate. Cool emulsion to 45°C and
add ammonium thioglycollate mix. Final pH must be adjusted to
9.5 ± 0.2 by further addition, if necessary, of ammonium hydroxide.
resulting in a less tightly curled appearance. As with the more drastic

caustic-based treatments, thioglycollate relaxing of the hair has an adverse
drying effect on the fibres-the hair will feel rough and have a greater
porosity. An elaborate, conditioning, aftercare programme is therefore
essential to keep the treated hair in optimum condition. Note that in the US
hair is straightened with caustic, a process which can result in much hair fall
and, if drastic, in baldness at the scalp. Soft curls are provided using thiogly-
collate treatment to relax the hair and then rolling onto rods (Jerry curls).
Ammonium thioglycollate products are formulated as gels or viscous
creams (Table 6.13). They are applied to the hair for up to one hour, prior
to wrapping the straightened hair on curling rods to style it. A slightly weaker
ammonium thioglycollate solution (often called a curl booster or charger) is
also applied. This is similar to thioglycollate permanent-wave treatments for
Caucasian hair.
The incorporation of a quaternised protein provides beneficial conditioning
effects, but these are merely temporary and will be removed when the hair
is next shampooed. A more permanent conditioning treatment (e.g. the
Kerasol* process) can also be incorporated into the thioglycollate treatment.
This procedure provides a conditioning action, which is effective through
numerous shampooings, by covalently bonding the conditioner protein
'Kerasol' to the hair between the reduction and oxidation steps in the waving
process. In addition to imparting general condition, the hair is left more
* Croda Chemicals patented process.

AFRO PRODUCTS 211
Table 6.14 Clear gel permwave C279
wt%

Procetyl A WS (PPG-5 ceteth-20) or Solan E (PEG-75 lanolin)" 1.00
Carbopol 941 (carbomer 941)b 1.86
Thioglycollate acid, 70% 7.24
Ammonium hydroxide, 28% 8.35
Sodium heptanoate dihydratea 0.10
'Croda Chemicals Ltd; bB.F. Goodrich

Method of manufacture: dissolve Procetyl AWS/Solan E in a little water. Dissolve
sodium heptanoate into 5% of water. Hydrate Carbo pol in rest of water; when
hydrated add ammonium hydroxide solution, then Procetyl A WS/Solan E
solution; lastly add sodium heptanoate dihydrate solution. pH should be 9.5 ± 0.1.
Note: hydroxyethyl cellulose may be employed as the gellant in place of the
Carbo pol if desired.
Table 6.15 Kerasol permanent conditioner Cl401
wt%
Kerasol (soluble animal keratin)" 5.00-l0.00

Crotein Q (steartrimonium hydrolysed animal protein)" 0.50
Deionised water to lOO

Method of manufacture: simple blend of components in water.
receptive to moisture, thus enhancing the effect of subsequent treatments

such as curl activators, and achieving maximum beneficial effect. The overall
process is as follows:
(i) Perm reduction step (Table 6.14)
(ii) Rinse
(iii) Kerasol conditioning treatment (Table 6.15)
(iv) No rinse
(v) Neutraliser oxidation step (Table 6.16)
The neutralising process, during which the sulphur linkages are reformed
and the hair is 'locked' into its new shape or style, uses products based on
peroxides or bromates. This is exemplified by the neutraliser shown in
Table 6.16, which is based on sodium bromate.
The thioglycollate treatment is normally concluded with a conditioner,
which must be light to avoid weighting down the curls. The product shown
in Table 6.17 combines a fatty quaternary and a humectant to aid in
conditioning and moisturising the hair. The use of a moisturising spray,
combining humectant (e.g. propylene glycol) and acetamide MEA, together
with protein additives, for remoisturising and improving the hair condition,
Table 6.16 Sodium bromate neutraliser C5045/hydrogen peroxide neutraliser

no. 5
wt%
C5045 no. 5
Croduret 40 (PEG-40 hydrogenated caster oil)a 3.00
CelIo bond HEC5000A (hydroxy ethyl celIulose)b 00-0.30
Sodium bromate 10.00
Disodium phosphate 0.50
Deionised water 85.20 89.50
Crillet I I perfume a 1.00 1.00
Hydrogen peroxide (30%) 6.50
Dow Corning Q2-7224c 4.00
Trimethylsilylamodimethicone (and)
dimethicone (and) octoxynol 40 (and)
isolaureth-6 (and) glycol
phosphoric acid to pH 3.4
a Croda Chemicals Ltd; b BP Chemicals; C Dow Corning Ltd.
Method of manufacture C5045: dissolve HEC in water and heat to 80°C, when
hydrated, add Croduret and CrilIet perfume blend, at 40-45°C add disodium
phosphate and sodium bromate, adjust pH to 7.00 + or - 0.30.
Method of manufacture no. 5: mix all ingredients in the order given. Adjust pH to
3.4 with phosphoric acid.
Table 6.17 Hair conditioner C1410
wt%
Conditioner base CB0967 (proprietary blend)" 4.00

Incromectant AMEA-70 (acetamide MEA)" 5.00
Lactic acid to pH 4.00-4.50

Method of manufacture: heat all components together to 65-70°C,
except perfume and lactic acid. Stir to cool, perfuming and adjusting
pH to 4.0-4.5 at 45°C. Fill off at 40°C.
is also popular. Further possible treatments include curl activator products,

hair-grooming creams and lotions, and moisturising and oil sheen sprays,
all of which can be used to impart gloss and sheen, and to enhance the lustre
of the hair. Curl activators based on Carbopol (see Table 6.18), contain a
high level of humectants to activate the curl. In temperate zones; where a
lighter treatment is required, propylene glycol in combination with glycerine
is the humectant; in hot climates, a heavier, more durable, higher gloss
preparation is recommended, with partial or total replacement of the glycol
with glycerine. The preferred ratio of glycerine to glycol is generally 2: 1.
Extremely hot climates require the inclusion of suitable block copolymers
(e.g. Ucon 50 HB660) to give a more lasting effect. The curl activator gel
AFRO PRODUCTS 213
Table 6.18 Curl activator gels based on Carbopol
wt%
C1391 C1398
Carbopol 940 (carbomer 940)' 0.50 0.66

Propylene glycol/glycerine 25.00 12.00
Crillet 1 (polysorbate 20), Procetyl AWS 6.00 5.00
(PPG-5 ceteth-20), or Croduret 40 (PEG-40
hydrogenated castor oil)b
Triethanolamine, 99% to pH 6.0-7.0
Croderol GA 7000 (glycerine)b 10.00
Diisopropy lamine to pH 6.5-7.0
Perfume, preservatives, colour q.s. q.s.
aB.F. Goodrich; bCroda Chemicals Ltd

Method of manufacture: hydrate Carbo pol in water (60-65°C). Add propylene glycol and
preservatives, neutralised to pH 6.5-7.0 with amine. Combine perfume and Crillet, and add to
Carbopol gel. Stir until a clear homogeneous gel is obtained. Fill ofT. Note: for the preparation
of heavier texture/improved durability, the propylene glycol may be wholly or partially replaced
with glycerine.
Table 6.19 Curl activator gel C1128
wt%
Crodafos N3N (DEA 0leth-3 phosphate)" 7.48

Volpo N5 (0Ieth-5)" 10.88
Incromectant AMEA (acetamide MEA)" 0.20
Sorbitol, 70% solution 11.00
Croderol GA7000 (glycerine)" 7.00
Hexylene glycol 2.00

Method of manufacture: heat oil phase to 65-70°C. Heat water
phase to similar temperature. Slowly add water to oils with stirring,
and cool rapidly.
shown in Table 6.19 is based on a microemulsion gel, a formulation which is

suitable for all climatic conditions. Again, high levels of propylene glycol!
glycerine are used. These systems are, however, sensitive to minor changes
in raw materials and, due to the inherently high surfactant level, can be
irritating to the eye.
Recommended formulations for emulsion-based hair-grooming products
(combining humectants and emollient oils), a moisturising spray, and a
comb-out oil are shown in Tables 6.20 to 6.23. These products are used at
the end of the thioglycollate treatment to help to maintain the hair in its
optimum condition.
Table 6.20 Hair grooming cream/lotion C1450
wt%
GMS A/S ES0743 (glyceryl stearate (and) 4.00

PEG-IOO stearate)"
Crodamol MM (myristyl myristate)" 4.00
Liquid base CB3929 (mineral oil (and) lanolin 3.00
alcohols)"
Crodalan LA4028 (cetyl acetate (and) 1.00
acetylated lanolin alcohol)"
GMS GE0803 (glyceryl stearate)" 2.50
Volpo CS20 (ceteareth-20)" 1.00
Squalene 0.60
Incromectant AMEA-70 (acetamide MEA)" 1.00
D-Panthenol 0.40
Incroquat SDQ25 (stearalkonium chloride)" 1.00
Perfume. preservatives q.s.

Method of manufacture: combine oil phase and water phase and
heat to 65-70°C. Add water to oils with stirring. Stir to 45°C and
perfume. Stir to cool.
Table 6.21 Hair-softening spray lotion C 1129
wt%

Perfume 0.20
Crillet I (polysorbate 20)" 2.00
Preservatives, colour q.s.

Method of manufacture: blend Crillet and
perfume, add Croderol, glycol, water and
preservative. Stir till clear.
6.4.1.3 Post-conditioning treatment Post-relaxation treatment to combat

the defatting nature of the relaxer includes use of a conditioner as in the
preconditioning programme (Tables 6.1 to 6.5), together with a scalp grease
(Table 6.24) to lubricate the scalp and prevent dryness and flaking between
the roots.
To complete the relaxation treatment the hair can be styled in the normal
way. Examples of a setting lotion and styling gels are given in Tables 6.25
and 6.26. A hair-groom cream, which is applied to provide a moisturising,
glossy effect, is shown in Table 6.27.
AFRO PRODUCTS 215
Table 6.22 Moisturising spray mist C5016
wt%

Incromectant AMEA-70 (acetamide MEA)a 1.50
Crotein HKP/SF (hydrolysed keratin)a 0.50
Crodacel QM (cocodimonium hydroxy
ethylcellulose)" 0.50

Method of manufacture: dissolve Crodacel QM in water. Add the
protein and amino acids. Blend in the remainder of the
ingredients. Fill 01T. This product is designed to be dispensed
from a mechanical pump applicator.
Table 6.23 Comb-out oil C5008
wt%
Lanexol AWS (PPG-12 PEG-50 lanolin)" 4.00

Crotein Q (steartrimonium hydrolysed animal
protein)" 1.00
Crodacel QM (cocodimonium hydroxy ethyl
cellulose )a 0.10
Dow Corning 1931luid (dimethicone copolyol)b 0.50
aCroda Chemicals Ltd; bDow Corning Ltd

Method of manufacture: combine ingredients under good agita-
tion.
Table 6.24 Scalp grease C5048
wt%
Paraffin wax (140/145°C) 5.00

Crodamol IPM (isopropyl myristate)a 6.00
Lanolina 10.00
Super Hartolan (lanolin alcohol)" 3.00

Method of manufacture: heat all ingredients together with the
exception of the perfume. Cool, stir in fragrance and fill.
Table 6.25 Setting lotion CI444
wt%
PVPIV A S630 (PVPIV A copolymer)a 1.50-3.00

Gafquat 755N (polyquaternium II)" 1.50-3.00
Crillet I (polysorbate 20) or Crovol 70 series
(ethoxylated vegetable oils)b q.s.
Preservatives q.s.
aGAF Europe; bCroda Chemicals Ltd

Method of manufacture: dissolve PVPIV A in water, followed
by Gafquat. Pre-dissolve perfume in Crillet or Crovol (ratio 3: I)
and add to water phase with stirring. Add preservative and
colour and fill off. Note: The ratio of perfume to Crillet or
Crovol may have to be altered to achieve clarity depending on
perfume used. One part perfume to four parts solubiliser is given
as nominal starting point.
Table 6.26 Hair styling gels
wt%
CI123 CI465
PVP K30 (polyvinylpyrrolidone)" 2.00 3.00

Carbopol 940 (carbomer 940)b 0.50 0.50
Vol po N20 (0Ieth-20)' 1.00
Procetyl A WS (PPG-5 ceteth 20)' 0.50
Ethanol 74.0P 15.00
Crotein 0 (hydrolysed animal protein)' 0.50
Uvinol D50 (benzophenone-2)d 0.10
Crillet 1 (polysorbate 20)' 0.50
EDTA 0.10
Diisopropanolamine 0.30
aGAF Europe; bB.F. Goodrich; 'Croda Chemicals Ltd; dBASF (UK)

Ltd
Method of manufacture:
(I) C1123: hydrate the Carbopol in one third of the water (60-6SOC).
Dissolve the remaining components in the rest of the water. Mix
together-the product will gel. Adjust to pH 6-7.
(2) C1465: hydrate the Carbopol in one third of the water (60-6SOC).
When fully hydrated, neutralise with amine to form the gel.
Dissolve PVP K30 in ethanol and add to gel. Pre-dissolve
perfume iT, Crillet, add to gel and stir to clear. Fill otT.
6.4.2 H air pomades and grooming aids

Hair pomades-the original hair products-are examples of mild products
offering modern formulations for use with a very traditional African hairstyle.
AFRO PRODUCTS 217
Table 6.27 Hair groom cream W /0 C953
wt%
Polawax GP200 (non-ionic emulsifying wax)' 5.00

GMS N/E GE0803 (glyceryl stearate), 0.50
Carbopol 934 (carbo mer 934)b 0.50
Triethanolamine, 99% to pH 6.8-7.0
Perfume, preservatives q.s.
'Croda Chemicals Ltd; bB.F. Goodrich

Method of manufacture: combine oil phase and heat to 70°e. Hydrate
Carbo pol in water phase, and heat to 70°e. Add oil to water with
efficient agitation. Add triethanolamine at 60°C followed by perfume at
50°e. Fill off at 40°e.
'Canerow' is the art of plaiting the hair close to the scalp in a variety of pat-
terns, a style which has passed from generation to generation amongst African
women. Traditionally, natural oils such as shea butter and coconut oil are
used to keep the scalp supple while the hair is being teased and stretched into
tight plaits. The modern formulation for a hair pomade, C1411 (Table 6.28),
consists of a blend of oil, petroleum jelly and waxes. This pomade is also
suitable for use during the 'hot-comb' procedure for temporarily straightening
the hair, a treatment which runs a considerable risk of burning the scalp and
also has a damaging effect on the hair shaft. The temporary straightening
achieved in this way only remains until the hair comes into contact with
moisture, when the crinkly appearance will re-occur.
Table 6.28 Hair pomade CI411
wt%
Lanolin a 4.00
White mineral oil (25 cSt at 25°C) to 100
Microcrystalline wax (78-82°C) 28.00
Aluminium stearate G b 1.20
Crodamol IPM (isopropyl myristate), 2.S0
BHT 0.01
'Croda Chemicals Ltd; bDurham Chemicals Ltd

Method of manufacture: add aluminium stearate to
cold mineral oil whilst stirring. Stir well until thoro-
ughly dispersed. Maintain mixing and heat oil to
IOS-110DC, adding microcrystalline wax. When the
aluminium stearate has completely dissolved, a sli-
ghtly gelatinous solution will form. Begin cooling,
adding the rest of the ingredients, except perfume, at
90°e. Add perfume at 7S°e. Fill off at 70°e.
6.5 Skin products
Dermatological problems can often arise due to the use of cheap semi-refined
materials; the use of reliable suppliers, coupled with an understanding of the
significance ofraw materials specifications, is an important step in producing
satisfactory results. Careful raw materials selection plays an important part
in designing formulations for any product, but is especially significant for
products designed for black skin. The cosmetic qualities of all materials must
be ensured.
6.5.1 Raw material selection-factors for consideration

6.5.1.1 Emollient comedogenicity The skin condition of acne (or comedone
formation) causes particular problems to black skin. Work on the comedo-
genicity of common cosmetic emollients to assess their potential to cause (or
aggravate) comedones, has resulted in the grading of emollients according to
low, medium or high comedogenic categories (Tables 6.29 to 6.31). This pro-
vides a useful guide when formulating. Low comedo genic rated products
(Table 6.29) are recommended for use in facial care products, materials with
Table 6.29 Emollient materials with a low comedogenic effect
Avocado oil Beeswax (25% in mineral oil) Candelilla wax

Castor oil Glycerine Cetyl alcohol
Cholesterol Lanolin oil Isocetyl stearate
Lanolin Pentaerythritol White mineral oil
PEG-200 tetraisostearate Penterythritol
Spermaceti wax Stearyl alcohol tetracaprylate
Stearic acid Diisopropyl adipate Propylene glycol
Octyl palmitate (5%) PPG-2 myristyl Dimethicone
Cyclomethicone propionate
Table 6.30 Emollient materials with a medium comedo genic effect
Glyceryl monostearate Myristyl myristate Octyl palmitate (50%)

Ethoxylated lanolin White petroleum jelly Capric/caprylic
triglyceride
Olive oil Arachis oil
Sesame oil Lanolin alcohols
Table 6.31 Emollient materials with a high comedogenic effect
Cocoa butter Isopropyl myristate Isopropyl palmitate

Acetylated lanolin Oleyl alcohol Crude petroleum jelly
Alcohols Isopropyllanolate Sweet almond oil
AFRO PRODUCTS 219
a medium rating (Table 6.30) can be used with caution, while a high
comedogenic rating (Table 6.31) identifies materials that are preferably
avoided or kept to a minimum.
6.5.1.2 Occlusivity Another important aspect of cosmetic products is the

degree to which passage of water (or gaseous vapour) to and from the skin is
controlled. Cosmetics that impede insensible perspiration are deemed 'occlusive',
a phenomenon attributed to the emollient phase having a linear structure,
which acts as a barrier on the skin. Occlusive preparations can lead to
uncomfortable sensations and give rise to localised heating of the skin and
prickly heat. However, if correctly manipulated, such a characteristic can be
used to advantage in creams designed for treatment of ultra-dry skin caused
by adverse physical and environmental conditions. By preventing moisture
loss, skin can be kept hydrated and moisturised from within. Materials
suitable for such applications (e.g. treatment of ashy skin at elbows and knees)
are high quality white mineral oils and petroleum jelly. Lanolin and certain
derivatives are similarly valuable since they are capable of retaining moisture
in an emulsified form at the skin's surface. Materials such as lanolin, liquid
lanolin, lanolin alcohols and lanolin absorption bases are all suitable for use
in preparations requiring occlusive properties. The traditional use of natural
vegetable oils such as shea butter and palm oil, which applied neat to the skin,
has generally been replaced by petroleum jelly and mineral oil. These achieve
a similar but more comfortable effect.
The formulation of products for hot humid climatic conditions, where water
loss from the skin is important, requires the use of ingredients that will operate
to reduce the occlusivity of the cosmetic product. In particular, inclusion of a
porositone (a branched chain ester) such as 2-ethyl hexyl palmitate (deemed
non-occlusive) serves to provide low occlusive, light-textured creams and
lotions. Other suitable branched chain esters are di-2-ethyl hexyl adipate,
cetostearyl octanoate, 2-ethyl hexyl coco ate, 2-ethyl hexyl succinate and
acetylated lanolin alcohol.
6.5.2 Emulsification systems

The traditional emulsification system involves the use of soaps, the properties
of which naturally confer an alkaline pH to the cosmetic product. This can
theoretically damage the acid mantle of the skin-part of the skin's natural
protective system-leaving it susceptible to bacterial attack and skin dis-
orders. Despite this, many market leader products with good safety records
have been based on amine soap systems, particularly the triethanolamine
stearate system with a pH of7.5-8.5. The aforementioned use of highly refined
materials for cosmetic products is particularly important in the case of amines;
low quality triethanolamine can contain secondary amines as impurities.
These materials are recognised for their potential for forming nitrosamines-
carcinogenic chemicals resulting from the interaction of secondary amines and

nitrites.
Preferred emulsification systems for more sophisticated products are
non-ionic materials. These give the formulator greater flexibility in terms of
the type of emulsion (oil-in-water or water-in-oil), pH and inclusion of
additional materials (e.g. cationic germicides). Favoured non-ionic emulsifiers
(and emulsifier combinations) involve sorbitan esters and their ethoxylated
derivatives, often in combination with glyceryl monostearate, self-emulsifying
waxes, acid-stable grades of glyceryl monostearate, ethoxylated castor oil
derivatives, and surface-active lanolin derivatives.
6.5.2.1 Humectant selection Most cosmetic creams and lotions contain

humectants to prevent the product drying out at the surface; the humectants
also act as moisturisers on the skin. In dry climates, the occlusivity approach
described in section 6.5.1.2 is a practical method for retaining skin moisture.
Table 6.32 O/W hand and body lotions
wt%
CI076MI Cl282B Cl437MI
Crodamol rPM (isopropyl myristate)' 5.00 3.00

Polawax GP200 (non-ionic self-
emulsifying wax)' 2.00 2.70
Crosterene SA4310 (stearic acid)' 1.00 0.18
Crodamol CAP (cetearyl octanoate)' 2.00
Silicone fluid 200/100 cSt (dimethicone)b 1.00
Crodafos CDP (DEA cetyl phosphate)' 0.50
GMS S/E GE0802 (glyceryl stearate S/E)' 1.50
Lanolin' 0.50
White mineral oil (25 cSt at 25'C) 5.00 2.00 2.10
Crodamol W (stearyl heptanoatej" 2.00
Crodamol OHS (octyl hydroxystearate)' 2.70
GMS A/S ES0743 (glyceryl stearate
(and) PEG-IOO stearate)' 6.00
Refined cocoa butter 1.50
Deionised water to 100 to 100 to 100
Propylene glycol 2.00 2.20
Croderol GA 7000 (glycerine)' 3.00
Sodium lactate/lactic acid buffer
solution (pH 5.5)a 1.00
Carbo pol 941 (carbomer 941)' 0.10 0.10
Triethanolamine, refined 0.60 0.10
Perfume, preservatives, colour q.s. q.s. q.s.
aCroda Chemicals Ltd; bDow Corning Ltd; 'B.F. Goodrich

Method of manufacture: heat oil and water phases separately to 65-70'C.
Where included, Carbo pol should be hydrated in the water phase first,
omitting the amine. Add water to oil phase under stirrer and stir to cool.
The Carbopol should be neutralised with amine at 60°C. Perfume at
40-45°C and fill off at 30'C.
AFRO PRODUCTS 221
In the lighter preparations, the cream itself can moisturise due to the inclusion
of suitable moisturising components in the formulation. Typical humectants
used to achieve this are glycerine, sorbitol, polyethylene glycol, sodium pyr-
rolidone carboxylate, sodium lactate/lactic acid buffers and urea. Acyl
alkanolamides have also been shown to be effective moisturisers.
Other highly successful materials for use in moisturising cosmetic products
are proteins and amino acids. These have the ability to retain high levels of
moisture while imparting a pleasant feel to the skin. Classically, collagen has
been employed in this role, but other useful protein derivatives include
hydrolysed animal- and plant-derived proteins, together with the somewhat
more evocative proteins derived from silk, egg and milk. In more up-market
products, special complexes of proteinaceous materials, such as hyaluronic
Table 6.33 All-over body creams
wt%
C1433 C1409 C1416
Liquid base CB3929 (mineral oil (and)

lanolin alcohol)' 6.50
Crodamol OP (octyl palmitate)' 4.00 2.00
Crodamol LA (cetyl acetate (and)
acetylated lanolin alcohol)' 3.50
Crodamol IPM (isopropyl myristate), 6.00
GMS A/S ES0743 (glyceryl stearate
(and) PEG-100 stearate), 4.30
GMS N/E ES0803 (glyceryl stearate)' 3.00 5.00
Vol po CSlO (ceteareth-l0), 1.00
Refined cocoa butter 2.00
Fluilan (lanolin oil)' 1.00
Crosterene SA4310 (stearic acid)' 4.30 3.00 2.00
Crodamol CAP (cetearyl octanoate), 3.00
Polawax GP200 (non-ionic self-
emulsifying wax)' 3.00 3.00
DL-Alpha tocopherol b 0.50
Silicone fluid 200/100 cSt (dimethicone)' 1.00
Almond oil 1.00
Cithrol6MS (PEG-12 stearate)' 1.00
Croderol GA7000 (glycerine)' 2.50 4.00
Carbopol934 (carbomer 934)d 0.25 0.25
Triethanolamine, refined 0.60 0.60
'Croda Chemicals Ltd; bBASF (UK) Ltd; cDow Corning Ltd; dB.F.
Goodrich
Where included, Carbopol should be hydrated in the water phase first,
omitting the amine. Add water to oil phase under stirrer and stir to cool.
The Carbopol should be neutralised with amine at 60°C. Perfume at
40-45°C and fill ofT at 30°C.
acid/protein complex and chondroitin sulphate/protein complex, have been

shown to improve extensibility and elasticity of the skin. Lanolin (see
section 6.5.1.2) is also a particularly valuable additive in this class of
moisturiser.
Table 6.34 W/0 general-purpose creams
wt%
C741 C436 C489M
Crill 6 (sorbitan isostearate)" 2.50

lanolin alcohol)" 5.00 12.00
White microcrystalline wax (78~82°C) 9.00 5.80 3.40
Hartolite (modified lanolin alcohols) 3.16
Aluminium stearate G b 0.10
Satulan (hydrogenated lanolin)" 2.50
White mineral oil (25 cSt at 25°C) 16.50 8.70 16.00
Ozokerite wax 65~ 70°C 2.20
Lanolin" 9.50
BHT 0.01 0.01 0.01
Crodacol CS/BP (cetostearyl alcohol)" 0.30
Croderol GA 7000 (glycerine)" 1.50 2.50 3.50
Magnesium sulphate 0.70 0.70 0.70
"Croda Chemicals Ltd; bDurham Chemicals Ltd

Method of manufacture: heat oil and water phases separately to 65~ 70°C.
Add water to oils with stirring. Stir to cool, adding perfume at 45°C. When
cool homogenise with triple roll mill, colloid mill or other suitable
equipment.
Table 6.35 O/W glycerine silicone hand creams
wt%
CI432MI CI502
Silicone fluid Flll/200 cSt (dimethicone)" 3.00 3.00

Crodacol C90 (cetyl alcohol)b 4.00 9.00
GMS N/E GE0803 (glyceryl stearate)b 2.00
Crodex A (anionic emulsifying wax BP)b 7.00 10.00
Crodamol rPM (isopropyl myristate)b 5.00
Crodamol OHS (octyl hydroxystearate)b 3.00
Croderol GA 7000 (glycerine)b 10.00 35.00
"Dow Corning Ltd; bCroda Chemicals Ltd

Method of manufacture: heat oil and water phases separately to
65~ 70°C. Add water to oils with mechanical stirring. Stir to 45°C
and perfume. Stir to cool and fill off.
AFRO PRODUCTS 223
6.5.2.2 Skin creams and lotions Skin creams and lotions fall into two
categories: (i) those for use in warm humid climates; and (ii) those for use in
dry climates or during the dry season. The first category comprises relatively
light-textured products with low occlusivity, exemplified by all-over skin-care
lotions (Table 6.32); and all-over body creams (Table 6.33). (Note that for
th~se, and all other formulations given in this section, full details of suppliers
can be found in Appendix I.)
For the second category, water-in-oil emulsions are favoured. The skin-
cream formulations shown in Tables 6.34 include a super-emollient moisturising
cream (C489M) designed for treating 'ashy skins'. The moisturising hand
creams shown in Table 6.35 are characterised by high levels of glycerine and
silicone incorporated into the emulsion system. These hand creams deposit a
wax-like film, which gives a dry emollience and avoids excessive oiliness.
An additional product that assumes importance in the black populace is
generally termed complexion or fade cream. This contains hydroquinone, a
chemical product that is used to lighten the skin, and is commonly
misunderstood as making black people whiter. In fact, hydroquinone creams
are more often used to lighten specific darker areas of skin (the result of
hyperpigmentation), thus 'evening-out' the skin tone. Formulations for
hydroquinone creams are shown in Table 6.36.
Table 6.36 Hydroquinone creams
wt%
CI420 C1564

lanolin alcohol)" 7.00 7.00
Crodacol CS/BP (cetostearyl alcohol)' 5.00 5.00
GMS A/S ES0743 (glyceryl stearate (and)
PEG-IOO stearate)a 10.00 10.00
Polychol15 (laneth-15)' 3.00
Croderol GA 7000 (glycerine)' 2.00
PEG-1500 4.00
Ascorbic acid 0.20 0.20
Citric acid to pH 4.00
Hydroquinone 2.00 2.00
Sodium metabisulphite 0.10 0.20
EDT A 0.30 0.35

Method of manufacture: heat the water and oil phases to
65-70°C. Add the water phase to the oil phase with stirring. Stir
until 40-45°C. Add, in order, sodium metabisulphite, ascorbic
acid, hydroquinone and citric acid. Perfume at 40°C (the perfume
must not react with hydroquinone or bisulphite). Adjust the pH
value, if necessary, to 4.00-4.50 with citric acid.
6.6 General practical considerations
Many of the precautions outlined in this chapter apply to the general

manufacture of make-up (colour cosmetics). The manufacture of ethnic
products, however, necessitates a complete range of different colour shades
that are complementary with black skin (see chapter 4). All the normal rules
for testing and evaluating product stability and safety apply, but particular
attention to the special marketplace conditions are essential. Severe conditions
of humidity, heat and UV radiation occurring in parts of Africa should be
carefully considered when determining test conditions and microbiological
preservation.
Further reading
Balsam, M.S. and Sagarin, E. (1974) (Eds) Cosmetic Science and Technology, 2nd edn, Vol. 3,
p. 178. John Wiley and Son, New York.
Chester, J. and Dixon, M. (1987) Manufacturing Chemist 58(5) 30.
Chester, J. and Mawby, G. (1987) Manufacturing Chemist 58(4) 53.
Coupland, K. and Smith, G. (1986) Speciality Chern. 6(3).
Fulton, lE. et al. (1976) Cutis 17344.
Fulton, J.E. et al. (1984) J. Am. Acad. Dermato!' 10(96).
IFSCC (1986) An approach to permanent hair conditioning. Proc. 14th IFSCC Congress,
September 1986. Preprints Vol II.
Kligman, H. and Mills, O. (1972) Arch. Dermato!' 106843.
Morris, W.E. et al. (1983) J. Soc. Cosmet. Chern. 34 215.
Munroe, L. (1986) Cosmet. Toilet. 101 63.
7 Dental products
M. PADER
7.1 Introduction
As the world's economy expands, so does the demand for improved

preventive health services and products. One of the consequences is that
substantial progress has been made in the development of over-the-counter
(OTC) cosmetics and toiletries, with an increasing trend to endow them with
properties which are biologically active, e.g. anti-dandruff shampoos. Oral-
care products have taken a similar trend, that is towards therapeutic and/ or
biological activity. The new trend has had a strong influence on the
formulation and other aspects of preventive oral care products worldwide.
These present both a challenge and an opportunity to marketers of dentifrices
and related products, particularly those who must depend largely on local
resources and must accommodate local customs and regulations. There are
a tremendous and growing number of oral-care products on the market. It is
obviously impossible to discuss them individually in this chapter alone.
Hence, this chapter will define only important principles governing the more
prominent oral-care products. The reader must seek other references for
details of the chemistry of the raw materials and finished products,
manufacture, etc. (Two reference works which are complete enough for most
of the detail needed to understand successfully, formulate and market
dentifrice are by Pader [1, 2]).
The role of oral hygiene products has traditionally been to keep the teeth
free of stain and to freshen the breath. To this must now be added the
prevention of diseases which can result in the loss of teeth, e.g. dental caries.
New ingredients and procedures have been introduced. Now, the emphasis is
on maintenance of a healthy dentition; stain removal and breath freshening
are features of oral hygiene which have generally been relegated to the
category of problems which have been solved. New claims for improved
tooth cleaning occasionally appear, but the principles of formulation of
products which clean teeth and breath are well established. Maintenance of
a healthy dentition, however, has achieved only limited success with current
dental science, and is the driving force behind most oftoday's dental research
on OTC oral-care products.
The two major arenas of preventive self-applied dental formulations have
been reduction of dental caries and prevention of gum diseases. Dental caries
affected as much as 95% of people in industrialized populations. The
incidence is now down to a small hard core of susceptible people; some
individuals have gone through childhood without experiencing the disease.
Periodontal diseases are still rampant in all populations, but this must be
put into perspective. There are many types and stages of periodontal disease.
If the disease is categorized in terms of disease which threatens tooth loss or
the need for major surgical measures, the incidence is relatively low in
industrialized societies, it has been suggested as even less than 2%. If all
conditions which cause mild inflammation or irritation are considered to be
periodontal disease, the incidence is considerably higher.
Good self-applied oral hygiene measures can go far in reducing sub-
stantially the incidence and severity of caries, periodontal diseases and other
dental disorders among those not afflicted with special dental disease
problems. This chapter will discuss the OTC products and practice of oral
hygiene which will help achieve the goal of a healthy mouth. They need not
be overly sophisticated, depending on the goals specified. Certainly, a clean
dentition is a first, necessary step towards a healthy dentition [2].
7.2 The human dentition and its environment
7.2.1 Teeth and associated oral structures

Figure 7.1 presents the anatomy of a tooth, as classically represented by
Schour [3]. Oral hygiene practices are designed to maintain the crown
enamel, dentin (if exposed) and gingiva in healthy states. Maintenance of these
structures is expected to result in the general health of the dentition, including
other hard and soft tissues and the supporting bony structure.
During childhood, humans have a complement of 20 teeth, which erupt
from 6 months of age (lower central incisors) to 20-24 months (second molars).
Adults normally have a complement of 32 teeth, erupting from 6-7 years of
age (first molars, central incisors) to 17-21 years (third molars). The teeth
are supported by a bony structure. The principle diseases causing loss of
teeth are dental caries and periodontal diseases. Good oral hygiene and
dietary habits are effective preventive measures. If left undisturbed, the carious
lesion will penetrate to the pulp and expand to destroy the crown. Similarly
unless tended to, periodontal disease will result in inflammation and
destruction of the soft tissue surrounding the tooth, and eventual loss of the
tooth.
7.2.2 Saliva and crevicular fluid

Saliva is a mixture of the secretions of the parotid, submaxillary, sublingual
and accessory salivary glands, occasionally along with the crevicular fluid.
DENT AL PRODUCTS 227
- - - - - - - - - - - - - - Enamel
Crown --
- - - - - - Gingiva
Pulp chamber --- - --
- - - - - - - Dentin
Root ----
---Periodontal
membrane
Pulp canal
--- Cementum
- - Alveolar bone
Apical foramen- - -
Spongy bone
Cortical bone
Figure 7.1 Diagrammatic representation of the tooth and periodontal tissues. From [3].
Saliva performs two functions: (i) it is involved in protection of the oral cavity
through several factor.'; related to the bacterial population of the oral cavity;
and (ii) it is involved in the initial processes of food digestion. Dawes [4]
suggested that saliva could be anti-cariogenic by: (i) increasing the rate of
carbohydrate clearance; (ii) reducing acid production by fermentative
pathways; (iii) buffering the drop in pH caused by acid production in plaque;
(iv) increasing the rate of glycolysis in plaque, thereby reducing the time the
plaque is below a critical pH for attack on enamel; (v) increasing enamel
resistance to demineralization by acid; (vi) increasing the degree of saturation
of plaque fluid with respect to hydroxyapatite or fluorapatite; (vii) promoting
remineralization of initial subsurface carious lesions; (viii) increasing bacterial
clearance from the oral cavity; and (ix) increasing the protection possibly
afforded by the dental pellicle that selectively deposits from saliva imme-
diately following cleaning of the teeth. Calcium ions present in saliva appear
to play an important role in microbiological processes involved in both
protection and destruction of the tooth by oral bacteria.
Crevicular fluid is introduced into the salvia through the gingival crevice.
It is not noticeable in a healthy dentition or the absence of teeth, and can
be an indicator of the extent of periodontal disease; more is exuded as the

condition worsens. Crevicular fluid exhibits enzyme activity that changes
with condition. Knowledge of crevicular fluid is still far from complete.
7.3 Oral accretions and conditions
7.3.1 Dental pellicle

Within minutes to hours after a tooth has been thoroughly cleaned, dental
pellicle, a film that deposits selectively from saliva, covers the tooth. It is this
film to which the bacterial mass (known as dental plaque) adheres, and which
stains when exposed to chromogenic materials. Dental plaque can be removed
without removing pellicle. Substantive tooth stains, however, are removed
only with removal of pellicle. Toothbrushing alone is inadequate to remove
pellicle and must be used in conjunction with an abrasive. Chemical removal
is possible, but only at the risk of damaging the underlying enamel.
Dental pellicle consists of glycoproteins selectively absorbed from saliva.
The amount of pellicle formed following brushing with an abrasive (pumice)
increases for about 1.5 h, then levels off. Pellicle may hinder penetration of
substances from plaque into enamel.
7.3.2 Dental plaque

Dental plaque is primarily a bacterial accumulation. It occurs surpragingivally
(above the gum line) and subgingivally (below the gum line). Figure 7.2 shows
a scanning electron microscope photograph of supragingival plaque, magnified
300 x. The actions of self-administered oral hygiene procedures are usually
limited to the supragingival plaque. Subgingival plaque is best cared for by
the dental professional.
Existence of a relation between dental plaque, periodontal disease and
caries is firmly established. Freedom from dental disease is usually a con-
sequence ofthe absence of plaque. Some investigators may not be very precise
in their definition of plaque, and different investigators measure plaque in
different ways with different results. For example, Bhaskar [5] reported
improvement in gum condition with use of an oral irrigator, even though
there was no major reduction in plaque as measured by a commonly used
technique.
Dawes et al. [6] defined dental plaque accurately, but inadequately, as
a soft and tenacious material found on surfaces of the teeth, readily removed
by mechanical means such as brushing or flossing, but not by rinsing with
water and other solutions. A more comprehensive definition is that of a mass
of oral bacteria, which initially accumulates around the teeth at the cervical
margin and then grows apically. In addition to a fairly characteristic microbial
DENTAL PRODUCTS 229
Figure 7.2 Dental plaque: scanning electron microscope. 300 x. Courtesy ofUnilever Research.
Port Sunlight Laboratory.
population, dental plaque contains leucocytes, desquamated cells, and other

oral debris. It undergoes maturation, which involves changes in the microbial
flora, possibly including calcification and loss of viability of some of the
bacteria. It resists removal by water and, when mature, can be removed only
by mechanical means. This definition acknowledges that plaque is a dynamic
system and that quantitative measurements must be reported only in the
context of that dynamism. A corollary would be that only a totally plaque-free
tooth can confidently be expected to be disease-free.
De la Rosa et al. [7] proposed a model for plaque development over time
(see Figure 7.3). Starting with a clean tooth, plaque accumulates to a plateau
level following a pattern of alternate build-up and removal by toothbrushing.
Each oral site may follow a different pattern, depending on efficacy of
brushing at that site. Plaque measurements at specific sites may be of greater
value than average values to elucidate clinical plaque status. Clearly the
status of the plaque at the start of a clinical experiment can influence the
apparent anti-plaque efficacy of an agent.
Inadequate control of plaque can lead to either or both of two serious
disease conditions, periodontal disease and dental caries [8]. A cause and
effect relationship between plaque and gum inflammation (gingivitis) was
convincingly demonstrated by L6e et al. [9]. These workers showed that
refraining from toothbrushing for several weeks, with subsequent build-up
of plaque, resulted in gingivitis. This was rapidly alleviated when the plaque
was removed by oral hygiene measures. Despite about three decades of
further study, however, there are many questions still to be answered about
the development and activity of dental plaque. Pader [10] has reviewed the
Plaque
level
(arbitrary
units)
o 5 10
Time (days)
Figure 7.3 Plaque growth and removal assuming only one brushing per day. A represents
plaque accumulation by a 'normal' individual before toothbrushing; B represents plaque
remaining after toothbrushing by a 'normal' individual. Curves C and D have the same meanings
for an unusually good brusher. (- - -) daily plaque accumulation; ( )( )( )( ) daily plaque
removal by toothbrushing. After [7].
problem and concluded that there is no simple proven quantitative relation-

ship between plaque and gum disease. Many questions remain unanswered.
Gingivitis does not develop in the total absence of plaque. But it has been
shown that some sites covered with plaque do not develop gingivitis, that a
clinical reduction in plaque need not be accompanied by an improvement in
total gingival health [11,12] and that in some instances removal of no more
than a minor amount of plaque reduces gingivitis significantly. But gingivitis,
itself, is not necessarily tooth threatening. Formulators of OTC dental-care
products must keep in mind the fact that gingivitis and tooth-threatening
periodontal diseases represent different levels of concern. The latter is still
understood only incompletely, including the role of anti-plaque agents in
OTC products in their control. Overall oral hygiene status, rather than
plaque status, has been postulated by Attstrom to be the better predictor of
total periodontal health [13].
DENTAL PRODUCTS 231
The relationship between dental plaque and caries is clear. Dental plaque
generates acid from carbohydrate, and this acid attacks the tooth enamel
and initiates formation of the carious lesion. The carious process has been
discussed at some length by Nikiforuk [8], Pader [2] and others.
7.3.3 Dental calculus (tartar)

Schroeder [14] examined dental calculus as understood up to about the year
1968. In 1986, Mandel and Gaffar [15] re-examined the subject. Schroeder
defined two types of dental calculus, supragingival and subgingival. The
former was explained as a hard, mineralized dental plaque and/or materia
alba permeated with crystals of various calcium phosphates covered with a
layer of 'vital, non-mineralized plaque'. Subgingival calculus was defined as
an organic structure of micro-organisms and intermicrobial matrix, containing
major amounts of crystalline calcium phosphates, different in amount and
distribution from those of supragingival calculus. A major impetus for the
study of dental calculus was the belief that this hard, rough accumulation,
(or the plaque concentrated on it), in direct contact with the gum tissue, was an
irritant leading to periodontal disease.
Supragingival calculus arises from the nucleation of calcium phosphate,
particularly in areas where the large salivary gland ducts secrete their saliva.
The calcium phosphate crystals in both supra- and subgingival calculus
consist of octacalcium phosphate, brushite, whitlockite and hydroxyapatite.
Subgingival calculus has a major amount of whitlockite and a reduced
amount of brushite compared to supragingival calculus. This suggests that
they have different origins. The contents of the periodontal pocket are ap-
parently able to fulfil the conditions necessary for nucleation and subsequent
crystal growth.
Dental calculus is formed fairly quickly. Schroeder [14] reported that a
four day old deposit (on a Mylar strip mounted on anterior teeth) was
mineralized about 40% (assessed by ash content), a twelve day old deposit
over 60%, and a two year old deposit about 80%. Mandel and Gaffar [15]
subsequently made a number of observations.
(i) Gingivitis can develop in the absence of supragingival calculus,
although it is not known to what extent the presence of the calculus
can increase gingival inflammation.
(ii) While calculus formation can be inhibited by chemical agents, the
reduction need not be accompanied by a reduction in gingivitis.
(iii) Subgingival calculus results from the interaction of subgingival
plaque with the influx of minerals that form part of the serum
transudate and inflammatory exudate.
(iv) Calculus is porous and can retain both bacterial antigens and easily
available toxic stimulators of bone resorption. This, together with
the increased accumulation of plaque on calculus, can produce more

severe destructive effects than the presence of plaque alone.
(v) Subgingival calculus contributes to the chronic character and to the
progression of periodontal disease, even though it may not be the
cause of the disease.
7.3.4 Periodontal diseases

Periodontal disease merits special attention in this chapter because it is of
major research interest to marketers of oral hygiene products. On the one
hand, dental caries has to all intents and purposes been conquered with
OTC fluoride toothpastes and rinses used in conjunction with water
fluoridation and other fluoride treatments. On the other hand, OTC products
offering the same degree of protection against tooth-threatening periodontal
diseases as fluoride does against caries are not yet available.
Van Dyke and Zinney [16] characterized periodontal diseases as "". a
family of chronic inflammatory infections affecting the supporting tissues of
the dentition." They stated that: "Modern periodontal therapy is based on the
tenet that supragingival plaque causes gingivitis, which is the precursor of
more advanced periodontal breakdown arising from subgingival growth and
apical extension of bacterial plaque." Pader [2] delineated several stages in
periodontitis. First, bacterial plaque forms at the gingival margin. If not
removed, it spreads. The bacteria generate toxins that inflame the soft gum
tissue, which becomes soft, puffy and red, and bleeds easily. Following this, a
periodontal pocket (a pathologically deepened gingival sulcus) may form in
susceptible individuals, without destruction of tissue. In the next stage, the
inflammatory process is aggravated: the pockets become enlarged and form
the receptacles for SUbgingival plaque bacteria, debris and exudates. The
surrounding connective tissue degenerates. With increasing challenge by the
bacterial mass, the pockets continue to deepen, and the teeth start to loosen.
Subsequently, the gums recede from the tooth crowns. Finally, microbial,
plaque toxins and other materials in the pockets intensify the inflammatory
process, supporting bone tissue is destroyed, and the teeth loosen and
eventually fall out or are extracted.
The relation between dental plaque and periodontal disease has been
discussed in detail in the literature [2, 10]. Some of the more important find-
ings relating to product development have been outlined by Attstrom [13]:
(i) Removal of supragingival plaque once every 24-48 hours is adequate
to preserve gingival health.
(ii) There is a close relationship between the subgingival location of the
advancing bacterial front and the level of connective tissue attachment.
The bacteria produce an inflammatory reaction apically/laterally to
the junctional epithelium.
(iii) Periodontal disease may proceed by bursts of increased inflammatory
activity. Dental plaque, gingival redness and bleeding on probing, and
initial pocket depth probing do not relate to the occurrence of probing
attachment loss. The incidence of periodontal disease sites in untreated
patients is low. The progression of periodontal disease does not
correlate with the presence of supra- and subgingival bacterial
colonization, and is probably related to the presence of specific
bacteria.
(iv) The level of oral hygiene correlates with the severity of periodontal
disease. Periodontal pathology and attachment loss are most severe
interproximally and least severe in the buccal sites. Supragingival
plaque removal by self-administered oral hygiene procedures slows
the progression of periodontal disease.
(v) The composition of the subgingival bacterial flora, and the progress
of periodontal disease varies from individual to individual, tooth to
tooth, and site to site on the same tooth. The pathological process
can be arrested by removal of subgingival bacteria along with
supragingival bacteria. Subgingival plaque is generally not affected
by supragingival cleaning once the subgingival plaque has established
itself in the more apical regions of the dentogingival area. However,
in untreated patients the composition of the subgingival flora is affected
by the presence of supragingival plaque.
(vi) Regular supragingival plaque removal can prevent infection of the
subgingival sites and maintain periodontal health, but not as effectively
in persons with a compromised defense system.
Burt has noted that epidemiological and clinical evidence indicates that most
gingivitis does not proceed to periodontitis, but periodontitis has not been
reported without a preceding gingivitis [17]. (Elucidation of this effect would
be useful in putting the value of gingival health products into better perspec-
tive.)
7.3.5 Dental stain

Vogel [18] proposed that the tooth stains accumulated by a significant
number of individuals are extrinsic in nature and result from discoloration
of pellicle and/or plaque. Eriksen and Nordb0 [19] proposed that extrinsic
staining may involve at least three mechanisms: (i) the production of colored
substances in plaque by chromogenic bacteria; (ii) the retention of colored
substances either from dietary factors passing through the oral cavity (berries,
tea, coffee) or from smoking; and (iii) the formation of colored products
resulting from the chemical transformation of pellicle components. Besides
tea, wine, tobacco smoke and other pellicle-reactive colored materials, oral
use of antimicrobial agents (including agents which have clinically exhibited

plaque control) has been implicated in stain formation.
7.3.6 Dental hypersensitivity

Dentinal or cervical hypersensitivity is experienced by some individuals after
their roots are exposed by gingival recession, or surgical or other periodontal
treatments. The condition, called 'dentinalgia', is characterized by pain when
the exposed dentin is SUbjected to thermal, osmotic, electrical or dehydrating
stimuli. Berman [20] and others have proposed theories to explain the
phenomenon. These are beyond the scope of this chapter, other than to note
that movement of fluid within the dentinal tubule can explain several
phenomena associated with hypersensitivity.
Desensitizing agents have successfully been incorporated into dentifrices.
Diverse agents are claimed to have desensitizing efficacy in a toothpaste
vehicle, indicating that hypersensitivity can possibly have multiple origins.
Certainly, different responses were obtained to different agents.
7.3.7 Oral malodor

Pader [2] has discussed oral malodor in terms of its bacterial origins. Bacteria
from virtually all sources in the oral cavity have been implicated. 'Morning
breath' has been attributed to the overnight putrefaction of food deposits,
salivary deposits, desquamated epithelial cells, and other types of oral accumu-
lation and debris. Malodor of other than bacterial origin (for example
due to the intake of odoriferous foods or to diseases which cause the exha-
lation of odoriferous metabolic products) cannot be eliminated by oral
hygiene measures.
The main cause of oral malodor is probably the putrefaction of sulfur-
containing protein substrates, predominantly by gram-negative bacteria. The
process is not limited to specific bacterial populations. Micro-organisms indi-
ginous to dental plaque, saliva, gingival crevice and tongue can participate, and
mixed bacterial populations are most capable of odor production. The
fermentation process releases hydrogen sulfide and methyl mercaptan (which
together account for 90% of the volatile compounds generated), dimethyl
sulfide and dimethyl disulfide. The mouth air also contains aliphatic and
aromatic alcohols, and indole. Mouth air and putrefying saliva from persons
with periodontal disease show higher than normal levels of sulfur compounds.
Mouth malodor can be controlled by vigorous oral hygiene practice. Most
of the hydrogen sulfide and methyl mercaptan in periodontitis-free individuals
derive from the dorsoposterior surface of the tongue and can be considerably
reduced by tongue brushing, toothbrushing, food ingestion and use of an
oral rinse that reduces oral bacterial populations.
7.4 Oral-care products
7.4.1 Product categories

Oral-care products can be divided broadly into mechanical devices and
chemical formulations. Additionally, one can include products designed for
use with prostheses, such as dentures, since some of the conditions affecting
the natural dentition can also affect those products as they are worn in the
mouth (for example, plaque and stain can accumulate on dentures).
The toothbrush is the most important part of the oral hygiene regimen.
Toothbrushing alone, without supplements such as toothpaste, can maintain
a reasonable state of oral health. Its value in this regard, however, is greatly
enhanced by supplementation with toothpaste, which contains materials to
remove stain, freshen the breath and accomplish specific functions. The
toothbrush is a mechanical device. Other mechanical devices include dental
floss, water irrigators and pics of various designs.
Increasingly, toothpaste is becoming a preferred vehicle to apply special
active substances to the dentition. This enhances the role of toothbrushing
in oral care. Toothpastes are now being marketed with special active agents
to combat dental caries, reduce the formation of dental calculus, combat gum
disease and reduce tooth hypersensitivity. Wide acceptance of toothpaste has
made it the vehicle of choice for applying therapeutic or special cosmetic
additives to the dentition. Toothpaste brands are proliferating as new health
benefit additives are discovered, and older concepts of toothpaste formula-
tion are no longer applicable.
The selected additive(s) must, of course, be compatible with and active
from the total formulation.
Oral-care products have been categorized as cosmetic or therapeutic,
depending on whether or not they contain a health benefit agent. The
definition of a health benefit agent is a very complicated matter and varies
from regulatory agency to regulatory agency around the world.
7.4.2 Toothpaste
Toothpaste fulfills two primary functions; removal of stain from the teeth
and freshening of the breath and mouth. Mild abrasives and appropriate
flavors, respectively, accomplish these objectives. These basic and essential
functions are being supplemented, but not reduced in importance, as it has
become recognized that additional functions can be beneficially built into
toothpastes.
Toothpastes on today's market present a wide range of rheological proper-
ties and appearances. The most common rheology is that of a paste that can
be extruded from a container onto a toothbrush as a ribbon which can
maintain its shape for the necessary time prior to brushing. Toothpastes are
marketed in a wide variety of physical characteristics and dispensers. These

include viscous liquids, pastes extrudable from a tube, pastes extrudable
from pumps, clear products (frequently referred to as 'gels'), products with
visual signals (such as sparkles or soft plastic particles with colors different
from the main toothpaste base), and products which are dispensed
simultaneously as multiple pastes with different colors. The rheological
properties of the paste components are key to the obtention of the various
toothpastes (toothpaste rheology will be discussed below).
Conventional toothpaste can remove accretions which dull the tooth
surface, that is stained pellicle, plaque. The consumer and regulatory
agencies recognize that toothpaste can not whiten teeth in the sense of
improving tooth color, which is determined mainly by the color of the dentin,
enamel playing only a minor role [21]. The dental professional has success-
fully made teeth whiter by the use of bleaching agents, primarily peroxides.
Although questions about the safety of prolonged, repeated application of
peroxide are still heard, the American Dental Association (ADA) has
recently approved as safe and effective two peroxide-containing products,
one for dental surgery use and one for daily use. Both products have been
extensively safety-tested and full reviews provided for the ADA. Nonetheless
the use of peroxide in OTC toothpaste, for as yet unspecified claims, is the
subject of major research and new dentifrice brands.
7.4.3 Tooth powder

Tooth powder is a forerunner of toothpaste. Once popular, it now has a very
low level of popularity. Toothpowder is a physical mix of dental abrasive,
flavor and foaming aid, packed in a rigid container equipped with an orifice
from which the powder can be shaken. Some users prefer to pour the powder
onto the hand and scoop it up onto the toothbrush, others to dispense it
directly onto the toothbrush. The disadvantages of tooth powder compared
with toothpaste and the difficulty of obtaining predictable doses of health-
benefit agents at each use, has led to the virtual demise of tooth powder as a
major oral-care product.
7.4.4 The toothbrush

The toothbrush is the real workhorse in oral hygiene. (It has been discussed in
detail in the first edition of this book). Toothbrushes are available as hand
operated devices and as mechanically driven devices. The major functions of
the toothbrush are to remove dental plaque and to work with toothpaste to
remove dental stain. The toothbrush also provides a mechanism with which
to apply toothpaste for its secondary benefits, such as anti-calculus activity.
The toothbrush, used alone, can remove soft dental plaque; dentifrice is not
necessary. The consumer, however, has been taught to use toothbrush and
toothpaste together and adheres to that practice. (In a study reported by de
la Rosa [7], use of dentifrice with the toothbrush for a period of 14 days
resulted in an increment of only 5% in plaque removal compared with use of
a toothbrush without dentifrice.)
Claims are frequently made for superiority of one type of toothbrush or
design over another. Such claims are difficult to support at the consumer level
because of the critical importance of non-structural factors in toothbrush
performance.
7.4.5 Oral rinses

Oral rinses supplement, but cannot substitute for the toothbrush. Most on
the market today are formulated to freshen the breath directly and perform
at least one secondary function, usually related to a health benefit, e.g.
destruction of plaque and other oral bacteria. The sale of oral rinses around
the world is variable. In the United States, oral rinse sales are about one-half
of toothpaste sales on a monetary level.
Some 'active' agents have defied incorporation into toothpaste because
they interact with toothpaste excipients. This problem has been overcome
by formulating the agents into oral rinses. In some instances, where the
agents are compatible with both paste and rinse, the rinse has shown greater
efficacy.
7.4.6 Mechanical devices

Mechanical devices to cleanse the teeth are becoming increasingly sophisti-
cated. Mechanical devices are available which not only cleanse the teeth, but
also are able to deliver agents to the dentition, e.g. anti-plaque agents from
water irrigators. The purpose of special mechanical devices (other than the
toothbrush) is to compensate for the inability of most consumers to realize
the full potential of the toothbrush (mechanical cleansing aids have limited
popularity and will not be discussed in this chapter).
7.5 Consnmer practices
The average consumer, including those in more industrialized countries, is

non-compliant in following dental care regimens advocated by dental
professionals [2]. A major objective of providers of oral-care products is to
make them easy and pleasant to use and more effective at the same given level
of compliance. Dental diseases and conditions caused by non-compliance are
not generally life threatening, and this is reflected in poor adherence to oral
hygiene measures.
Plaque removal has come to be recognized as a most important objective of
self-applied oral care; breath freshening and stain removal are expected
functions of toothbrushing with paste. Studies have shown that the average
consumer does far less than is necessary for maximum plaque control [2], this
despite the large number of highly effective devices and chemical treatments
available. Reasons for non-compliance in disease treatment have been
studied [2]. In oral hygiene practice, major factors are lack of motivation to
follow the regimen properly, not being able or willing to follow label
instructions, not understanding the regimen and cost of adhering to a
regimen. In toothbrushing, for example, individuals frequently do not brush
long enough, do not attempt to reach the more inaccessible parts of the
dentition (e.g. interproximal spaces), generally are not adept at manipulating
the toothbrush, do not fully understand the reasons for toothbrushing, use
old, worn-out toothbrushes which provide only reduced efficacy and do not
use enough toothpaste.
Individuals frequently disregard use directions provided by oral rinse
marketers. Sometimes the reason lies with refusal to endure the discomfort
of maintaining the rinse in the mouth for a long time (e.g. 30 seconds)
especially if it has a high alcohol content and burns. But not infrequently,
the consumer does not differentiate between oral rinses, and even will use
one specified for pre-toothbrushing in the same way as most rinses are used,
viz. after brushing. The benefits of oral rinses, in particular, are usually
established via clinical trials wherein use conditions are specified, especially
frequency and time of use and dosage. It is obvious that non-compliance with
use directions can seriously compromise the benefits studied in the clinical
trial.
Supplements to toothbrushing fare no better than toothbrushes them-
selves. Dental floss, for example, is recommended as a routine procedure,
but in fact not more than a small percentage of a population in an
industrialized society even attempts to use it. Flossing requires a degree of
patience and skill which severely decreases motivation. Years of research
have failed to produce a dental floss which overcomes the basic failures of
common flosses.
Water irrigators and mechanically driven toothbrushes have been intro-
duced to overcome the deficiencies of hand-operated tooth brushes. These
products have developed a substantial market. They are effective, but very
expensive, and it has yet to be demonstrated convincingly that they can
perform substantially better than a conventional toothbrush when the latter
is operated by a knowledgeably motivated brusher. Nonetheless, their
efficacy in the hands of the average brusher can be expected on the theoretical
grounds to be superior to that of hand brushing.
Many studies have been conducted to determine how long people brush
(see Rugg-Gunn and MacGregor [22] and Kleber et al. [23]). The results of
such studies have been conflicting. This is not unexpected, because brushing
time is influenced by the brushing environment (laboratory or at home),
DENTAL PRODUCTS 239
observed versus hidden, gender of study participants, non-conformity
among investigators in measuring the end-point (which frequently is residual
plaque level) and other factors. Times reported have been from a few seconds
to several minutes. Many dental investigators have, despite this wide
variation, elected to have subjects brush for 60 seconds in studies in which
brushing time can influence the results, e.g. comparisons of performance of
different toothbrushes. An average of 30 seconds is a good guess, but only a
guess and oflittle significance considering the interaction of many factors in
toothbrush effect.
7.6 Oral-care product marketing
7.6.1 Targeting consumer groups
The oral-care market is much more competitive today than it was only a few
decades ago because new innovations, in products and packages, has vastly
increased the number of product niches. At one time, the major concern of
the consumer was whether to use a product for its therapeutic benefits
(fluoride) or its purely cosmetic benefits (flavor, etc.) [2]. Almost all tooth-
pastes now contain fluoride, so realistically fluoride can be eliminated as an
influence on the toothpaste purchase decision. New 'therapeutic' functional-
ities have been introduced into toothpastes and oral rinses, however, and the
consumer still is swayed to purchase on the basis of interest in a product's
'therapeutic' benefits as opposed to satisfaction with cosmetic properties,
such as flavor.
Products are available which fall into the following categories:
Toothpastes With low abrasion
For tooth 'whitening'
To inhibit calculus (tartar) formation
To relieve hypersensitive teeth
To reduce plaque
To freshen breath (mouthwash effect)
To provide a special 'clean feeling' (as claimed for
baking soda)
To provide special beneficial ingredients for confi-
dence in using products used historically by the
dental profession, e.g. peroxide
For children (special appearance and flavor)
With combinations of one or more of the above
With 'natural' ingredients
Oral rinses To freshen the breath
To destroy bacteria that can cause bad breath
To treat the dentition with fluoride
To help inhibit calculus

To help remove plaque, especially when used before
toothbrushing
To reduce plaque and plaque-related gingivitis
Toothbrushes Which are manipulated by hand
Which are driven mechanically
With special configurations of bristles and arrange-
ments thereof
With special head designs
With inflexible or flexible shafts
F or children
Dental floss Thread-like or ribbon-like
With or without fluoride
Waxed or unwaxed
Flavored or unflavored
Denture cleansers With toothpaste characteristics
To remove plaque and debris by soaking
To remove plaque and debris in a foaming medium
The huge array of oral-care products now available makes targeting
towards specific but large target groups very difficult, especially when
consumer preference is frequently influenced by his or her concern for
'therapeutic' versus cosmetic attributes. Fortuitously, 'therapeutic' agents
used in toothpaste are for the most part compatible with toothpaste excipi-
ents. As a result, toothpastes are being marketed which claim to be effective
simultaneously in one or more of cleaning teeth, protecting against caries,
combating plaque and gingivitis and inhibiting calculus. In some circum-
stances, advertising may concentrate on only one facet, perhaps calculus
inhibition, in the hope that the consumer recognizes other attributes without
prompting.
There is considerable disarray overall in the oral care area. Promoters of
oral-care products in the US (mainly new to the market) are introducing
new products which can provide the ultimate in what the consumer seeks in
oral care, namely, teeth which are truly whiter optically, actually bleached.
This is the ultimate toothpaste function. A toothpaste which achieves this
objective conveniently and at reasonable cost undoubtedly will be the OTe
dentifrice product with greatest consumer demand.
7.6.2 Regulation of the industry

The oral-care product industry is regulated to greater or lesser extents
depending on the country involved. Usually, the ultimate authority is the
national government. Indirect regulation, however, not infrequently is
exerted by non-governmental bodies and by marketing pressures. In some
DENTAL PRODUCTS 241
instances, however, there is no substantial regulation at all and ludicrous
claims may be made.
Elements of the working of the regulatory process can be illustrated by
reference to features of the United States system. The authoritative body is
the Food and Drug Administration (FDA), an arm of the federal govern-
ment. The FDA categorizes the OTC oral-care products as either drugs or
cosmetics. Toothbrushes and other mechanically operated products are
considered to be drug devices. Chemical agents, such as toothpastes which
combat dental caries, are also categorized as drugs. The two types of drugs
are regulated by different groups within the FDA. The FDA is responsible
for both efficacy and safety. Products which do not affect disease status of
the oral cavity are treated as cosmetics, and regulation thereof by the FDA
is minimal, depending on individual situations.
A next level of regulation is the dental profession, usually acting through a
central association or society. Examples are the American Dental
Association (ADA) and the British Dental Association. These groups
frequently consult with the government regulatory body. Some formally
endorse oral products. The ADA gives its 'seal of acceptance' to products
which have demonstrated safety and efficacy to the ADA's satisfaction. This
level of regulation is especially powerful when the endorsement can be used in
advertising. The ADA's seal is valuable because it can be used in commercial
advertisements. The ADA has a long history of product approval via the seal,
and from time to time has issued guidelines for proving safety and efficacy to
the ADA's satisfaction. Among OTC drug products, there are available
guidelines, for example, for proving out fluoride products and making
changes in them [24], and for demonstrating the safety and efficacy of oral
rinses which reduce gingivitis associated with supragingival plaque.
Less direct regulation of oral-care products may be exerted via advertising
agencies or advertising review groups. Reputable agencies usually require
substantiation of advertising claims. The depth of substantiation varies from
agency to agency. Another related regulatory process is challenge of a
company's claims by a competitive company. This may be resolved by the
judicial system.
The restraints that are placed on advertising OTC oral-care products are
substantial, especially in advanced industrial markets. Significantly, quanti-
tative comparisons of product performance, such as product A is twice as
effective as product B in performance, are rare. There are several reasons for
this, one unfortunately, being lack of consensus on evaluation methodology.
Space prohibits detailed descriptions of guidelines recommended by
authoritative bodies for proving the safety and efficacy of new OTC oral-care
products. New guidelines are constantly being developed. It behoves
promoters of OTC oral-care products to assure themselves that such
products can be supported by appropriate guidelines, if they exist. Guidelines
prepared by authoritative groups exist for the determination of toothpaste
abrasivity, fluoride product efficacy, efficacy of pastes for hypersensitive

teeth and products to reduce plaque and gingivitis.
7.6.3 Product evaluation; support of marketing claims

Evaluation of product performance is unusually difficult in the arena of oral
hygiene products, with few exceptions. Major areas where product perfor-
mance must be substantiated to support marketing claims are toothbrush
performance, tooth cleansing (stain removal), anti-plaque efficacy, anti-
caries activity and other areas where the activity concerns specific biological
factors, such as anti-calculus and reduction in tooth hypersensitvity. The
depth of scientific support required to market a product varies from country
to country, and, as discussed above, with the nature of the regulatory agency,
e.g. governmental or advertising agency, and whether an authoritative guide
to testing has been established.
7.6.3.1 Hierarchy of claim support Depending on circumstances, four

interrelated levels of claim support can be considered. The lowest is
laboratory data (including animal data). Such data may suffice in some
regulatory climates, but are weak as support unless backed by a strong
correlation between them and more advanced levels of evaluation. A next
step above laboratory data is short term use in the human under controlled
conditions. The results may be quite misleading in predicting long term
efficacy. However, the studies can be structured to incorporate conditions
which take them a step closer to real life. The next rung of the testing ladder
is long term clinical testing under carefully controlled conditions, wherein
compliance with the use regimen is enforced and product distribution, etc. is
carefully monitored. Finally, long term clinical trials in which the test
product is used under true home-use conditions, i.e. without supervision.
There are innumerable wrinkles in the conduct and interpretation of the
results of each of these trials to support claims for efficacy. It is beyond the
scope ofthis chapter to discuss these trials fully, e.g. statistical requirements,
logistics, etc., but a few examples are provided here for clarification.
7.6.3.2 Laboratory data Laboratory data can be very convincing in

supporting in vivo performance claims, but can be misleading, and even
counterproductive, unless they are grounded in an extensive data base
generated over the course of time by reliable investigators, and have been
clearly correlated with the results of more advanced evaluation procedures.
Several examples can be cited. The relationship of abrasivity of toothpaste
to removal of tooth stain has been studied for at least a century. The in vivo
work preceded the in vitro and over the course of experimentation the latter
was developed to a fine art and it was established that a minimum radioactive
DENTAL PRODUCTS 243
dentine abrasion (RDA) for a toothpaste of about 15 was prerequisite for
removal of stained pellicle [2]. Today, the RDA value (or equivalent) can
usually be relied on to assure that a toothpaste can clean away stained
pellicle. The addition of fluoride to toothpaste is now common. The possible
anti-caries efficacy of fluoride was recognized as the result primarily of
epidemiological observations. The mechanisms of fluoride action were even-
tually established by laboratory studies (including animal studies) of high
investigative quality. Reputable dental investigators now accept specific in
vitro studies of fluoride toothpaste as being reliable predictors of the anti-
caries activity of a toothpaste in the human, and forego the costly, lengthy
clinical trials once required to prove efficacy.
The discouraging side of in vitro testing of oral hygiene products is that
most relevant in vivo aspects are difficult, if not impossible, to mimic in vitro.
Quantitative comparisons of product performance based on in vitro data are
generally invalid because of the uncertainties associated with duplicating real
life conditions. Measurement of toothbrush performance is an outstanding
example. It is simple enough to design a brushing machine, an arrangement
of teeth or another substrate, and an artificial soil, but the almost infinite
possibilities of variation in consumer brushing habits and tooth accumula-
tions make it implausible to generalize quantitatively on the results obtained
with only one variable usually in play in an in vitro study.
Laboratory data, alone, have occasionally been used as claim support. The
marketer, however, is obliged to point out to the consumer that the basis for a
claim is laboratory data.
7.6.3.3 Short term human studies Short term human clinical studies can
yield valuable predictive data, and are preferred by far to in vitro tests. A
classical example is the L6e model for gingivitis [9]. Here, the subject refrains
from all oral hygiene practice for a period of about 2-3 weeks. This simulates
the worst case of poor oral hygiene. Plaque and gingivitis develop profusely.
The effect of treatment on these conditions can then be determined. They can
be reversed, for example, by returning to a good toothbrushing regimen, or
by an effective anti-plaque agent, such as chlorhexidine. This type of test
and variations thereof have in many circumstances been able to predict
whether oral hygiene agents and devices have the potential to be useful in oral
care.
A variety of other short term clinical studies has been used productively.
One is the half-mouth technique. Here, the dentition on one side of the mouth
is treated with the test material and the other side acts as control. The plaque
removal ability of a product or process can be estimated semi-quantitatively
by testing for plaque removal effects using subjects who already had
accumulated plaque during normal living. (In the case of plaque studies, the
results can be severely confused by inadequacy of the plaque measurement
procedure [10]).
7.6.3.4 Major scale clinical trial A full blown trial is the ultimate test for
efficacy. Individual investigators have tended to use their own designs, with
the result that consensus on the test agent has not always been possible.
However, guidelines for conducting clinical trials for specific purposes are
being developed, e.g. to evaluate the efficacy of agents which reduce plaque-
induced gingivitis. Clinical trials are very expensive and time consuming.
Early trials of fluoride toothpastes, for example, ran for at least two years
and involved hundreds, even thousands, of subjects. Protocols are still
controversial. Many investigators prefer to include in the trial design at least
one supervised use of product per day when the subjects are available,
thereby ensuring a degree of compliance with the use regimen. Others aver
that a more realistic situation in the test of an OTC agent is to omit supervised
use, making the test conditions closer to real life. There are several ways to
conduct clinical trials, depending on the objectives, logistics and ethical
considerations. In the long run, it is preferable before starting clinical trials
to consult with regulatory agencies which may have a voice in the interpret-
ation of the results.
7.7 Principles of product formulation
7.7.1 The toothbrush and other mechanical aids
7.7.1.1 Toothbrush function The toothbrush is a device, and those

involved in the development of oral hygiene products must understand its
functioning if they are to be able to design suitable supplemental products.
The toothbrush is the key to oral cleanliness. Alone (or with water) it can
maintain the mouth in a satisfactory state of hygiene. However, as mentioned
previously, the vast majority of the population do not employ the toothbrush
properly, or with adequate frequency. As a result, supplemental products
have been developed. These include (i) dentifrice, to be used with the tooth-
brush; (ii) oral rinses, to be used before or after the toothbrush; and (iii)
devices to supplement the mechanical action of the toothbrush, e.g. dental
floss.
7.7.1.2 Plaque removal The toothbrush alone, used with care and dili-
gence, can remove enough plaque for the maintenance of a satisfactory state
of oral hygiene. Conventional toothpaste may improve plaque removal by
only about 5%. Toothpaste, however, depending on its composition, can
offer a route to substantially increased plaque reduction or other therapeutic
function, e.g. inhibition of calculus formation. Figure 7.3 depicts the typical
route of plaque removal by toothbrushing. The efficacy of the toothbrushing
operation is determined, however, by factors over which only the tooth-
brusher (not the toothbrush manufacturer) has control:
(i) motivation to brush properly;
(ii) brushing for a long enough time;
(iii) ability to manipulate the toothbrush;
(iv) knowledge of how to brush; and
(v) use of a toothbrush in good condition.
7.7.l.3 Stain removal A second major role of the toothbrush is to act in

concert with the abrasive to remove stained pellicle. Here, the toothbrush
applies the force needed to provide abrasive cleaning.
7.7.l.4 Toothbrush construction and design The toothbrush consists of a

handle, a neck and a head. The functionality is in the head, which contains
rows of bristles, usually nylon filament. Hog bristles, popular at one time,
have now been replaced by nylon for reasons of sanitation, cost, safety and
reproducibility. Nylon bristles can be made to uniform, strict standards.
Bass [25], an early investigator of toothbrushes, recommended a straight
handle, an overall length of about 6", width about 7/16", three rows of nylon
bristles, six tufts to the row, about 80 bristles per tuft, 0.007" diameter
bristles, straight trim, finished to 13/22" length, bristle ends rounded. Very
few toothbrushes with those dimensions are being marketed today. Rather,
toothbrush marketers have let their creativity run amuck, and the range of
toothbrush innovation has run from the Bass-type brush to brushes with
diamond-shaped head, flexible handle and bristles which vary in length on
the same head. Support for superiority of the new designs is meager, usually
based on in vitro experiments, uniqueness and the investigator's creativity.
Mechanically driven toothbrushes have been developed. These should
theoretically perform better than manual brushes, by making the brushing
experience less dependent on the individual. The question of whether or not
they are more effective in the home-use situation is still to be answered.
7.7.1.5 Other mechanical aids Toothbrushing alone, as practiced by most

individuals, is inadequate to remove plaque. The interproximal and sub-
gingival sites are the loci of a major proportion of plaque-caused diseases,
and clearing those areas of plaque with the toothbrush requires an extra-
ordinary degree of motivation and dexterity. Consequently, a large pro-
portion of the population needs additional help to control plaque. This help
is available from a variety of mechanical devices. The available mechanical
supplements cannot all be reviewed here, but some of the more useful devices
are:
• Oral irrigator- highly effective at reducing gingivitis, despite apparently
limited plaque removal.
• Dental floss-can remove plaque, improve gingival condition, but re-
quires high manual dexterity for maximum effect.
• Wooden tips-made from soft wood to prevent injury to the gingiva.

Not recommended where interdental space is fully occupied by the
papillae.
• Rubber tips-pointed, pliable rubber tips mounted on the toothbrush
handle distally to the brush head.
• Interdental brushes-marketed either as a single tufted brush or a
miniature bottle brush. Not popular, but highly effective.
7.7.2 Toothpaste formulation practice
7.7.2.1 General concerns As recently as thirty to forty years ago, denti-

frices were designed to fulfil two major functions: (i) to act as vehicles for
abrasives to remove stained pellicle; and (ii) to flavor and freshen the breath.
Today, dentifrices also act as vehicles to introduce active agents into the oral
cavity. Although dentifrice is not a requirement to remove or control dental
plaque [7], few people would brush enthusiastically without one. The
accumulation of new plaque may be slightly retarded due to the surfactant's
effect. Although some investigators claim dentifrice can increase the amount
of plaque removed by toothbrushing, most evidence indicates that the same
amount of plaque is removed, whether a highly abrasive, a non-abrasive, or
no toothpaste is used [2]. The need for abrasive to remove stained pellicle,
however, was firmly established by Kitchin and Robinson [26], who asked
'How abrasive need a dentifrice be?' They reported a trial with 113 dental
students, in which stains ranging from minor to heavy were readily removed
by brushing 1-2 times with an abrasive dentifrice, whereas toothbrush and
water alone had little effect.
A breath-freshening quality in a dentifrice is now expected by the consumer.
Although the cost of flavoring a dentifrice can be higher than that of all of
the other ingredients together, most people would agree that dentifrice usage
would be significantly lower today, were the easily perceptible stain removal
and breath-freshening performance of dentifrice less than satisfactory. Flavor
can determine consumer purchase decision, all other factors being equal.
Toothpastes are now being marketed with flavors that appeal only to limited
segments of the market.
Dentifrices are marketed as pastes, liquids, and powders. Paste is the
predominant form, both because of its inherent consumer benefits, and
because it is the preferred dosage vehicle for special therapeutic and cosmetic
agents. Powders, once very popular, have fallen considerably in market
appeal. Concentrated liquids have maintained a small share of market.
The major ingredients of dentifrices and their functions are outlined in
Table 7.1. (For further details, the reader is referred to Pader [2]). The
economics of many dentifrice raw materials differ in different parts of the
world; the formulator may find one particular type of formulation less
Table 7.1 Dentifrice ingredient functions
Ingredient Function Example
Abrasive Helps remove stained pellicle, acting in Precipitated chalk

concert with the toothbrush. Hydrated silica
Humectant To provide a bacteriologically-stable, 70% sorbitol
fluid, creamy base, which resists 'drying
out' and in which other ingredients can
be suspended or dissolved.
Binder To develop a cohesive structure with Precipitated silica
the desired rheological properties. Calcium carrageenate
Carboxymethyl cellulose
Surfactant To provide foam and detersive action Sodium lauryl sulfate
during use; possibly may offer anti-
microbial and other benefits.
Flavor To make the toothbrushing experience Peppermint oil
pleasant, and to leave a residual Saccharin
freshness and cooling.
'Active agents' To provide therapeutic and/or other Fluoride
special benefits.
Water To assist formulation.
expensive in an Asian country than in, say, Europe, and vice versa for another
type offormulation. The cost difference may be very significant. Consequently,
the formulator must carefully balance the type of formula against the cost
factor; a dentifrice that has optimal characteristics of, for example, performance
and consumer appeal, in one country may not be economically feasible in
another.
7.7.2.2 New toothpaste functions The sudden proliferation of new tooth-

paste functions, packaging and visual signals has made formulation much
more complicated than heretofore. It is in the best interests of the marketer
capable of handling a range of toothpastes to simplify the formulations in
the interest of ease of manufacture. It is worthwhile to develop a base
formulation which can be modified easily. For example, most toothpastes
offered today contain fluoride. It is advantageous to restrict all the tooth-
paste formulations in the line to one which is compatible with fluoride. That
approach is espoused here; multiple types of formulation in the same
manufacturing facility can be disastrous economically. Today's technology
allows major variations in toothpaste appearance, flavor, etc., by simple
changes in the same base formula.
Toothpastes must be stable during shipping and storage (6 months at
12S0F). They should be esthetically appealing. They should function as
promised by the marketer. A deficiency in any of these parameters can
seriously impair acceptance by the consumer, and each brand hopefully will
show a unique difference from competitive brands.
Toothpastes are now available with various 'therapeutic' functions. The

main functions are:
• to help prevent caries
• to promote gum health (anti-gingivitis)
• to reduce plaque
• to reduce sensitivity of hypersensitive teeth
The same 'active' sometimes is offered in both toothpaste and oral rinse
vehicles, e.g. fluoride toothpaste and fluoride rinse. Incompatibility between
toothpaste excipients and the agent will prevent this in some instances. A host
of agents has been proposed to function in specific oral therapeutic modes. In
the usual course of development of an agent, initial studies are conducted
with simple liquid systems. The toothpaste formulator must later ascertain
that the toothpaste vehicle developed does not negate the positive activity
already demonstrated with the agent dispensed as a simple oral rinse.
Unfortunately, the selection of a therapeutic active for a toothpaste has been
clouded by such factors as the regulatory climate, inappropriate research to
support marketing claims, lack of consensus among investigators on the
interpretation of laboratory and/ or clinical trials, use of conflicting
methodologies by different researchers, etc. The agents of greatest current
interest in OTe oral-care products are discussed briefly, below (section 7.9).
7.7.2.3 Toothpaste ingredients and their functions Toothpaste is generally

formulated along either of two lines: (i) low abrasive level/high humectant
level (Type I) or (ii) high abrasive level/low humectant level (Type II).
Table 7.2 Example of a Type I dentifrice"
wt%
Active agent Sodium monofluorophosphate 0.78

Abrasive Silica xerogel b 14.00
Binder(thickener Carboxymethyl cellulose' 0.30
Hydrated silica d 8.00
Polyethylene glycol 1450 5.00
Humectant Sorbitol, 70% 46.72
Glycerin, 96% 20.90
Surfactant Sodium lauryl sulfate (dentifrice grade) 1.50
Flavor Mint-type 2.00
Saccharin 0.20
Color Aqueous solution of permissible dye 0.50
Preservative Sodium benzoate 0.10
aAfter Pader [34]

bSylodent 750; W.R. Grace & Co., Davison Chemical Division
'Grade 9MX; Hercules, Inc.
dSylodent 15; W.R. Grace & Co.
DENTAL PRODUCTS 249
Table 7.3 Example of a Type II dentifrice'
wt%
Abrasive Calcium carbonate 48.00

Binder/thickener Carrageenan b 0.94
Humectant Glycerin 22.00
Surfactant Sodium lauryl sulfate 2.00
Flavor Flavor oil 0.80
Sodium saccharin 0.20
Preservative Sodium benzoate 0.50
Other Water to 100.00
a From FMC commercial bulletin (1988)

bViscarin R TP 389
Table 7.2 presents an example of a Type I toothpaste, Table 7.3 that of a

Type II dentifrice [1].
7.7.2.4 Toothpaste rheology It is necessary to understand relevant

features of paste rheology to formulate and manufacture toothpaste variants
economically and expeditiously. The rheological properties affect many
esthetic and functional attributes. The ideal rheological profile is a rigid
gelatinous structure which becomes deformed and flowable with the
application of minimal stress and which re-establishes its original structure
almost instantaneously. The preferred rheological properties of a paste
include [27]:
(i) A homogenous ribbon is formed upon extrusion from the container.
(ii) The paste does not flow from the open container (uncapped tooth-
paste tube) in the absence of an extrusion pressure.
(iii) Only minimal effort is required to extrude the paste.
(iv) The extruded ribbon of paste breaks sharply and cleanly onto the
toothbrush.
(v) The extruded ribbon 'stands up' on the brush; it does not sink
between the bristles or roll off the sides.
(vi) The paste disperses quickly in the mouth and does not feel gummy.
(vii) The flavor releases quickly.
(viii) The foam quality is pleasant and the amount appropriate.
(ix) The foam rinses from the mouth easily, leaving no residual gummy
feeling in the mouth.
(x) Spittle is easily rinsed from the sink.
(xi) The paste is stable during shipping and storage.
(xii) Dispensing of the paste is compatible with the dispensing
mechanism.
The best rheological properties are obtained with formulations with

relatively high viscosity along with a relatively high yield point [27].
Preferred rheological properties are most readily achieved with Type I
toothpaste. Acceptable pastes, however, can be obtained with Type II. The
formulator may select either depending on quality standards required or
marketing concerns in a local market and/ or availability and cost of local
supplies. Type I formulations are more versatile with respect to developing
a range of products from a single base composition, whether therapeutic or
cosmetic.
Type I formulations frequently rely on amorphous silica for cleaning/
abrasion as well as rheological structure. The Type II formulation rheology,
however, relies largely on the sheer bulk of the abrasive.
Rheological additives for the Type I and Type II toothpastes have been
discussed in detail previously [1]. The principles of their selection will be
discussed here.
Type I toothpastes are more restricted in the choice of a rheological
additive system than Type II toothpastes. In both instances, the toothpaste
structure derives from abrasive particles suspended in a three-dimensional
network of a polymer, or, more usually, a mixture of polymers. The demands
of Type II toothpastes are few, because structure and stability thereof are the
result of what may be only a loose agglomeration of abrasive particles in a
viscous liquid medium, the concentrations of which limit mobility of the
abrasive, as though it were a pile of sand. A polymer is added to improve flow
characteristics and prevent separation of aqueous and particulate phases, i.e.
to retard settling of the particles by increasing the viscosity of the liquid
phase. Any number of polymers have been used for the purpose-sodium
carboxymethylcellulose, guar gum, gum arabic, xanthan, locust bean gum,
etc.
A different situation prevails in Type I toothpastes. Here, the abrasive or
other particles are suspended and immobilized within a three-dimensional
network of polymer chains which is essentially rigid when at rest but readily
takes on the flow properties of a liquid when it is subject to a stress. These
polymeric structures exhibit yield values; they are immobile until a certain
stress is exceeded, as by squeezing the tube of toothpaste. They are restored
to their original structure when the stress is removed, almost instantaneously.
7.7.3 Basic dentifrice ingredients

7.7.3.1 The abrasive Pader [2] defined an abrasive as " ... a solid,
particulate material which, when applied under pressure, can dislodge
foreign material from a surface." He also noted that for an abrasive to be
effective, it must remove a finite amount of dental enamel along with stained
pellicle, and also some dentin if the dentin is exposed to the abrasive's action.
Abrasives are preferably chemically inert. They must:
DENTAL PRODUCTS 251
(i) resist interaction with the other dentifrice ingredients and be essentially
tasteless;
(ii) maintain their integrity in the dentifrice product-salt and sodium
bicarbonate have frequently been proposed and used as dentifrice
abrasives, although the latter is used in marketed dentifrice to a very
limited extent;
(iii) be safe for their intended use;
(iv) be capable of being formulated into a stable, smooth, extrudable paste
that tastes good, is quickly dispersed in the mouth, and has satisfactory
rheological properties.
Four physico-chemical characteristics are important in selection of an
effective, safe abrasive for dentifrice use: (i) hardness; (ii) toughness; (iii) degree
of chemical inertness; and (iv) particle size and shape.
R ardness The ideal abrasive will be no harder than necessary to attack

its dental substrate (i.e. stained pellicle). The vulnerable underlying enamel
and any dentin that may be exposed must be considered. Hardness is generally
stated in terms of the Mohs scale of hardness. In this scale, talc is rated 1
and diamond 10. The Mohs hardness of dental enamel is 4-5, and of dentin
2-2.5. There is no hard and fast rule for selection of abrasive on Mohs
hardness, because the safety and efficacy of an abrasive is critically dependent
on its performance in the presence of the total dentifrice formulation. As a
general rule, however, the prudent formulator will avoid excessively hard
crystalline materials for abrasion. The relative abrasivity of an abrasive
material in a series of abrasives is not determined solely by its Mohs hardness,
but also depends on the substrate used. The prudent formulator will seek
an abrasive that yields a formulation, the abrasivity of which is such that it
will remove a minimal amount of dentin, compatible with pellicle removal
using dentin as a test substrate.
Toughness This is defined as the ability of an abrasive to withstand the
forces brought to bear on it when in use. Although not previously given great
attention, toughness may become increasingly important. This is because
tailor-made dentifrice abrasives are formed by controlled agglomeration of
small particles. Crystalline silicon dioxide is extremely abrasive and, as an
amorphous, friable particle, is relatively soft and therefore an ideal dentifrice
abrasive.
Degree of chemical inertness Dental abrasives should be chemically inert.
The importance of this becomes increasingly evident for formulations with
therapeutic action; containing potentially chemically reactive materials, such
as fluoride.
Particle size and shape These strongly influence performance, safety and
esthetics. Particles with diameters of about 30.urn or more will be detected
as objectionably gritty in the mouth. An average particle size of about 3-12 nm

will generally be acceptable to the consumer. Tight specifications on particle
size are critical to the manufacture of a safe, pleasant dentifrice-particular
attention must be paid to the particle size range achieved during manufacture
by careful milling and sizing.
The ability of an abrasive to remove stained pellicle will generally increase
with its concentration in the dentifrice, with particle size, and with hardness.
The abrasivity of a given formulation will vary according to external forces
(including the toothbrush), the vigor with which it is used, and the characteri-
stics of the individual dentition [28].
Abrasion for dentifrice application can be measured by many methods.
The two most popular are the radioactive dentin abrasion (RDA) method
and the surface profile method. Both have been described by Pader [2]. In
the RDA method (most frequently used), extracted teeth are subjected to a
neutron flux under standardized conditions. They are then mounted in a
machine equipped to allow controlled brushing with a toothbrush and a
dentifrice slurry. After brushing for a given time under a specific toothbrush
e
pressure, radioactivity 2 p) in the slurry is measured. A calcium pyrophos-
phate abrasive system is the reference abrasive standard, set at a RDA value
of 100. Generally speaking, a dentifrice with an RDA value of 60-100 is
adequate to maintain teeth essentially free of stain. A dentifrice with an RDA
value over 250 is probably unnecessarily abrasive.
Cleaning (removal of stained pellicle) is related to abrasivity: the higher
the abrasivity (up to a limit), the better the cleaning. Although RDA is
considered to be an adequate method for assessing cleaning, it has been
difficult to develop an in vitro cleaning test due to the lack of a suitable artificial
stain. Stookey et al. [29] devised a stain which reportedly was adequately
resistant. These workers correlated their in vitro method with a laboratory
'cleaning ratio'. The American Dental Association [30] conducted a study
wherein three dentifrices with abrasivity indices of 85, 170 and 255, respectively,
were compared with respect to ability to remove or to prevent the accumulation
of stained pellicle in vivo. The results validated the premise that abrasivity of
a dentifrice to dentin can be used to assess cleaning power.
Several dental abrasives are available. Some of the more popular ones will
be discussed in the following sections.
Hydrated silica Intensive investigation of dental silica technology has

demonstrated the potential of tailor-made silica products to meet the needs
oftoday's dentifrice market. Figure 7.4, for example, shows the relationship
between RDA and silica gel loading for a range of silica xerogel abrasives
developed by a single manufacturer. Hydrated silica precipitates, with
abrasive properties, are also available, developed as alternatives to the silica
xerogel. Xerogels and precipitates can be formulated into dentifrices; both
can give clear, abrasive dentifrice gels. One marketed hydrated silica
DENTAL PRODUCTS 253
150
140
130
120
c
0 110
'Cij
~
.0
100
ell
c
90
E
(lJ 80
"0
(lJ
>
70
U
ell 60
0
'6 50
ell
a:
40
30
0 5 10 15 20 25
Percent xerogel in dentifrice
Figure 7.4 Effect of silica xerogel structure and level in dentifrice abrasivity. Courtesy of W.R.
Grace & Co., Davison Chemical Division.
preCIpItate is a mixture of large and small particles; the former provide

abrasion, the latter, gel structure.
Calcium phosphates Di- and tricalcium phosphates have been widely used
as dentifrice abrasives. They belong to the family of calcium phosphates repre-
sented by the CaO- P 20 5 - H 20 system. They are not compatible with sodium
fluoride, but are used with sodium monofluorophosphate. Dicalcium phos-
phate dihydrate (DCPD), CaHP0 4 '2H 20, is not stable in dentifrice systems.
On heating, or even storage, the water is lost and the anyhydrous salt (DCP)
forms. DCP is considerably harder than DCPD, therefore more abrasive. In
dentifrice, the conversion of DCPD to DCP may be accompanied by firming
of the dentifrice, but DCPD can be stabilized by the addition, during manu-
facture, of tetrasodium pyrophosphate or trimagnesium phosphate. DCPD
for dentifrice use has been manufactured with RDA values of 200-1350
(reference calcium pyrophosphate, set at 500). Consequently, it is relatively
low in abrasion, but quite adequate for most situations. DCP, being very hard,
can be admixed with DCPD to raise DCPD dentifrice abrasivity.
Calcium carbonate Precipitated calcium carbonate is an inexpensive, but
effective dentifrice abrasive. Its high reactivity with fluoride limits its use to
sodium monofluorophosphate dentifrices. Even then, fluoride bioavailability
may be poor. Several commercial grades of precipitated calcium carbonate
are available, ranging in particle size.
Alumina trihydrate This abrasive is used in several marketed dentifrices and

is available with a broad variety of specifications. Chemically, it is A1 20 3 ' 3H 2 0
or AI(OHh. Careful selection of particle size is essential since the material is
generally derived from the alumina manufacturing process. In its gibbsite form,
used primarily, alumina trihydrate has a Mohs hardness of 2.5-3.5. Excessively
abrasive grades are commercially available, but selection of a grade suitable for
dentifrice is a simple matter because of the excellent formulation abilities.
Alumina trihydrate is more reactive with fluoride salts than is, for example,
hydrated silica, but is less reactive than calcium carbonate. Sodium monofluoro-
phosphate, in combination with aluminum trihydrate, has been shown to be
clinically active against caries. Alumina trihydrate dentifrices can corrode alumi-
num tubes if no precautions are taken.
Other abrasives A host of particulate minerals and organic polymers have
been used or proposed for use as dentifrice abrasives. Among them are insoluble
sodium metaphosphate, sodium aluminosilicate, melamine-formaldehyde, poly-
styrene, polyethylene, and polymethacrylates.
7.7.3.2 Humectants The function ofa humectant can be divided into two
categories: (i) bulk dentifrice properties; and (ii) in-use properties. The humectant
contributes to the bulk properties of the dentifrice by:
(i) providing a vehicle that carries abrasive, flavor, drug and other compo-
nents, to give a smooth, homogeneous, functional dentifrice;
(ii) maintaining an extrudable paste that resists 'drying out' when exposed
to the atmosphere for prolonged periods of time;
(iii) providing microbiological stability;
(iv) developing a paste structure in conjunction with the thickener;
(v) assisting maintenance of phase stability, i.e. preventing separation of
the aqueous and non-aqueous components; and
(vi) providing the means to formulate a translucent/transparent 'gel' dentifrice.
Features of the dentifrice that are humectant-dependent are:
(i) flavor release and impact, and sweetness of the flavor by virtue of the
inherent sweetness of the humectant;
(ii) amount and character of the foam; and
(iii) dispersibility and spreadability of the dentifrice in the mouth.
Sorbitol solution and glycerin are the predominant humectants for denti-
frices, alone or in combination. The 'sorbitol' solution is usually a 70% aqueous
solution of sorbitol, or a sorbitol modification that resists crystallization due
to its content of higher hydrogenated polysaccharides. The amount of poly-
saccharides in the final sorbitol syrup can be determined during the manu-
facturingprocess. Pader [31] described a sorbitol with relatively high amounts
of hydrogenated polysaccharides, which was used advantageously in toothpastes.
Two microbiological aspects of the humectants are important: (i) ability of
the humectant to resist microbial growth in the toothpaste; and (ii) resistance
to metabolism and subsequent production of acids by oral organisms. The
water activity (a w), defined as the vapour pressure of the solution divided by
the vapour pressure of water at the same temperature, determines whether
or not a solution will support microbial growth. Normally, values of aw
above 0.9 are required for growth. The addition of glycerin or sorbitol lower
the aw of the dentifrice to a point where microbial growth is suppressed. In
addition, the osmotic pressure is increased, and cannot be tolerated by most
organisms. The humectant, however, cannot be relied on entirely. Even
properly formulated dentifrices have been known to deteriorate microbiologi-
cally (sometimes with gassing) during storage. Contamination must be mini-
mized, from the raw materials through to the final, manufactured dentifrice.
In pure solution, a 30% solution of glycerin or a 40% solution of sorbitol
will stabilize against bacterial attack. Moulds and yeasts, being more tolerant
to environmental conditions, are kept under control with chemical preserva-
tives (e.g. benzoate and derivatives). The refractive indices of glycerin and
70% aqueous sorbitol are both about 1.47, therefore the preparations can
be used interchangeably in so far as a particular refractive index is needed
to formulate clear dentifrices (where humectant and abrasive refractive indices
must be similar).
The humectant must not be fermentable by micro-organisms resident in
the oral cavity, such as Streptococcus mutans. As discussed previously, meta-
bolism of carbohydrate by such bacteria, to produce acids, is a route to caries.
Hydrogenation of glucose and glucose polymers derived from starch hydrolysis
makes the sugars essentially non-fermentable by oral micro-organisms.
7.7.3.3 Binder/thickener The importance of rheological control of tooth-

pastes was discussed above (see section 7.7.2.4). The binder I thickener is the
key to the achievement of the desired rheological properties.
Besides the functional attributes of the polymer, attention must be given to
its ease of incorporation during the manufacture of the toothpaste, its resi-
stance to microbial, enzymatic, chemical and thermal challenges, and its
cost-effectiveness. Dozens of organic polymers and inorganics (both natural
and synthetic) capable of forming three-dimensional structures have been
proposed for toothpaste use [1]. Few (if any) have all of the rheological
attributes required, and frequently it is advantageous to mix polymers, for
example a polymer with high yield value with one that has no yield value.
Every polymer that is useful in toothpaste formulation is able to form a
three-dimensional network in systems containing low water concentrations.
Both organic and inorganic materials can be used in such systems. A common
feature of organic polymers is the presence, in the dry state, of tightly aggre-
gated molecular chains, which, on solvation, open to form strong gel-like
networks of polymeric chains. This phenomenon is pH- and/or temperature-
dependent for some polymers. Maximum strength is obtained with certain

polymers only in the presence of a sufficient amount of appropriate cations.
The strength of the polymeric structure depends on the polymer concentra-
tion, the presence of surfactant, flavor and other additives, and the composition
of the humectant system. The rheological properties of the binder will have
a strong influence on these features of the polymeric structure, and will carry
through to the final toothpaste.
Polymers used in major dentifrice brands are: alginates, carboxymethyl
cellulose, carrageenan, gum tragacanth, locust bean gum, xanthan gum,
polyacrylates and hydrated silicas. Other possible thickening polymers currently
available are gum arabic and gum ghatti. As mentioned previously, combi-
nations of polymers are frequently used.
A 'viscosity bonus effect', whereby glycerin addition to aqueous solution
increases the viscosity, can be observed with many polymer-lean-solvent
systems. For example, sodium carboxymethyl cellulose dispersed in a mixed
solvent system (glycerin:water, 60:40) is about ten times as viscous as in water
alone. A brief outline of the use of polymers in dentifrice applications will
be given in the following sections. For further details, reference [32] should be
consulted.
The number of polymers used extensively in major toothpaste brands has
decreased in recent years. Some manufacturers, generally in order to cut
ingredient costs or because they do not have a need for best toothpaste
rheology, have used less than optimal toothpaste polymers. Only those which
are most valuable in obtaining the rheology discussed in section 7.7.2.4 are
discussed here.
X anthan gum This is a polysaccharide produced by the micro-organism
X anthomonas campestris in pure culture fermentation. The structure of the
main chain of xanthan gum is that of cellulose, and contains sodium, potassium
and calcium ions. The rheological properties ofxanthan gum are very favorable
for the manufacture of toothpastes, particularly low abrasive/high humectant
products. Aqueous systems exhibit high pseudo-plasticity along with a definite
yield value. The viscosity decreases when shear stress is applied, and the gum
recovers almost instantly when the stress is removed.
Xanthan gum can exhibit very reproducible and predictable suspending
power over a wide range of conditions. It has high viscosity at low shear rates.
At very low shear rates, suspended particles remain essentially stationary
because of the very high apparent viscosity of gum solutions below the yield
value. Shear rates of pouring or sq ueezing are large enough to reduce apparent
viscosity. Under high shear rates, low viscosities are observed, and little
apparent viscosity is exhibited during operations such as pumping. Xanthan
gum solutions are resistant to even the high shear imparted by a colloid mill
or homogenizer. The viscosity of xanthan gum solutions is almost independent
of pH or temperature. Xanthan gum will tolerate high levels of water-miscible
solvents. It is even soluble in glycerin at 65°C, but the solution is stringy. It
is compatible with most salts, although it may gel under prolonged exposure
to some salts at sufficiently high concentrations. A small amount of salt helps
to develop optimum rheology in xanthan systems. Xanthan gum is compatible
with many gums, and the rheology of its solutions can be modified by the
addition of other gums. Xanthan gum systems generally require preservation.
Acrylic acid polymers Acrylic acid polymers have excellent rheological

properties for high humectant dentifrices. The Carbomer® resins are carboxy-
vinyl polymers, ranging in molecular weight from about 450000 to 4000000,
and containing -(CHzCHCOzH)-groupings, which may be cross-linked, as
with a polyalkenyl polyether. The dry powders in aqueous dispersion show a
pH of 2.8 to 3.2, depending on concentration. In this state, prior to solvation,
the molecule is tightly coiled and provides only limited thickening. On hy-
dration in water, some uncoiling occurs, but full development of viscosity
potential requires uncoiling of the molecule- best achieved by elevation of
the pH.
The resins form highly pseudoplastic solutions. Their ability to stabilize
suspensions and emulsions is related to high yield value rather than visco-
sity. Consequently, stabilization of suspensions is achievable at low resin
concentration.
The high molecular weight polymers are most effective at pH 6 to 8; viscosity
decreases sharply on either side of this pH range. A 1%, neutralized aqueous
system is a firm gel-like mass. Soluble salts, including sodium chloride and
di- and trivalent cations, considerably reduce the viscosity of the resin solution.
The salt effect varies with the system's composition. For example, it is reduced
in oil-in-water emulsions compared to in water alone. The resins are generally
incompatible with cationic compounds but cationic compounds of a moderate-
to-high molecular weight, exhibiting steric hindrance, will not interfere with
the polymer's thickening action.
Acrylic acid polymer resins are sensitive to high shear, and permanent loss
in viscosity may occur with excessive shear. Temperature has only a small
effect on the viscosity of neutralized polymer solutions, which resist freezing
and thawing, and solutions of the 4000000 molecular weight polymer are
stable to prolonged exposure at 70°C. Acrylic acid resins are compatible with
other polymeric materials, such as xanthan gum and hydrated silicas and do
not support microbial growth.
Silica powders The major silica powders used for dentifrice thickening are
the silica aerogels, silica precipitates and pyrogenic silicas. These powders are
chemically dissimilar from the organic gums mentioned previously, but have
in common with them the ability to form a three-dimensional structure
capable of maintaining abrasive particles in suspension. The silica powders
have found greatest use in low-abrasive/high-humectant formulations, although
they have been used in high abrasive/low humectant dentifrices.
The silica thickeners most widely used in toothpaste in the US are the
aerogels and precipitates. All are amorphous and have a refractive index about
1.46, making them suitable for clear-gel toothpastes. They are variable with
respect to patricle size, surface area and pore structure, and function primarily
by formation of a solvated gel-type structure, which provides a ready route
to the establishment of thixotropy in toothpastes. Silica thickeners exhibit a
yield point, and are excellent agents for the suspension of abrasive particles.
The silica aerogels and precipitates are used in low-abrasive/high-humectant
pastes at loadings of about 5 to 15%. The rheological properties of the gelatinous
structures formed can be modified by the addition of organic polymeric
materials.
Not all silica preparations will develop the desired structures. Thickening
effects are observed only when particles of colloidal size form a network
through the liquid phase. Maximum network formation and thixotropy occur
when small, three-dimensional aggregates are linked together by forces such
as hydrogen bonding. These linkages are broken easily by shearing, and are
re-established when the shear is removed.
Carboxymethyl cellulose Carboxymethyl cellulose is offered mainly as
the sodium salt (SCMC). It does not have the rheology of, say, polyacrylates.
It yields non-Newtonian solutions. The degree of thixotropy oflean-solvent
systems containing SCMC is a function of many factors, such as degree of
substitution (DS) of the polymer backbone, uniformity of substitution, water
content, heat, long hold-times and shear. Thixotropy can vary at a given DS,
depending on processing conditions and raw materials.
SCMC alone will not provide the rheological properties of a Type I tooth-
paste, but may find use in such as a supplemental polymer for its water-
binding and thickening properties. SCMC (as well as gums such as locust
bean gum, gum acacia, carrageenan gum and other vegetable gums) finds
extensive use in Type II toothpastes, where the structural nature of the gum
is less important.
7.7.3.4 Surfactant The surfactant is most important because the amount

and character of the foam generated by a dentifrice affects its consumer
acceptability. Slight improvement in plaque removal can be attributed to the
detergent, which possibly inhibits recolonization of the tooth surfaces [7].
Virtually every detergent developed has been recommended, at one time or
another, for use in dentifrice. In the case of anionic detergents, the limitation
has frequently been the flavor-even trace amounts of impurities can be
detected as a soapy, bitter flavor note. Cationic detergents exhibit inherent
bitter, astringent notes, relatively poor foam generation and doubtful safety.
Non-ionic detergents have been developed for dental specialities, but not for
general use.
Sometimes, addition of a surfactant may result in inexplicable effects on
toothpaste rheology, e.g. increasing fluidity. These effects have not all been
explained. Reaction of the binder/thickener polymer with the detergent
probably is a factor. The detergent may influence solvation of the polymer.
It may, thereby, interfere with function of the three-dimensional solvated
polymer. It is useful to solvate the polymer(s) completely before using it in
toothpaste manufacture, to promote product uniformity and maximum
utilization of the polymer.
Three anionic detergents have been widely used in toothpastes. These are
sodium lauryl sulfate, sodium dodecylbenzene sulfonate and sodium lauroyl
sarcosinate.
Sodium lauryl sulfate Sodium lauryl sulfate (SLS) is the long-chain fatty
acid sulfate, RS0 3 Na, where R is a mixture of long-chain saturated alkyl
chains derived from coconut or similar oils and ranging mostly between C 10
and C 16, principally C 12 . Some grades are available with almost all e l2 cut.
SLS is synthesized through a fatty alcohol route, and the residual fatty alcohol
content must be very low to ensure good flavor. Dentifrice grade SLS is freely
available, in a range of particle size and alcohol chain length (R) distributions.
Larger particle size is preferred for handling in the plant, to cut down dusting.
SLS is a primary irritant but, used at appropriate levels, is safe in toothpaste.
The low toxicity level of SLS when judiciously used in toothpaste is supported
by decades of use in dentifrices around the world, as well as by in-depth studies
of toxicity (cf. [2]). No studies have shown that SLS reduces the efficacy of
fluoride, indeed it has been reported that SLS can enhance in vitro fluoride
uptake by dental enamel [33].
Sodium dodecylbenzene sulfonate Sodium dodecylbenzene sulfonate (DOBS)
is represented by RC 6H 4 S0 3 H, where R is a long-chain fatty acid radical,
mostly dodocyl. Commercial preparations comprise both branched- and
straight-chain radicals. DOBS is an excellent foaming agent and provided it
is specially 'cleaned up', has a low order of toxicity. The preference for SLS
can probably be attributed to the development of pure grades of SLS.
Sodium lauroyl sarcosinate Sodium lauroyl sarcosinate is represented by
CH3(CH2)loCON(CH3)CH2C02Na. It was used extensively in dentifrices,
anti was claimed to possess anti-caries activity, but clinical testing failed to
support this. In 1980, the US Advisory Review Panel on aTC Dentifrices and
Dental Care Products observed that sodium lauroyl sarcosinate was a cause
of oral mucosal irritation. Following this, the sarcosinate was replaced by SLS
in offending dentifrices and, although still employed, its use is limited.
Other anionic detergents A large number of detergents have been proposed
for dentifrice use, including IX-olefin sulfonates, sulfocolaurate, sodium mono-
glyceride sulfonate, and others.
7.7.3.5 Flavor and other cosmetic attributes Dentifrice flavor plays two
roles: (i) provision of a refreshing taste and feel in the mouth and (ii)
masking of the natural flavors of the dentifrice raw materials. Tastes vary
according to the target market but the most popular flavors are mints
(peppermint, spearmint), cinnamon and mixtures (modified as deemed
necessary to develop individuality and appeal). The flavor can be a source of
irritation or sensitization and should be carefully tested for these and other
toxicological properties before being released to the consumer. In some
countries there are lists of permissible flavor oils. The creator of the flavor is
responsible for compounding the flavor oils according to regulations, but a
safety check must still be performed on the final flavored dentifrice.
Visual effects are becoming popular and include colors other than white,
sparkles, stripes, speckles, etc. Clear hydrated silica formulations are used
advantageously to obtain these effects.
7.7.4 Type I versus Type II toothpastes

As stated previously (section 7.7.2.3) two types of dentifrice formulations pre-
dominate today: (i) relatively low abrasive/high humectant (Type 1); and (ii)
relatively high abrasivejIow humectant (Type II). Both types can be formulated
over a similar range of abrasivity to dentin. Examples of Type I and Type II
formulations are given in Tables 7.2 and 7.3, respectively. The type most
suited to a particular market can vary according to local preference, raw
material availability, cost, and performance requirements. Products that are
intermediate between Type I and Type II in terms of properties may be
desired. Advantages of Type I are:
(i) with silica abrasive (today, a virtual requirement for Type I), bioavai-
lability of fluoride in the product is very high and remains so during
storage, regardless of whether the fluoride is derived from sodium
fluoride, sodium monofluorophosphate or stannous fluoride;
(ii) it is possible to prepare transparent or translucent dentifrice;
(iii) the range of cosmetic or therapeutic 'actives' that can be used is
extensive;
(iv) there is greater flexibility in tailor-making the dentifrice with respect
to abrasion level, flavor, and visual effects;
(v) the specific gravity of the Type I dentifrice is considerably lower than
that of the Type II;
(vi) despite a lower level of abrasive material, high abrasivity for cleaning
the tooth surface can be maintained; and
(vii) there are numerous manufacturers of silicas, many capable of providing
technical assistance in dentifrice applications.
Advantages of Type II are:
(i) there is a wide selection of abrasive materials from which one or more
can be chosen with economic advantage, depending on the comparative
costs of the abrasive and the humectant;
(ii) the Type II paste has a higher specific gravity than the Type I; and
(iii) less sophisticated, less expensive packaging materials can be employed
depending on the Type II formulation, ranging from simple collapsible
aluminum tubes to laminates of paper/aluminum foil/polyethylene.
7.7.5 Dentifrice manufacture

Toothpaste can be manufactured either automatically, semi-automatically, or
batch wise. It is usually manufactured with the aid of techniques and equipment
devised by the manufacturer in response to required production schedules.
Toothpaste manufacturing processes are outlined in Figure 7.5. Most formu-
Liquid
mix
Adjustments, e.g.
pH, minor additives
Powder I
Powder II
,. Deaeration .,
Figure 7.5 Schematic diagram of toothpaste manufacture.

lations can be prepared by simply mixing all the ingredients in one vessel and
deaerating the final product. This is wasteful of time, energy and equipment,
however, because of the inordinately long mixing time that would be required
to achieve an equilibrium state.
Toothpaste can be made at any convenient temperature. It can be made by
a cold process, such as outlined in Figure 7.5. Subsolutions are made of the
various ingredients, with the exception of the powders, sodium lauryl sulfate
and flavor. The subsolutions are pumped into a suitable vacuum mixer,
followed by sucking-in the powders. After all the powders are 'wetted' out,
the mixer is run until a uniform paste has developed. Following this, either
the sodium lauryl sulfate submix and flavor are added and cautious mixing
continued to prevent excessive foaming, or only the flavor is added and the
submix is injected into a stream of product as it is pumped through a mixer
and a de aerating device on the way to a holding tank. Manufacturing
equipment must be tailored to the type of formula, handling properties
of ingredients and submixes, size of the operation, and other usual
manufacturing concerns. A suitable stainless steel is the preferred construction
material.
7.7.6 Dentifrice packaging

Toothpastes are packed in flexible collapsible tubes and, to a lesser extent,
pump dispensers. The first tubes in the 1850s were fabricated out of tin, used
because of its resistance to corrosion at the high pH values of dentifrices
formulated with soap and alkaline abrasives used at the time. Eventually most
of the tin was eliminated, and tubes, made by extruding slugs oflead and coating
with tin (1.5 to 10%), appeared. The tin covering was not very uniform, and a
layer of wax was sprayed on to the interior surface of the tube to protect the
dentifrice from being contaminated by the lead. Gradually, lead tubes were
replaced by all-aluminum tubes, which are still popular where their use is
possible. Many newer formulations, however, corrode aluminum tubes and,
consequently, lacquered aluminum tubes are used and corrosion inhibitors
introduced directly into the dentifrice. Low pH toothpastes (e.g. the first fluori-
dated toothpaste) and hydrated silica pastes placed great demands on the
coated aluminum tube, and it has now been replaced by laminated tube con-
struction, whereby the dentifrice is totally protected from contact with the
aluminum by lamination with polyethylene, aluminum and paper. A poly-
ethylene layer is the inmost layer in contact with the toothpaste, preventing
contact with the aluminum foil layer and providing a means to seal the tube.
Tube decoration is excellent and aluminum content is minimal.
Dispensing toothpaste from a container equipped with a pumping mechanism,
a relatively recently developed alternative to a tube, is expensive. Two types
of pump mechanism are in use, one based on a vacuum principle, the other
DENTAL PRODUCTS 263
on mechanical forces. For further details of construction and operation of the
devices, the reader is referred to the packaging manufacturers' literature.
Several brands of toothpaste are dispensed from their containers as striped
ribbons. There are several ways to achieve the effect. One is to insert a
striping device in the nozzle of the tube. A small amount of colored paste is
placed at the nozzle and the tube is filled with regular paste. The paste is
expressed through a tube which has several orifices in the colored paste. The
colored paste is drawn through the orifices as stripes onto the surface of the
major ribbon of paste as it is extruded. Another technique involves
co extrusion of different colored pastes into the tube as it is being filled [35].
The filled tube consists of separate strips of the different colored pastes
aligned side-by-side. On applying pressure to the tube the different ribbons
are extruded side-by-side. The pastes have similar rheologies. In yet another
procedure, different pastes are packed into separate containers which are
side-by-side. The pastes are extruded via a common pump. Each paste is
extruded as a separate entity. A multi-colored paste ribbon is obtained by
placing the two extrusion orifices adjacent to each other.
7.8 Oralrinses
7.8.1 Function
The present discussion of oral rinses will be limited to those that are claimed
to have oral hygiene benefits. These oral rinses are characterized by two
common features: (i) antimicrobial action; and (ii) ability to freshen the breath.
Some also contain fluoride for its anti-caries activity. The antimicrobial
activity is credited with several benefits: reduction of dental plaque, mainte-
nance of periodontal health, and reduction of oral malodors of microbiological
origin. Breath freshening is attributable to both the flavor, and the cleansing
action of the rinse.
Recently, major emphasis has been placed on therapeutic benefits of oral
rinses, such as inhibition of gingivitis by the control of plaque. As stated
previously, the toothbrush is the key to plaque control, but is inadequate.
Mandel and Gaffar [36] observed: 'Despite the proven efficiacy of adequate
mechanical removal of plaque (Frandsen 1985), the level of patient involvement
is so demanding that only about 30% of the population in the developed
countries, and a small fraction of that in the undeveloped countries can be
expected to practice adequate plaque removal. Clearly, the availability of
chemical agents that supplement or even supplant the purely patient-dependent
mechanical regimen are essential (Mandel 1972) if the plaque diseases are to
be dealt with on a population basis.'
7.8.2 Dosage forms and formulations

Oral rinse products can be categorized broadly as: (i) aqueous solutions, to
be used 'neat' or diluted with water; (ii) aerosol sprays, to be directed into
the oral cavity; (iii) concentrates, to be diluted with a relatively large amount
of water; and (iv) specialty forms, such as powders, to be 'reconstituted' with
Table 7.4 Mouthwash ingredients and functions
Ingredient Functions Examples
Alcohol Adds bite and freshness

Enhances flavor impact
Helps solubilize some flavor components
Contributes to cleansing action and
antibacterial activity
Flavor Makes mouthwash pleasant to use Mint, cinnamon
Adds a refreshing cool quality to oral cavity
immediately, and for some time after use
Makes breath temporarily pleasant by
imposing a pleasant note over breath aroma
Some flavors exert significant antibacterial
effect
Humectant Adds 'body' to product Glycerin
Inhibits crystallization around closure
Surfactant Solubilizes flavor Poloxamer
Provides foaming action 407, sodium
Assists removal of oral debris by lowering lauryl sulfate
surface tension
Can be antibacterial
Water Major vehicle to carry other ingredients
Special ingredients
Antibacterial agent Enhances antibacterial efficacy
Astringent salts Can interact with proteins of saliva and Zinc chloride
oral mucosa
Fluoride Anti-caries agent Sodium fluoride
Table 7.5 Formulation ofa mint-type mouthwash
wt~~
Ethyl alcohol 10.0

Flavor (menthol, 30~<,; methyl salicylate. 30':~; 0.25
peppermint oil. 30'/0; eucalyptol. 10~'0)
Glycerin 10.0
Polyoxyethylenejpolyoxypropylene block 2.0
polymer (Poloxamer 407)
Saccharin sodium 0.05
Water to 100.00
From [2]
DENTAL PRODUCTS 265
water by the user. All but the first form have minor markets and will not be
considered here.
The composition and function of an oral rinse is described in Table 7.4. A
typical formulation for a breath-freshening oral rinse is given in Table 7.5
Alcohol is a key ingredient, but an excessive amount can cause a strong
burning sensation, not tolerated by some users.
Oral rinse directions generally call for 'swishing' for approximately 20-30
seconds. The flavor must not be so strong and biting as to reduce compliance
with the usage directions. Some marketers claim that strong flavor is
appealing because it implies high efficacy. The formulator must strike a
balance between flavor strength, marketing image, and compliance with usage
instructions.
7.8.3 Pre-brushing dental rinse

The pre-brushing, anti-plaque dental rinse (PBDR), introduced to the market
in the mid-1980s is not a mouthwash in the classical sense. It is used just
before toothbrushing to increase the amount of plaque removed at each
toothbrushing event. Its mode of action is radically different from that of
conventional mouthwashes based on antimicrobial agents.
The PBDR is based on the premise that plaque removal by toothbrushing
can be enhanced if the plaque is 'softened' and 'loosened' prior to tooth-
brushing, and that at least some plaque can be removed by purely detergent
action in the classical sense of separation by detergent of a soil from its
substrate. Sodium lauryl sulfate was selected as the detergent. The rinse
marketed originally was clinically tested extensively for anti-plaque efficacy.
Positive clinical results supported the postulated mechanism of action, i.e.
detergency. This suggested that enhancement of efficacy could be obtained
by addition of a detergent builder. Consequently, pyrophosphate was added.
The new product was quite effective in plaque reduction as shown by clinical
trials [11, 12]. Surprisingly, plaque reduction was not accompanied by
improvement in gingivitis level. (The results confirmed that simple reduction
in plaque does not necessarily lead to a reduction in gingivitis. Obviously, a
quantitative change in plaque level cannot be relied upon to predict the effect
of a product on gingival status, i.e. gingivitis.)
7.8.4 Manufacture and packaging

The manufacture of oral rinses is straightforward. Ingredients are dissolved
in the main body of water, with or without the use of submixes as required.
For elegance in appearance, the final product may be filtered, the final
filtration through sub-micron filter. Where a gum has been added, filtration
is not indicated. Despite the presence of antibacterial substances, the
manufacture of oral rinses must be carried out with appropriate microbiological

precautions.
F or packaging of oral rinses, clear glass or plastics are preferred for esthetic
value. Two of the more commonly used plastic constructions are polyvinyl
chloride and polyethylene terephthalate. Flavor quality is a very important
feature of many oral rinses, and should not be compromised by packaging in
containers from which off-flavor can be leached into the product, or flavor
can be lost through the wall.
7.9 Active agents
Therapy is now an integral part of OTe oral-care products. Agents able to

prevent or alleviate the severity of certain problems associated with the
dentition are now marketed. Pertinent features will be discussed here briefly.
7.9.1 Anti-caries agents

Fluoride has been proven in numerous clinical and epidemiological studies
favorably to influence the progress of dental caries. Fluoride is active
delivered from a toothpaste or an oral rinse. Three species have been used
extensively in marketed products-sodium fluoride, sodium monofluoro-
phosphate and stannous fluoride.
Fluoride acts by making tooth enamel more resistant to attack by plaque-
generated acids, promoting remineralization of early carious lesions and
attacking bacteria involved in the formation of caries. The active species is
the fluoride ion. Sodium monofluorophosphate appears to be hydrolysed to
provide free fluoride ion before it exerts anti-caries activity. Free fluoride ion
may react with the enamel surface to form a coating of calcium fluoride,
which can act as a fluoride reservoir.
Achievement of maximum fluoride effect with toothpaste requires that the
fluoride ion in the toothpaste does not react with toothpaste excipients, such
as the abrasive. Numerous clinical trials have shown that unsupervised use of
a fluoride toothpaste with 1000 ppm fluoride can be expected to reduce caries
incidence by about 25%, and a fluoride oral rinse with about 0.05% sodium
fluoride by about 40%. Fluoride toothpastes undoubtedly have contributed
in a major way to the decline in caries in industrialized societies.
7.9.2 Reduction in tooth hypersensitivity

Potassium nitrate (5%) in a properly formulated toothpaste has been shown
effectively to reduce tooth hypersensitivity in those subjects afflicted with the
condition. Strontium chloride is also effective, but for the efficacy, formula-
tion and use characteristics potassium nitrate is preferred [37].
7.9.3 Reduction of plaque and calculus and improvement in gingival
health [38]
7.9.3.1 Chlorhexidine Chlorhexidine is perhaps the most effective agent

available to reduce plaque and gingivitis. It is a bis-biguanide antiseptic.
Inability to formulate the compound into a conventional toothpaste has
limited its use mainly to oral rinses. It can cause staining of the teeth, taste
modification and increased calculus formation.
7.9.3.2 Essentialoils These chemicals can have strong antiseptic proper-

ties. An oral rinse containing a mixture of eucalyptol, menthol, thymol and
methyl salicylate in an aqueous-alcoholic base has been 'accepted' by the
American Dental Association (ADA) for anti-plaque! anti-gingivitis
activity. The essential oils have characteristic flavors which are difficult to
mask. Nonetheless, their use as oral antiseptics is widespread.
7.9.3.3 Quaternary ammonium compounds Those used in oral-care

products include cetylpyridinium chloride, benzethonium chloride and
domiphen bromide. They have not been used in toothpastes because they
are inactivated by the anionic detergent used for foaming. A cetylpyridinium
chloride oral rinse has shown anti-plaque activity. Effects on gingivitis,
however, have been equivocal. Cetylpyridinium chloride is effective in
reducing oral bacteria in general, including those involved in the generation
of 'bad breath'. It is used in a popular US oral rinse, supplemented with
domiphen bromide.
7.9.3.4 Triclosan Triclosan can reduce both plaque and gingivitis. It has
the advantage over, for example the quaternary ammonium compounds, of
not having a strong astringent flavor and of being compatible with anionic
detergents. Thus, it can be incorporated into toothpaste as well as into oral
rinse. It is claimed that the efficacy of triclosan can be enhanced by supple-
menting it with either zinc citrate or Gantrez, a copolymer of polyvinyl-
methyl ether and maleic acid [1, 39]. The combined formulations also are
reported to reduce dental calculus.
7.9.3.5 Herbal compounds Sanguinarine is an extract from a blood root

plant. It is available both in oral rinse and toothpaste delivery systems.
Claims have been made that it has anti-plaque and anti-gingivitis efficacy.
However, these claims have been supported only by mixed clinical results,
and the ADA has not granted its seal of acceptance to products containing
sanguinarine for gingival health.
7.9.3.6 Stannous salts Stannous fluoride is the basis for a recently intro-
duced gum-care toothpaste, with claims of reduced gingival bleeding and
gingival inflammation. Stannous fluoride has not been formulated into

OTC oral rinses because of stability problems, although preparations in
glycerin to be diluted with water just prior to use have been approved in the
United States for anti-caries effect.
7.9.3.7 Zinc salts Zinc citrate trihydrate (ZCT) can be formulated into
commercial toothpaste and a soluble form thereof into oral rinses [1,2]. Zinc
salts have many oral care benefits. ZCT has anti-plaque activity and inhibits
the formation of calculus. It can be delivered from toothpaste vehicles. Zinc
salts combine with organic sulfides (e.g. dimethyl sulfide) which are major
contributors to 'bad breath'.
7.9.3.8 Complex phosphates Phosphate salts such as pyrophosphates are

the basis for toothpastes which can inhibit the development of calculus. They
can be delivered from toothpaste and oral rinse. Pyrophosphate is preferred.
It is stable and essentially non-reactive with conventional Type I toothpaste
excipients with silica abrasive.
7.9.3.9 Sodium lauryl sulphate (SLS) SLS delivered from an oral rinse
can reduce plaque. It also can remove oral bacteria from various sites, and
helps to keep the bacterial count down for several hours [33]. Clinical evalua-
tion of a pre-brushing rinse containing SLS confirmed its ability to reduce
plaque accumulation, but this reduction was not accompanied by improve-
men t in gingival health [11].
7.9.3.1 0 Hydrogen peroxide Hydrogen peroxide has shown some promise

in controlling plaque and gingivitis. Long term safety has been demon-
strated. It is a relatively new addition to the list of OTC oral care agents.
OTC products are formulated with hydrogen peroxide in one base and a
second base comprising sodium bicarbonate which is codispersed with the
first from a dual pump system. Dentifrice containing hydrogen peroxide
and baking soda has in preliminary studies been shown to be safe and on
completion of further studies has been approved by the ADA as safe and
effective [40]. A toothpaste containing hydrogen peroxide (0.67%), sodium
bicarbonate (5.48%) and fluoride (1100 ppm) as sodium fluoride was
significantly superior to a fluoride control at reducing the concentration of
oral precursors found in saliva [41].
7.10 Specialty products
7.10.1 Tooth whiteners

Tooth whitening preparations, once exclusive to the dental profession, are
now being marketed with increasing enthusiasm directly to the general public.
The consumer market is still very small, but can be expected to grow at an
DENTAL PRODUCTS 269
accelerating rate. The potential size of the market in the future is huge if
product performance can be made to equal product expectations.
The active ingredient in most of the whitening agents is 10% carbamide
peroxide, which reacts with water to release hydrogen peroxide. Also used
is calcium peroxide. The unsupervised use of peroxide to bleach the teeth has
been of concern to some professional groups. The ADA has questioned the
safety of unsupervised use of peroxide for the purpose, reasons including
potential carcinogenicity, effect on wound healing and other potential
problems. Recently, however, the ADA granted its seal to a tooth bleaching
product to be used at home with the proviso that it be dispensed by a dentist.
7.10.2 Products for the edentulous

Denture cleansers and adhesives represent two major categories of products
for the edentulous. The former are marketed mainly in two forms: (i) an
effervescent tablet or powder with a dye marker to signal when the cleansing
process is complete; and (ii) a fairly conventional toothpaste. Denture
adhesives are generally formulated around a gum (karaya is popular) that
swells and becomes sticky, and acts as an adherent between the denture and
the oral tissue.
Many of the proprietary powders and tableted denture cleansers comprise
a bleaching agent, which is usually a compound that releases the peroxide ion
(e.g. sodium perborate, sodium percarbonate, or an alkali metal salt of
monopersulfuric acid). Alkali may be added to perborate or percarbonate
compositions to enhance release of the peroxide ion. Builders, such as sodium
bicarbonate, sodium carbonate, sodium sulfate and sodium chloride, are
added to the formulation. Chelating agents may also be added to remove
calculus and to prevent precipitation in hard water. In tablets, effervescence
is needed to facilitate rapid disintegration. This may be produced by an-
hydrous sodium perborate or a mixture of citric acid and sodium bicarbonate.
(In powders, breakdown of the peroxide can yield mild effervescence.) Other
ingredients include flavor, detergent, tableting aids and binders. A typical
tablet composition might contain the following: potassium monopersulfate,
30%; sodium bicarbonate, 65%; sodium perborate, 2%; sodium lauryl sulfate,
0.5%; blue dye, 0.1%; flavor, 0.3%; other builders, to 100%.
Paste denture cleansers are formulated much like toothpastes, taking
precautions to avoid a degree of abrasivity which can harm the denture.
Denture adhesives are based on gum karaya or another gum, plus fillers,
flavors, and colors. A formulation may contain the following: petrolatum,
50%; gum karaya, 45%; magnesium oxide, 3%; fillers.
References
1. Pader, M. (1992) Dentifrices. In Chemistry and Technology of the Cosmetic and Toiletries
Industry, Williams, D.F and Schmitt, W.H. (Eds). Blackie, London, Chapter 7.
2. Pader, M. (1988) Oral Hygiene Products and Practice, Marcel Dekker, New York.
3. Schour, I. (1938) Tooth development. In Dental Science and Dental Art, Gordon, S.M. (Ed.).
Lea & Febiger, Philadelphia, Chapter 1.
4. Dawes, e. (1979) In Proceedings, Saliva and Dental Caries, Kleinberg, 1., Ellison, A. and
Mandel, I.D. (Eds). Special Suppl. Microbiology Abstracts, p. 505.
5. Bhaskar, S.N. (1981) Role of pulsating water lavage in plaque control. In Prevention of
Periodontal Disease, Caranza, F.A. and Kenney, E.B. (Eds). Quintessence, Chicago,
Chapter IV.
6. Dawes, e., Jenkins, G.N. and Tonge, e.H. (1963) The nomenclature of the integuments of
the enamel surface of teeth. Br. Dent. J. 11565-68.
7. De La Rosa, M.R., Guerra, J.Z., Johnston, D.A. and Radicke, A.W. (1979) Plaque growth
and removal with daily toothbrushing. J. Periodontol. 50 661-664.
8. Nikiforuk, G. (1985) Understanding Dental Caries, Karger, Basel.
9. Loe, H., Theilade, E. and Jensen, S.B. (1965) Experimental gingivitis inman. J. Periodontol.
36177-187.
10. Pader, M. (1992) Dental plaque. Cosmet. Toilet. 10781-89.
II. Schiff, T. and Borden, L. e. (1994) The effect of a new experimental pre brushing dental rinse
on plaque removal. J. Clin. Dent 4 107-110.
12. O'Mullane, D.M., Whelton, H., Phelan, J. and Gleeson, P.A (1994) A 12-month efficacy
study ofa pre-brushing rinse on plaque removal. J. Periodontol. 65611-615.
13. Attstrom, R. (1988) Does supragingival plaque removal prevent further breakdown? In
Periodontology Today, Guggenheim, B. (Ed.). Karger, Basel, pp. 251-259.
14. Schroeder, H.E. (1969) Formation and Inhibition of Dental Calculus. Hans Huber, Berne.
15. Mandel, I.D. and Gaffar, A (1986) Calculus revisited. A review. J. Clin. Periodontol. 13
249-257.
16. Van Dyke, T.E. and Zinney, W.B. (1989) Biochemical basis for control of plaque-related
oral diseases in the normal and compromised host: Periodontal diseases. J. Dent. Res. 68
(Special Issue) 1588-1596.
17. Burt, B.S. (1988) The status of epidemiological data on periodontal diseases. In
Periodontology Today. Guggenheim, B. (Ed.). Karger, Basel, pp. 68-76.
18. Vogel, R.I. (1975) Intrinsic and extrinsic discoloration of the dentition. A literature review.
J. Oral Med. 30 99-104.
19. Eriksen, H.M. and Nordb0, H. (1978) Extrinsic discoloration of the dentition. J. Clin.
Periodontol. 5 229-236.
20. Berman, L.H. (1985) J. Periodontol. 56 216.
21. ten Bosch and Coops, J.C. (1995) Tooth color and reflectance as related to light scattering
and enamel hardness. J. Dent. Res. 74374--380.
22. Rugg-Gunn, AJ. and MacGregor, LD.M. (1978) A survey of toothbrushing behavior in
children and young adults. J. Periodontol. Res. 13 382-389.
23. Kleber, e.J., Putt, M.S. and Muhler, J.e. (1981) Duration and pattern of toothbrushing in
children using a gel or paste dentifrice. J. Am. Dent. Assoc. 103723-726.
24. Council on Dental Therapeutics (1985) J. Am. Dent. Assoc. 110545-548.
25. Bass, e.e. (1948) Dent. Items Interest 70696.
26. Kitchin, P.e. and Robinson, H.B.G. (1948) How abrasive need a dentifrice be? J. Dent. Res.
27 501.
27. Pader, M. (1993) Dentifrice rheology. In Rheological Properties of Cosmetics and Toiletries,
D. Laba (Ed.). Marcel Dekker, New York, Chapter 7.
28. De Boer, P., Duinkerke, A.S.H. and Arends, J. (1985) Caries Res. 19232.
29. Stookey, G.K., Burkhard, T.A and Schermerhorn, B.R. (1982) In vitro removal of stain
with dentifrices. J. Dent. Res. 61 1236-1239.
30. Hefferen, J.J. (1977) ADA dentifrice function program. Collaborative study of clinical
methodology. I. Methods to assess dentifrice cleaning function, May, 1977.
31. Pader, M. (1984) Humectants for clear gel dentifrices. US Patent 4,435,380 (March 6, 1984).
32. Pader, M. (1988) Binders and Thickeners for toothpaste. Cosmet. Toilet. 10384-93.
33. Pader, M. (1985) Surfactants in oral hygiene products. In Surfactants in Cosmetics, Reiger,
M.M. (Ed.). Marcel Dekker, New York, Chapter 10.
34. Pader, M. (1987) Toothpaste gels. Cosmet. Toil. 10281-87.
35. Chown, J.P. and Healey, J.M. (1976) US Patent 3,980,767 (Sept. 14, 1976).
DENTAL PRODUCTS 271
36. Mandel, I.D. and Gaffar, A. (1986) Calculus revisited. A review. J. Clin. Periodontal. 13
249-257.
37. Hodosh, M., Hodosh, S.H. and Hodosh, A.I. (1994) About dentinal hypersensitivity.
Compend. Continuing Educ. Dent. 15658-667.
38. Mandel, I.D. (1994) Antimicrobial rinses: overview and update. J. Am. Dent. Assoc. 125
(Suppl) 25-85.
39. Bolden, T.E., Zambon, 1.1., Sowinski, 1., Ayad, F., McCool, 1.1., Volpe, A.R. and DeVizio
(1992) J. Clin. Dent. 3125-129.
40. Fischman, S.L., Truelove, R.R., Hart, R. and Cancro, L.P. (1992) The laboratory and
clinical safety evaluation of a dentifrice containing hydrogen peroxide and baking soda. J.
Clin. Dent. 3104-110.
41. Grigor, 1. and Roberts, A.I. (1992) Reduction in the levels of oral malodor precursors by
hydrogen peroxide: in vitro and in vivo assessments. J. Clin. Dent. 3 111-115.
8 Perfumery
A. DALLIMORE
8.1 Introduction
The object of this chapter is to give the reader an overview of the subject of
perfumery. It will cover the role offragrance, the raw materials used, and the
creative approach and construction (including technical constraints, quality
aspects, and health and safety). Fragrance briefing, current trends and issues,
and a short glossary of perfumery descriptors are included. A brief description
of some other special additives used in perfumery, or closely related to
perfumery materials, is given.
8.2 Fragrance-a definition

The terms 'fragrance' and 'perfume' are synonymous and are used
interchangeably throughout the perfumery and cosmetics industries. This
will also be so throughout this chapter. Fragrance (or perfume) is a blend
of two or more materials characterised by having olfactive properties, and
is incorporated into a preparation with the intention of imparting specific
odorous characteristics to that preparation. Very occasionally, the fragrance
may consist of one raw material only.
8.3 Role of fragrance

The most important function of the perfume is usually to impart a pleasant
and suitable odour to the product into which it is to be incorporated. It is
the job of the creative and evaluation teams to define the terms 'pleasant'
and 'suitable' for each particular brief that is received. The perfume may also
be required to perform other roles in the product, which may take priority
over, or be additional to the primary role of imparting odour.
Most cosmetic products have a mild but detectable odour, which is derived
from the raw materials in the formulation. Although this 'base' odour is
usually inoffensive, it can detract from the overall aesthetic character of the
product and should at least be 'masked'. This can be effectively achieved by
the use of a suitable fragrance. Very pungent bases, such as permanent-wave
lotions, are almost impossible to mask, even with the strongest of perfumes.
PERFUMERY 273
The role of the perfume in these products is therefore to produce as pleasant
an odour as possible, and this can often be attained by harmonising the
fragrance with the base odour.
Fragrances can be designed to give subliminal support to a particular
product. For example, a fragrance may appear to make a shampoo wash
the hair more cleanly, a perfumed night cream may seem more nutritional
to the skin, or a perfumed body spray may appear to impart all-over freshness,
all-day. In other words, the perfume may have the role of apparently en-
hancing product performance.
Some fragrance materials have antimicrobial activity, particularly against
bacteria. Both bacteriostatic and bacteriocidal properties are evident. Con-
sequently, fragrance blends often take on the antimicrobial activity of some
of the individual components. Fragrances that have spicy and herbal notes
usually exhibit some antibacterial activity owing to the presence of phenols
such as eugenol (from clove oil), and thymol and carvacrol (from thyme oil).
Consequently, the fragrance may also have the role of assisting the pre-
servative system and even in extreme cases, of replacing the preservative
system altogether. Similarly, the fragrance may assist a bacteriocide/bacterio-
stat in its effect on the skin's microflora (reducing body odour) or may be
required to carry this attribute of the finished product on its own.
8.4 Perfumery raw materials
The basic components or raw materials that are used to manufacture

fragrance compounds number in the region of 4000-6000. Although estimates
vary from source to source, this range is widely accepted as typical. Of
these materials, approximately 100 items are key ingredients, comprising
the majority of most formulations by weight. Most formulations contain a
significant number of these materials. Examples of key raw materials are
benzyl acetate, cedarwood oil, geraniol, geranium oil, lavender oils, lemon
oil, linalol, methyl ionones, oakmoss and treemoss products, phenyl ethyl
alcohol, vanillin, and ylang oils.
Perfumery raw materials fall into two distinct groups: (i) natural; and (ii)
synthetic. Natural components are of animal or plant origin, while synthetic
materials are produced from a wide range of starting materials, using diverse
reactions and synthetic pathways.
8.4.1 Natural perfumery raw materials

8.4.1.1 Animal products The use of animal products is a very topical and
emotive issue, and it is quite clear that the perfumery industry is rapidly
heading towards the exclusion of this group of raw materials. Traditionally,
extracts of musk from the musk deer, castoreum from the beaver, civet from
the civet cat, and ambergris from the sperm whale were all used in fragrance
compositions, especially those created as skin perfumes. However, with
modern analytical techniques and the ability of the aroma chemical industry
to analyse and synthesise many of the active components, excellent substitutes
are now available to the perfumer, often at much lower cost.
8.4.1.2 Plant products A vast range of plant extracts can be used in the
creation of perfumes. The extracts are prepared in several ways, the most
important of which are steam distillation and organic solvent extraction,
particularly ethanolic extraction. Steam-distilled products are called 'essential
oils'. Solvent-extracted products are generally referred to as 'concretes' with
the alcoholic extracts having several names depending on the starting
material. 'Absolutes' are ethanolic extractions of concretes, while 'tinctures'
are ethanolic extracts of the raw plant material. Tinctures of animal products
are also prepared. Plant resins and resinous materials may be used in the
untreated states or processed by extraction. Organic solvent extraction,
usually hydrocarbon based, produces the so-called 'resinoid', which may be
further extracted with ethanol to give a 'resin absolute'.
Due to the presence of odorous materials in specific organs, particular
parts of plants are extracted. In some instances, different parts of the plant
produce olfactively differing extracts. A typical example is the bitter orange
tree, of which the fruits give bitter orange oil, the flowers give neroli oil,
and the leaves and twigs give petitgrain oil. Although the odour of these oils
is related and many of the constituents are common, the oils have distinctive
odours and composition. Some examples of commonly used plant products
are rosemary, rose, lemongrass, clove, caraway and rosewood oils, oakmoss
and jasmin absolutes, and olibanum and labdanum resins.
The preparation of plant extracts for use in perfumery is a worldwide
industry and is subject to unpredictable factors such as climatic conditions,
political changes and economic uncertainty. As a result, it is not unusual to
have to deal with the problems of fluctuating crop availability, pricing and
quality.
8.4.2 Synthetic perfumery raw materials (aroma chemicals)

The use of synthetic organic chemicals with organoleptic properties follows
the advances made in organic synthesis from the middle to late nineteenth
century up to the present day. A vast range of aroma chemicals is now available
to the perfumer, ranging in complexity from the relatively simple esters, alde-
hydes and alcohols (such as n-hexanol) to macro cyclic molecules like cyclo-
pentadecanolide. Most companies involved in the manufacture of aroma
chemicals are actively engaged in the search for new compounds. A new
fragrance chemical must have certain characteristics in order for it to become
a part of the standard perfumery repertoire. First and foremost it must be safe
PERFUMERY 275
both for the fragrance manufacturer to handle, and in its destined consumer
product. Second, it must be chemically stable over a range of conditions, cost-
effective in use and possess a useful odour property. Finally, it must appeal
aesthetically to the creative perfumers who will use it as a part of their palate
of raw materials, thus ensuring its economic viability and long-term success.
Particular emphasis is presently being placed on the development of
chemicals, especially those with: (i) sandalwood characters; (ii) fruity components,
especially those that are nature identical; (iii) exceptional stability in adverse
media, for example media with extremes of pH or powerful oxidisers; (iv)
unique odour or blending properties; and (v) versatile, economic properties.
The two main feedstock sources for aroma chemicals are turpentine oil and
crude oil. Many synthetic processes are used to produce a wide range of high
quality, standardised materials suitable for perfumery use. A number of examples
from the hundred or so key aroma chemicals used in the fragrance industry
are given below.
Benzyl acetate Characteristic jasmin note, light floral and slightly fruity;
widely used; very economic.
Benzyl salicylate Warm, balsamic note, blending well with musky and
floral notes, and giving body to the composition.
iso-Bornyl acetate Fresh, piney; cheap and stable; important component
of all synthetic pines, in which it may be used at concentrations as high as 80%.
p-t-Butyl cyclohexyl acetate (PT BCH A) Soft woody note; stable and
widely used in soap perfumery; low cost; provides good support for all other
woody notes, particularly patchouli.
Cedryl acetate Sharp, woody material, particularly useful in masculine
perfumes; derived from cedarwood oil.
Citronellol Main component of rose oils, therefore widely used as a key
element of rose fragrances; also an effective floraliser in citrus blends; manu-
factured synthetically.
Dihydro myrcenol Citrus, especially lime and lavender aspects; very
volatile; a valuable, stable topnote material at concentrations of 0.1 % to 20%.
Geraniol Floral, rosy; found naturally in geranium, rose, palmarosa and
citronella oils.
H eliotropine Sweet, floral, powdery odour; will discolour in some finished
products, e.g. soap.
Hexyl cinnamic aldehyde Homologue of amyl cinnamic aldehyde, to
which it is similar in character and properties, and with which it is often
combined; overall more light and delicate; used extensively in modern fine
perfumery in accord with methyl dihydro jasmonate.
Indole Chemically heterocyclic; floral, ani malic odour; found in jasmin

and orange flower absolutes; discolours readily and sublimes.
y-Methyl ionone Woody, floral, violet notes; used in many fine perfumes
for its unique effect; also supports the iris character in a composition.
Musk ketone Musky, ani malic, warm, powdery; one of the nitromusks;
very long lasting but can cause discoloration at high levels.
Phenyl ethyl alcohol Floral, faintly green; main component of rose water
and, hence, rose fragrances; excellent blender; deceptively powerful despite
being weakish in odour in the pure state.
Vani/lin Sweet, powdery, ambery, vanilla; extremely powerful material that
will impart softness, warmth and depth to almost any fragrance; very widely
used; at concentrations as low as 0.01 %, can still be effective and is a note that
is almost universally liked and accepted; at high concentrations (0.5% and
above), will rapidly dominate the creation if not well blended; develops as
the freshly compounded fragrance matures; disadvantage of discoloration
(especially in alkaline media such as toilet soap), producing a dark brown
colour; discoloration is accelerated by an increase in temperature.
8.5 Development of a fragrance
The development of a new fragrance follows a clearly defined route from the
customer's briefing to the production or manufacture ofthe selected formulation.
8.5.1 The brief

A perfumery company requires certain basic pieces of information in order
to select a suitable fragrance from the library or to create a new, specific
fragrance to satisfy the client's request. The brief should be in written form
and discussed with the perfumery company's representatives, who may include
a perfumer, fragrance evaluator or marketing person. The following items of
information are essential to the creative team.
8.5.1.1 Product The application for which the fragrance is intended. Details
of the formulation are useful (sometimes essential), especially if unusual, novel
or reactive raw materials are being incorporated. Ideally, a quantity of the
unperfumed formulation (usually referred to in perfumery circles as 'unperfumed
base') should be provided for the perfumery house to conduct its testing. The
intended colour for the final product should also be indicated, since the
harmony between colour and odour is of utmost importance in the overall
integrity of the product.
PERFUMERY 277
8.5.1.2 Packaging The proposed packaging for the new product. Although
perfume/packaging interactions are infrequent, they can and do occur.
8.5.1.3 Fragrance area The particular fragrance type required for the
proposed product. If possible, the fragrance area should be described using
perfumery terms, but the use of specific raw materials, even of marketed
products, can form the basis of a common language and can therefore be
used as a reference point. Although the language of smell is probably the
least developed for all the senses, perfumers and their clients can often broadly
understand each other by using such reference points. Interim meetings between
the client and perfumer during a project can provide valid direction in the
creative task, and regular discussion brings a common awareness, on both
sides, of what is required versus what can be achieved.
8.5.1.4 Cost The cost limits for the perfume submission. Pro-rata dosing
should always be considered if feasible for the project, and comprises the in-
corporation of a more expensive perfume at a lower dosage, or a cheaper perfume
at a higher dosage, both giving the same cost contribution to the final product
formulation. The cost limits are usually expressed as pounds sterling per kilo,
or dollars per kilo or pound but, under a pro-rata option, may be expressed
as pounds sterling, or dollars, per unit weight of finished product.
8.5.1.5 Number of submissions The number of submissions permitted per

product. The submission of two ideas per product allows the perfumery house
to comply closely with the customer's request and to suggest an idea of its
own-a 'flier'.
8.5.1.6 Marketing information The market positioning of the product. It

is vital that the right type of perfume is created for the product. Consequently
the proposed market positioning of the product, including such items as
geographical distribution, should be made as clear as possible.
8.5.1.7 Timescale The deadline date for submissions. Most perfumery

houses will be able to turn a brief round within two to four weeks if the
submission is taken from the library and submitted as such, or perhaps
modified slightly. However, the creation of a new fragrance should be considered
in terms of months rather than weeks, and it is the plea of many perfumers
that the fragrance should not be an afterthought but an integral part of the
product at the concept stage.
8.5.1.8 Safety Conformity to regulations. Although conformity with

guidelines set out by the Research Institute for Fragrance Materials (RIFM)
and the International Fragrance Association (IFRA), and with local national
legislation is standard with all reputable companies, the briefing company
should make suppliers aware of any particular restrictions that they impose
on materials not covered by the current recommendations. From time to time,
new evidence on the safe usage level of a fragrance raw material may be
produced, with the effect that current compounds may need modification to
comply with the latest safety developments. It is the obligation of the perfumery
house to make their customers aware of this, and the obligation of the cosmetic
and toiletries houses to accept a slight change in their fragrance compounds
should there be no alternative. However, in the author's experience, expert
evaluators can often detect minor odour changes in a product, while most
consumers, in whose interests the changes are being made, cannot.
8.5.1.9 Submission size The quantity of oil required, for the client's test pro-
gramme. The customer should also stipulate whether the perfume submission
should be demonstrated in the base, i.e. the final product, preferably the client's
own.
8.5.1.10 Testing Stability testing and panel testing. Clients should indicate
to the perfumery house any specific stability testing that is required. Most
perfume houses undertake their own stability testing as a matter of course,
using perfumed and unperfumed samples, with conditions of low, elevated and
ambient temperature, in the light and dark, as standard. If any panel testing
of support data is required, this should be discussed fully at the initial briefing
so that appropriate tests can be designed.
8.5.2 The creative process

When creating a fragrance, the perfumer must take into account the following
parameters.
(i) Odour type
(ii) Suitability for product
(iii) Performance (strength)
(iv) Cost
(v) Stability
(vi) Health and safety and other legislation
(vii) Consumer acceptability
(viii) Timescale
(ix) Possible scale-up (manufacturing) problems
(x) Availability of raw materials
Each perfumer has his or her own individual method, which is usually a combi-
nation of techniques. The combinations and techniques used vary with the
type of project. The first requirement is usually the creation of the appropriate
odour theme, while simultaneously taking into account the various limita-
tions. Some constraints may be ignored during the early stages of develop-
PERFUMERY 279
ment and attended to as the project progresses. For example, the perfumer
may not adhere to the cost limits whilst exploring the main theme but, once
a satisfactory odour type is achieved, then he or she may set about working
it into the designated price area.
Several techniques form the basis of the methodology of creating the right
odour, although it must be stated that the methods used by perfumers are
diverse and individual in their nature and combination. Some of the more
important of these methods will now be discussed. Using these techniques,
along with skill, experience, patience and, on some occasions, considerable
trial and error, a finished product will be obtained.
8.5.2.1 Binary blending The mixing of two components in varying pro-

portions. As an example, consider the 10% blend of lemon oil and lime oil
to give a final range of 0%-100%. The perfumer will choose the blend that
appeals to him or her most. This may be the blend that has an emphasis on
either the lemon or the lime, or it may be the blend at which neither compo-
nent is dominant and perhaps a harmony or a novel effect is achieved. An
analogy is the blending of the two colours yellow and blue across a range.
Somewhere in the middle of the range an apparent 'new' colour~green~will
be seen. This is the aim of the perfumer when binary blending.
Although appearing to be a basic starting procedure, binary blending may
also be used at the final stage of development. For example, it may be used
to obtain the optimum level of the green note that is being added at the final
stage to 'finish-off' the newly created perfume.
8.5.2.2 Formation of accords The balancing of several components to give

an interesting or novel effect. For example, a simplejasmin accord could be:
Accord 1 Wt%
Hexyl cinnamic aldehyde 50
Methyl dihydro jasmonate 25
Benzyl acetate 20
Dimethyl benzyl carbinyl butyrate 3
Indole 2
A floral accord could be:
Accord 2 Wt%
Phenyl ethyl alcohol (rose-like) 40
p-t-Butyl-(a)-methyl hydrocinnamic
aldehyde (muguet-like) 30
Hexyl cinnamic aldehyde Uasmin-like) 20
y-Methyl ionone (violet-like) 9
Phenyl acetaldehyde (hyacinth-like) 1
This accord is very simple, but could be made more sophisticated and more
interesting by substituting the individual raw materials with representative

accords.
Accord 3 Wt%
Rose accord 40
Muguet accord 30
Jasmin accord 20
Violet accord 9
Hyacinth accord
Once an accord has been made, other notes may be added to accent certain
aspects of the developing fragrance. In accord 3, for example, a green topnote
may be blended into the composition in the form of galbanum oil or
cis-3-hexenol.
8.5.2.3 Thematic construction Using this method of creation, the perfumer

selects the basic fragrance notes and builds them in situ. A simple example
could be the creation of an aldehydic, woody, green floral fragrance. The
components for each odour theme within the perfume are listed, and quan-
tities decided.
(i) Aldehydic part representing 2% of the total
Undecylenic aldehyde, 1%
Lauric aldehyde, 1%
(ii) Woody part representing 55% of the total
Cedarwood oil, 10%
y-Methyl ionone, 15%
p-t-Butyl cyclohexyl acetate, 30%
(iii) Green part representing 2% of the total
Methyl phenyl carbinyl acetate, 1%
Phenyl acetal dey de, 1%
(iv) Floral part representing 41% of the total
Hexyl cinnamic aldehyde, 15%
Terpineol, 21 %
Phenyl ethyl alcohol, 5%
Again, this is a relatively simple demonstration, since a fragrance is not

limited to just four themes, or just a few ingredients within these themes.
One fragrance may consist of just two items, or may contain several hundred.
8.5.2.4 Assessing a fragrance compound Each perfumer has his or her own
way of smelling. During training it is imperative that creations are
incorporated into the intended end-product and the relationship between
the concentrate and how it performs in the product is understood. This
enables a more predictive approach to be made to experimentation as time
goes by. Fragrance concentrates should always be assessed on a smelling strip
PERFUMERY 281
or blotter, which should be dipped to a depth of about 2-3 cm. The blotter
should be held 6-10 cm from the nose and the aroma inhaled. The environ-
ment in which smelling is undertaken should be at a temperature and
humidity level that is comfortable for the assessor. The fragrance should be
evaluated over a period of time, possibly up to 48 hours and notes made for
reference. Final assessment should always be made in the end-product and in
an in-use situation.
8.5.3 Evaluation and marketing of the new creation

The objectives of the perfumer are: (i) to create a product that will fulfil the
client's request; and (ii) to ensure that the client's product succeeds in the
marketplace, with the fragrance playing its required role. Much research
concerning the influence of perfume within a finished product has been
undertaken. It is clear that certain perfumes can complement certain types
of products, syngergise with particular colourways, subliminally support
certain product attributes, and even act as a link across a product range.
Fine fragrance is marketed in such a way that, as well as perfuming the
individual, the use of the scent may signify lifestyle, describe personality or
alter ego, attract the desired partner or stimulate emotions in a way not
thought to be possible. Once created, therefore, the fragrance is often tested by
an in-house evaluation panel, which may consist of a mixture of expert 'noses'
(perfumers and trained evaluators) and lay 'noses' (usually other staff, or
possibly a local residents panel) to assess its suitability for the brief. The
result may indicate that a reworking of the creation is needed, and the panel
test may then be repeated. An outside panel may also be used to support
the fragrance submission, and the client will most likely undertake their
own market test regime before the product is finally launched.
8.6 The current market in fine fragrance
The current couture fragrance market for women is designer-dominated and

is characterised by the launch of a profusion offragrances that are considered
fresh and natural. Predominant themes are ozonic and watery elements, light
flowery notes, citrussy topnotes and fruity aspects that vary from discreet to
most evident. The fruity notes are typified by blackcurrant, peach and pine-
apple with more tropical notes such as mango and passion fruit beginning to
appear. Base combinations of musk, amber, moss and wood notes are
frequently used. The overtly powerful sea themes have been replaced by more
sophisticated marine blends, whilst several brands have been launched as
lighter versions of their respective 1980s successes. The use of unusual or even
unique natural extracts has appealed to many marketeers and the incorpor-
ation of nature-identical synthetics, especially those identified by headspace
analysis, continues to grow. There is a recent trend using the vanilla note as
the key theme. Already several mass market brands are in the marketplace
with successful products.
The current fine fragrance market for men is also heavily influenced by
designer creations, with the Fougere theme being the most in vogue. The
accord of allyl amyl glycollate, dihydro myrcenol! dimethyl heptanol and
absolute oakmoss continually recurs in new launches, as do the powerful
woody-sandalwood aroma chemicals. An accord of sandalwood notes,
patchouli oil, methyl dihydro jasmonate and a macrocyclic musk forms a
very latent, diffusive base, which is used across a wide range of masculine
themes. Vetivert characters, sea aspects and ozonic notes are more in
evidence and may yet form the foundation of a significant stage in the
evolution of the men's market.
It is clear that innovation in the fine fragrance market for men and women
usually takes place in small increments and that a quantum leap in terms of
'new' odours occurs very rarely. However, once a truly innovative perfume is
accepted by the market, this theme may act as an inspiration to marketing
companies, designers and perfumers for a plethora of developments in which
the theme itself is key.
8.6.1 The trickle-down effect

Fine fragrance themes act as inspiration for creative ideas for functional
cosmetic products, with some odour types lending themselves to easy modifi-
cation for a whole range of end uses. For example, aldehydic, woody or floral
perfumes can be found in body sprays, skin-care products, hair-care products,
bath products, toilets soaps and, although beyond the subject matter of this
book, even in fragranced household and industrial products.
The translation of a fine fragrance theme in order to make it suitable for
cosmetics and toiletries involves adjusting the formulation to ensure that it
is chemically stable, performs strengthwise, is a balanced perfume, is consumer
acceptable, and conforms to the lower cost limits demanded by these types
of products.
8.7 Odour types
The many different odour types fall into four categories: (i) simple notes,
which are representative of naturally occurring aromas such as fruits, herbs,
spices, flowers and animal smells; (ii) complexes, which are combinations of
singular characters-for example green floral, spicy citrus and fruity floral;
(iii) classic accords such as Fougere, Chypre and Opoponax; and (iv) multi-
complexes, represented by many fine fragrance types which can have up to
PERFUMERY 283
12 identifiable simple themes within the total structure. The definition of an
odour type is very subjective. Opinions can be very disparate, but there is
no real right or wrong. In fact, subjectivity reigns supreme.
8.8 Technical performance of perfumes
The custom-creation of a fragrance relates not only to the style of odour

required, but also to the proposed end usage, with specific products posing
specific compatibility problems. The following general comments apply: (i)
oils and powders require the heavier aspects of the fragrance to be accentuated;
(ii) aerosol products require less emphasis on the topnote; (iii) aqueous
products require a strong, well-supported topnote; and (iv) soaps and
emulsions require an evenly balanced composition.
Aerosols The perfume must be well balanced for aerosol use, topnotes being
accentuated strongly by all propellants. The perfume must also mask or
harmonise with any propellant odour, especially in the case of the 'ozone-
friendly' hydrocarbon propellants. Interaction between the perfume and
any active ingredient, e.g. an antimicrobial, must not take place. Finally, the
perfume must be soluble and not precipitate, which could cause valve blockage.
Antiperspirants The acid medium of aluminium chlorhydrate based formu-

lations is very aggressive towards some fragrance materials. Traditional citrus
and lavender notes are very susceptible, but more stable versions can be
made using a series of synthesised aroma chemicals. The comments made
concerning aerosols also apply to antiperspirants.
Antiperspirant and deodorant sticks Performance, coloration, discoloration

and reaction with the active constituents are factors to be aware of.
Body sprays and deosprays When perfuming these products, the points to
note are the same as those that apply to aerosols in general, but special
care should be taken to avoid suppression or potentiation of the active
components.
Skin creams and lotions Discoloration and emulsion stability are potential
problems. Some emulsions effectively absorb the fragrance, reducing its
overall impression. If this occurs, rebalancing of the perfume is required.
H air products
Conditioners Usually, the same compound is used to fragrance the
shampoo and conditioner of a single range. Dosage in the conditioner is
lower, and the conditioner base promotes different aspects of the fragrance.
Careful balancing is needed.
Mousse Base stability, and performance of the fragrance are the two key
aspects to be aware of.
Permanent waves The alkaline environment of 'perms' can present diffi-
culties for the perfumer, and off-notes and discoloration are frequently
encountered. Chemical stability is very important-the raw materials used
in the perfume should be thoroughly tested before being used. Permanent
waves also have powerful odours of their own, which are impossible to
mask. Consequently, a strong perfume that will ameliorate these base odours
and harmonise with them will prove to be the most acceptable answer.
Shampoos Points to consider are solubility of the perfume in the base,
and acceptable performance from the bottle and in-use.
Spray Base notes from the active agents and propellants need to be
harmonised with the perfume. The general comments made about aerosols
also apply.
Styling gels Solubility and perfume performance are the two major
sources of problems.
Bath products
Foam baths Particular problems are lack of perfume performance,
insolubility, discoloration, and separation (possible precipitation) of the
pea ding agent where used.
Shower gels The comments are the same as those for foam baths, with
the additional problem of base thinning by the perfume.
Bath oils Solubility and performance are the main technical points for
the perfumer. Bath oils readily envelop fragrances, and the use of very
powerful ingredients in the topnotes is one method of achieving perfume
performance. Raw materials, such as fruity esters, essential oils containing
pyrazines (galbanum, petitgrain and vetivert), and essential oils that are high
in the terpene hydrocarbons (olibanum, nutmeg and orange), will all give
beneficial results.
Talcs Points to note are the loss of volatiles and oxidation over the
exceptionally high surface area, and discoloration of components like indole
and vanillin, which, odourwise, are very effective in tales.
Toilet soaps Coloration and discoloration can occur in pale-coloured and

white soaps. Very volatile materials may be lost both during the soap-making
PERFUMERY 285
process, and during storage. At high levels, fragrances may affect the finish
on the final stamped soap bar.
Suncare products The perfumer must bear in mind that suncare products
are usually applied to the skin when it is very warm or when it will become
very warm. The profile of the fragrance should not alter drastically over
these temperature ranges. Safety of ingredients is particularly important in
suncare products, since some materials are photo-sensitisers.
Baby-care products Once again, safety is of paramount importance, and

fragrance should convey the desired safe and 'caring' messages. Fragrances
for baby care products must also be effective at low concentrations.
Lipsticks Clearly, the flavouring aspect of the fragrance must be considered

along with effective base cover. Sweating can be an occasional problem, and
is associated with insolubility of the perfume.
Face powders Oxidation and loss of volatiles can present difficulties. The
perfumery is very similar to that for talc.
Shave products Performance and odour type are usually the main areas of
difficulty, although in terms of safety, the perfumer must bear in mind that
the skin is abraded during shaving.
8.9 Stability testing
A standard regimen of testing of a perfumed cosmetic or toiletry should be

based around the following framework.
(i) Samples of perfumed and unperfumed base.
(ii) Storage at (1) O°C (control); (2) ambient conditions (dark); (3) ambient
conditions (window or artificial daylight); and (4) oven temperature
(40°C).
(iii) Assessments at one month, two months, three months and six months.
(iv) Evaluation of samples for product stability (i.e. colour consistency,
etc.), perfume character and perfume strength.
(v) Packaging to ideally be customer-provided for the specific project;
otherwise an inert material (e.g. glass, lacquered cans, etc.).
As information from the stability programme builds up, the perfumer becomes
more aware of potential problems and potentially unstable raw materials,
and can take appropriate measures when working on a brief. However, all
fragrances should be tested in the final product prior to market launch, since
combination effects, both synergistic and antagonistic, can and do occur.
8.10 Compounding
Compounding is the term used by the fragrance industry for the bulk
production of perfume concentrates. The compounding of quantities of
perfume is basically simple, but must be carried out with the utmost precision
and accuracy. Fragrance manufacture is usually a straightforward mixing
procedure, therefore requires very few processing operations. However, the
presence of crystals, resins and other solids or semi-solids in the formulation
demands an efficient mixing regime and careful formulation by the perfumer
to ensure that, once homogeneously mixed, the fragrance will not suffer from
deposits of crystalline components on standing. Resinous materials are
usually stored in a warm-room to keep them in a pourable state and, conse-
quently, easier to handle. Thermolabile materials are kept refrigerated, but
most other items are stored at room temperature. The ideal storage conditions
for most fragrances and fragrance ingredients are those where heat, light and
air are excluded or reduced to an absolute minimum. Readily oxidised
materials are best kept under an atmosphere of nitrogen.
The normal sequence of addition of the formulation components is: (1)
solids; (2) resins; (3) stable aroma chemicals (to act as solvents for the first
two items); (4) the remaining aroma chemicals; (5) essential oils; and (6)
speciality bases, sub-compounds or premixes, and highly volatile materials.
High-speed stirrers will dissolve most solids and resins in the solvent part
of the formula, and will give a rapid, effective mix of the total fragrance when
all the ingredients have been added. Stainless steel vessels stirrers and other
ancillary equipment are used universally for fragrance compounding. Once
mixed the fragrance will be filtered by one of several techniques and when
approved by quality control, packed into containers for shipping.
Automation and computer-controlled compounding are now being used
in some of the larger fragrance houses. Traditional compounding as carried
out by the majority of the trade is a highly skilled job, and full training takes
at least 18 months. Knowledge, technique, accuracy and efficiency are the
hallmarks of a top-grade compounder.
8.11 Quality control
The main parameters assessed during the quality control of fragrance

compounds are odour, colour, physical state, density and refractive index.
Occasionally, infra-red (IR) spectrographs and gas-liquid chromatographs
(GLC) are used as fingerprints, and optical rotation (OR) may be important
in the case of some compounds with optically active components, e.g. citrus
blends. The odour of a fragrance compound should always be evaluated
against a standard by a panel of at least two qualified or trained persons,
and should be assessed on smelling strips, both fresh and after drying down
PERFUMERY 287
for a minimum of six to eight hours. Since most fragrances are multi-
component, a period of maturation may be expected, and all fragrances
noticeably change in odour during the 24 hours following manufacture.
Although the colour of a specific perfume may vary slightly from batch
to batch (often due to the variation in the natural raw materials), the clarity
and mobility should not. Only in exceptional circumstances should a perfume
be anything but clear. Lack of clarity suggests a non-homogeneous mix and,
possibly, the presence of water.
Measurements of density (SG) and refractive index (RI) are undertaken
universally, by fragrance houses and perfume purchasers alike. These physical
tests give an indication that the raw materials within a specific formulation
are reasonably consistent, both qualitatively and quantitatively. However,
perfumery materials, especially natural products, vary from batch to batch
and crop to crop. Consequently, the SG and RI of a specific perfume will
vary slightly, with variations in the individual components being either
compensating or cumulative. As a result, realistic ranges are set for SG and
RI values. Fingerprinting by IR and GLC is less frequently used, although
the very specific results achieved by a GLC assessment can be a valuable
back-up when trouble-shooting problems, shown up by non-conformity of
a sample to one or more of the other tests, occur.
The use of a computer 'nose' can be expected to increase. This technology is
in its early stages but is progressing rapidly and is based on the principle of
specific polymer receptor sites generating a response that can be interpreted
and plotted by a computer. Advances in this area will take place in the struc-
ture and size ofthe receptors and the complexity of the computer software.
The tests described above are also carried out on all raw materials and
sub-compounds being used in production, and it is at this stage that many
potential problems can be eliminated. Good quality raw materials, screened
by an efficient quality control procedure, are absolutely essential. In fact, the
consistent quality of a company's products depends on this and many other
factors. With all these factors, reputable suppliers, effective internal systems,
well-trained development, production and qU:llity control staff, and top-level
management policy are crucial.
8.12 Special additives
Many essential oils used as perfumery raw materials exhibit desirable

cosmetic and therapeutic properties and may, therefore, be used as 'special
additives' in a cosmetic or toiletry formulation. Camomile and lemon are
examples of two such oils. Several fixed oils are also incorporated as active
ingredients. Aloe vera, jojoba and evening primrose oils are all currently
enjoying popularity as additives that give cosmetic benefit. These fixed oils
usually have relatively low odours and are often included in the formulations
at low levels, presenting few problems to the formulator in terms of their

effect on the overall odour of the product.
Both aqueous and glycolic extracts of plants and herbs have demonstrable
beneficial properties and are used particularly in skin, hair and bath
preparations. These extracts contain components that are not always present
in the respective essential oils, therefore the incorporation of the essential oil
may not give the desired effect. Where an essential oil does contain the
required components for the cosmetic chemist, it is often possible to develop
the perfume with the specific oil or oils as a part of the theme.
8.13 Glossary of odour descriptors
Aldehydic sharp, fatty or soapy; characterised by the straight chain

aliphatic aldehydes in the range C s to C 12 .
Amber sweet, warm, slightly animalic; frequently vanilla-like.
Animalic redolent of animal odours; includes civet, musk,
ambergris and castoreum.
Balsamic warm, sweet and resinous with a faint medicinal aspect.
Camphoraceous medicated; reminiscent of camphor and eucalyptus.
Chemical usually harsh, aggressive and basic odours; typified by
products such as amyl alcohol, acetophenone and
diphenyl oxide.
Citrus fresh, tangy and zesty; smelling of lemon, lime, orange,
mandarin, grapefruit, bergamot or combinations of
these.
Earthy usually a combination of green, rooty and dank aspects.
Fatty having the odour of animal or vegetable oils or fats.
Floral having the odour of flowers, e.g. carnation, honeysuckle,
jasmin, lily, rose, tuberose, violet or ylang.
Fresh used subjectively depending on personal taste and
experience; commonly citrus, light floral, green or fruity.
Fruity any natural fruit note.
Green light intense; redolent of leafy, grassy aromas.
Herbal fresh plant odours, e.g. lavender (floral), rosemary
(medicinal), camomile (fruity), basil (culinary) or
coriander (spicy).
Leather phenolic, warm, animalic.
Light discrete; usually floral, green, citrus or combinations of
these.
Medicinal phenolic, camphoraceous, herbal; often pungent.
Mossy earthy, woody, phenolic, green.
Nutty sweet, oily, natural nut odours.
Pine redolent of pine wood, needles and resins.
PERFUMERY 289
Powdery soft, gentle; often balsamic, ambery and musky.
Resinous warm, sweet, balsamic; sharp in the topnote.
Spicy pungent, hot and culinary, e.g. bay, cardamon, cinnamon,
clove, cumin, ginger, nutmeg and pepper.
Sweet heavy, cloying; typified by vanilla and sugary notes.
Warm typically ambery, animalic, balsamic and sweet.
Woody natural wood notes such as sandalwood, cedar and
gUaiac.
Further reading
Arctander, S. (1969) Perfume and Flavor Chemicals. S. Arctander, Montelair, New Jersey.
Arctander, S. (1960) Perfume and Flavor Materials of Natural Origin. S. Arctander, Elizabeth,
New Jersey.
Poucher, W.A. Perfumes, Cosmetics and Soaps. 8th edn: Vol. 1 (1974), Vol. 2 (1975) and Vol. 3
(1975); 9th edn: Vol. 1 (1991) and Vol. 3 (in press). Chapman and Han, London.
Appel, L. (1982) The Formulation and Preparation of Cosmetics Fragrances and Flavours,
Novox, NJ, USA, ISBN 1-870228-10-3.
Bauer, K. and Garbe, D. (1985) Common Fragrance and Flavour Materials, VCH, Weinheim,
ISBN 0-89573-063-4.
Lawless, J. (1992) The Encyclopedia of Essential Oils, Element Shaftesbury, UK, ISBN 1-85230-
311-5.
Van Toller, S. and Dodd, G. (1988) The Psychology and Biology of Fragrances, Chapman & Hall,
London, ISBN 0-412-30010-9.
9 Personal hygiene products
M.J. WILLCOX
9.1 Introduction
The basic concept of personal hygiene is a relatively recent phenomena and,

throughout history, mankind has probably been far more concerned about
external appearance rather than about the general condition of the body.
This chapter will consider current trends in personal hygiene products with
some reference to the historical background.
9.2 Soap and other solid bathing products
9.2.1 Toilet soaps

Soap in its multitude of different forms would probably be regarded as the
most basic material for personal hygiene. The history of soap and soap-
making in its broadest sense stretches back to around 2800BC, although in
those days the products would most probably have been used for washing
garments rather than for personal hygiene. Soap-making originally developed
in the Mediterranean basin. Soap would have been regarded as a luxury
item, therefore its availability would be quite restricted. It was not until the
production of cheap caustic materials in the 19th century that any
recognisable industry developed.
The basic chemistry of soap-making has hardly changed since its earliest
days and involves the reaction of neutral fats or fatty acids with caustic alkali
to form a soluble soap product with surfactant properties. Today, volume
soap production is a highly automated process, far removed from the days
of processing in open pans, although such production techniques are still
widely practised by smaller manufacturers and are often considered to
produce soap of a premium quality when the highest quality raw materials
are selected.
Since the formulation of the basic soap does not vary greatly, the present
discussion on formulation and development will be restricted to the many
modifications that can be made to create a wide range of interesting and
novel products. Development trials can be conducted with full-scale plant
but it is more appropriate to carry out initial formulation trials using
PERSONAL HYGIENE PRODUCTS 291
laboratory-scale equipment. This type of equipment replicates the full-sized
plant and, as an absolute minimum, requires a triple roll mill and an extruder.
Additional equipment such as a mixer and a stamper are ideal but not
essential.
9.2.1.1 Basic formulation requirements Soap is a remarkably versatile

medium and the choice of possible additives is almost limitless. The most
basic formulation requirements will now be considered.
Soap base to 100.00

Titanium dioxide 0.1-0.4
Colour q.s.
Perfume 0.5-1.0
Soap base The initial selection of the appropriate soap base is important
as it can affect colour, odour and performance. The soap base should contain
an appropriate preservative system, the selection of which normally depends
on the preferences of the base manufacturer. Most preservative systems are
combinations of a chelating material such as EDT A to take care of any free
metal ions, and an antioxidant material to prevent the possible oxidation of
the fatty constituents of the base itself. If there are any doubts about the
long-term stability of the base material itself, the formulator may consider
it appropriate to add further EDT A and antioxidants.
Depending on the choice of fatty materials used in manufacture, the soap
base can vary in colour from an almost pure white through to a dirty, creamy
yellow. The odour will also vary accordingly.
Titanium dioxide This is widely used as an opacifier to provide a
consistent background on which to create a wide range of different colours.
Although the anatase grades have been preferred, current environmental
pressures indicate that the rutile grades may become a more acceptable
alternative. The latter have the disadvantage of being slightly less opaque,
and of having a yellower tint.
Colour The selection of appropriate colouring materials depends on a
number of factors including processing techniques, current legislation and
the final market place for the product. The ideal ingredients will: (i) be readily
dispersible throughout the soap mass to produce an even colour; (ii) have
good tolerance to a pH of 10; and (iii) have good light stability. Inorganic
pigments that fulfil these criteria include: (i) iron oxides (red, yellow and
black); (ii) ultramarines (blue, pink and violet); and (iii) chrome oxides. Such
pigments, however, only permit the formulator to create a limited range of
final shades. Consequently, they are often complemented with organic pig-
ments that also have good light stability and tolerance to alkaline conditions.
Although these particular colours will not necessarily have been developed
for use in soap (but probably more specifically for use in the plastics and
paper industry), experience will have shown then to be excellent for use in
soap. Advice on colours can be obtained from reputable cosmetic colour
suppliers, who will share their knowledge and experience. Both organic and
inorganic pigments can be incorporated into soap either as fine powders or
as paste dispersions~the final decision will be determined by the style of
processmg.
Within the EC, colouring materials are covered by a number of positive
lists, which relate to specific areas of use. It is essential to ensure the
acceptability of any proposed colour system. Such considerations become
even more important when export to the US and Japan is considered since
regulations in both of these countries can further restrict the choice of colours
(see chapter 11). For example, although soap as an individual item is not
covered by the Food and Drug Administration regulations in the US, it is
often considered prudent to approach formulation work as if it were. This
can restrict choice to the inorganic pigments mentioned earlier, together with
a limited range of certified organic dyestuffs that have poor light and product
stability. Japanese regulations are very precise, and the choice of pigments
and dyestuffs are quite restrictive. Certain parts of the spectrum cannot be
obtained without the use of colours with extremely poor light stability.
Perfume Once an appropriate colour for a new soap formulation has

been decided on, the next task is to develop a suitable fragrance. The expertise
of one or other of the many fragrance supply houses may be utilised to
provide a suitable perfume, at an appropriate price to satisfy the brief supplied
by the marketing department, or by the customer.
As with any perfume development project, it is essential to provide the
perfumer with as much information as possible regarding the base material,
and with other pertinent comments. Although soap is a reasonably hostile
environment to perfume, the range of perfumery raw materials with ac-
ceptable stability enables the competent perfumer to achieve most of the
desired fragrance notes. In some areas, however, perfume interaction can
cause coloration and discoloration problems. Perfumes with significant levels
of vanilla notes suffer from particularly severe discoloration. For the majority
of development projects, it is possible to eliminate or minimise discoloration
problems, but more basic problems can be encountered when the soap is
'intended to form part of a product range based on a specific alcoholic
fragrance. In some cases, the only option is to accept the discoloration and
aim to produce a soap colour that masks or complements it. Many of the
soaps produced for French couturier houses contain no colouring material,
and the final colour of the product is determined by the coloration or
discoloration due to perfume alone.
The level of fragrance likely to be included in the more basic formulations
would probably be no more than 1%, but this is by no means absolute and
normally the upper limit will be determined by cost and/or processing
restrictions. Even at the upper levels, it is possible to further increase perfume
performance without adversely affecting process performance. This can be
achieved by the partial use of micro-encapsulation for some of the perfume
dosage.
Once the initial outline formulation has been selected, pilot production
trials are essential to ensure that the new formulation provides the desired
characteristics for colour and perfume, both on initial manufacture and after
a series of controlled stability tests. These production trials will also enable
the formulator to determine how the new product behaves during manufacture.
At this stage it may even be necessary to consider modifying the forqlulation.
This may be as simple as adjusting the level of colour to correct for process
scale-up, but could, under the worst conditions, require a major rethink of
the basic formulation itself. Samples stored at elevated temperatures are very
useful for determining whether any discoloration is likely to take place, while
samples stored in daylight indicate the light-stability performance of any new
formulation. It is often useful if the perfumer conducts parallel stability trials
using samples produced to the final formulation.
9.2.1.2 Variations on the basic formulation As mentioned earlier, soap is a

very versatile product and the range of possible additives is almost limitless.
The only restrictions are (i) the exclusion of raw materials that are potentially
harmful to the processing conditions, workers and equipment; and (ii) the
exclusion of materials that degrade under alkaline conditions. All additional
formulation components should be chosen so as enhance performance (either
actual or perceived) and, possibly, to support specific product claims, thus
giving marketing staff the selling points required to compete in the
marketplace.
Superfatting agents Soap is a relatively harsh washing medium in its own
right and it is therefore considered beneficial to improve the perceived
performance with the use of superfatting agents. The average consumer is
also much more aware of the concept of 'moisturising' since the introduction
into the marketplace of cleansing/ cream bars. These products have been sold
in the United States for many years using well proven technology which is
considered later in this chapter, but are relatively new to the European
market. The formulator is often faced with the challenge of trying to
reproduce the washing characteristics of these cleansing bars by the addition
of cost effective superfatting systems.
The system can be based on either single products or complex cocktails of
oily and emollient chemicals. Originally the most frequently used materials
included mineral oil, petroleum jelly, lanolin and nut oil fatty acids at levels
of 0.5-1.0%. More recently more complex molecules often based on
quaternary compounds are found to be very effective at levels up to 2.0%.
However there can often be associated processing difficulties and ideally such
additives should be included earlier in the soap making process prior to
drying. Fatty chemicals from the oil phase of simple emulsion systems can
also be included to substantiate market claims such as 'contains cold
cream'. In reality, the formulator may choose to include a low level
of the actual cream whilst incorporating higher levels of other
appropriate fatty chemicals such as octyl hydroxy stearate or glyceryl
ricinoleate, which can impart the desired feel to the soap tablet and allow
consumers to draw their own conclusions regarding enhanced product
performance. As with perfume, it is possible to use encapsulation techniques
to increase the levels of addition without the consequent production
difficulties that would normally be associated with additive levels of oils and
fats in excess of 2%. The formulator should never forget that products must
be capable of being produced on full-scale plant, therefore plant trials on
soaps containing new and exotic oily cocktails are essential.
Natural oils and extracts With current trends towards more natural
products, it is possible to incorporate a wide range of natural oils such as
jojoba, avocado, apricot, cherry kernel, hazelnut, etc. With these oils, it is
often wise to include an appropriate antioxidant to prevent any tendency
for rancidity. A wide array of natural extracts can also be used to further
substantiate product description claims. In practice, these often contain very
little of the true natural product but do seem to be widely used, albeit at
relatively low levels, either separately or in combination.
Abrasives Oils and natural extracts can impart improvements to the feel
and texture of the soap bar, but it is also possible to use soap as a vehicle
to carry abrasive materials and create an astringent product that is still
pleasant to use. Once again the choice of possible additives is very compre-
hensive and includes: oatmeal, pumice, various crushed nut kernels, seaweed,
herbs and spices. The formulator is limited only by the effect that processing
may have in breaking down particle size and the attractiveness of the final
product. The alkaline nature of soap can also cause some added natural
products, such as flower petals, to change colour but this can only really be
determined by trial and error.
Deodorants In addition to formulations with aesthetic qualities it is also
possible to create products that have specific treatment properties, parti-
cularly in the deodorant area. Soap is an ideal vehicle for deodorant materials,
with those most frequently used being triclosan (Irgasan DP 300) and
triclocarbon (TeC), either individually or in combination. Raw material
suppliers can provide detailed information regarding optimum levels of
addition, although certain specific combinations of the two materials that
provide the best synergist effects may well be covered by patents. Triclosan
and triclocarbon have significantly different kill spectrums. The choice must
be balanced against the discoloration that results from the use of triclosan
following exposure to light. It is also possible to substantiate general claims
of a deodorant effect by the use of specific perfumes-fragrance suppliers
will be able to advise on this point.
Alternative base materials Regular toilet soap is still mainly produced
from raw materials based on tallow although with increasing influence of
animal welfare groups, there is growing interest in the use of base materials
that are totally derived from vegetable feed stocks. Such soaps are normally
produced by the substitution of palm oil or palm oil fatty acids for the tallow
or tallow fatty acids in the regular material. The resulting bases can range
in colour from white to cream but, as far as the formulator is concerned,
they should be treated as separate raw materials. All of the previous comments
on raw materials remain relevant.
9.2.2 Shaving soaps

Many of the comments and observations concerning the formulation of toilet
soaps (section 9.2.1) also apply to shaving soaps. Shaving soap base differs
from toilet soap mainly by the addition of caustic potash at the saponification
stage. This change, in combination with the correct choice of fatty acids,
creates a softer base material with enhanced lathering characteristics. To
facilitate processing, the moisture content of the base material is normally
reduced to around 8%. The control of free alkali is crucial, and it is not
uncommon to finish shaving soaps with a slight excess of free fat to avoid
the possible risk of reaction to free alkali during use.
The choice of possible options for the formulator are much more restricted
than for toilet soap, with the principal requirements being fragrance and
skin-feel. The earlier comments made on such items as opacifiers, colours,
sequestering agents and antioxidants also apply here, and the general
philosophy with regard to fragrance selection remains constant, although
the levels of incorporation are often 10-20% higher than one would normally
expect to use for the equivalent toilet soap.
The use of superfatting systems in shaving soaps improves the skin-feel
after shaving, although it is important to keep the levels of oily constituents
at around 1% to prevent any significant effect on lathering.
9.2.3 Transparent/translucent soaps

The recent trend towards 'natural' products has seen a marked interest in
'clear' products of all types, and soap is no exception.
9.2.3.1 Transparent soaps True transparent soaps can be produced in a

number of different ways. One of the oldest methods involves dissolving soap
in alcohol with gentle heating to form a clear solution, which is then coloured
and perfumed. The colour of the finished bar depends on the choice of
starting materials and, unless a good quality soap is selected, may well be
quite yellow. This presents difficulties with certain colours.
The traditional process involves partial removal of alcohol by distillation,
and casting of the liquid soap into blocks. The blocks are left to condition
for up to three months before being moulded and packed into their final
presentation. This process, by its very nature, is expensive and is restricted
to some familiar products that have been in the marketplace for many years.
It is unlikely that the formulator would need to deal with this particular
style of formulation, since alternative, cheaper methods have been developed
using castor oil and sugar in addition to the regular soap-making
raw materials. With these methods, it is possible to produce transparent/-
translucent soaps directly from the constituent raw materials, without any
need to pre-prepare the soap as an intermediate stage in the process. A typical
basic formulation for this type of transparent soap is shown below.
Wt%
Tallow fatty acids 27.00
Coconut oil 7.00
Castor oil fatty acids 5.00
Alcohol 10.00
Sodium hydroxide 6.20
Sugar 15.50
Glycerine 9.00
EDT A 0.25
Water to 100.00
The selection of raw materials particularly the fatty ones, will have a
significant effect on the colour of the finished product. As always, there has
to be a commercial balance between the most refined, and therefore most
expensive materials if one is to achieve a realistic end cost for the product.
Castor oil is usually considered to play an important part in the formulation
in achieving optimum clarity, although it does have the disadvantage of
giving the finished tablet a distinct yellow colour. Other alkaline materials
(e.g. triethanolamine) may be used to effect saponification, although the
resulting bars are often much softer than those produced with caustic soda.
The method of production involves the melting of the fat phase and the
preparation of a water phase in which the sugar, glycerine and preservatives
are dissolved. These two phases are reacted with an alcoholic solution of
caustic soda under controlled heating. Some simple refluxing is an advantage.
Having allowed the reaction to subside, the soap mass is checked to ensure
complete saponification with a very slight free caustic finish (less than 0.1%).
This soap mass is then available for colouring and perfuming.
The choice of perfumes, additives and colouring materials is more
restricted because of the process conditions and it is essential that none of
these additives have any adverse effect on the transparency of the finished
bar.
It is very important that the choice of perfume should take account of
process heat (up to 4 hours at 70°C) and it is essential to avoid the more
volatile perfumery materials along with those which may be prone to change
colour / degrade at these elevated temperatures. Natural extracts, oils and
vitamins may also be added, always bearing in mind the comments regarding
transparency. Organic dyestuffs are probably the best choice for colouring
the bars but as they can have poor light stability it is often prudent to include
an ultraviolet screen to minimise fading problems.
Following colouring and perfuming, the finished soap is poured into
separate moulds or cups and allowed to set before packing. The process can
be scaled up for bulk production without any major difficulty, although the
systems for dosing and solidification become relatively sophisticated.
The use of alcohol can be considered something of a problem as it does
necessitate the provision of controlled production areas and equipment to
avoid any risk of explosion. More recently transparent soaps are being
produced using combinations of soap and detergent which result in products
with excellent colour and clarity. An outline formulation for this type of
transparent soap is shown below:
Wt%
Stearic acid 15.00
Coconut fatty acid 6.00
Glycerine 8.00
Sodium hydroxide 4.20
Sugar 10.00
Sodium laureth sulphate 16.00
Sodium lauryl sulphate 12.00
EDTA 0.20
BHT 0.20
Water to 100.00
As one is able to select virtually water-white raw materials the resulting bar
has a very pale colour and consequently it is possible to obtain more delicate
pastel shades. The method of production is similar to the method given above
with the surfactants and the propylene glycol being combined with the fatty
phase. With the high level of volatiles it is essential that the finished bars are
wrapped in a film with adequate barrier properties and this also has the added
benefit of enhancing the visual appearance of the bar.
9.2.3.2 Translucent soaps A recent development has been the appearance

of translucent soaps either tallow-based or produced totally from vegetable
raw materials. Unlike transparent soaps, these are produced on regular soap-
making equipment by extrusion. This means that they are capable of being
moulded into a wide range of shapes, which tend to be simple distortions of

oval or rectangular blocks.
It has long been recognised that soap passes through a translucent phase
during the processing of the basic soap base. The ability to control the pro-
duction of this translucent phase by the addition of glycerine or other polyol-
type materials, linked with processing modifications, has allowed the soap
manufacturer to develop a wide range of novel presentations. The formulator
need not be concerned with the formulation of the soap base itself, and the
following comments relate to the options available for the development of
the finished formulation.
(i) As with transparent soap, the most important consideration is to
ensure that nothing is done to affect the translucency of the finished
soap tablet. It should also be recognised that the translucency of these
soaps is often enhanced during storage.
(ii) The selection of colours will follow the same general consideration
mentioned previously although, as the level of colour required is normally
very low, it is possible to use organic pigments in addition to organic
dyestuffs. One disadvantage of the low level of incorporation is the
possible reduction in colour stability on exposure to light. This is parti-
cularly relevant to translucent soaps which are most often presented
unwrapped or with a clear film overwrap.
(iii) The selection of perfume is critical since certain perfumery raw
materials affect translucency. The competent perfumer will be able to
provide a wide range of interesting fragrance alternatives once the
limitations of the final presentation are made known, and provided
he or she is able to work with the relevant soap base material.
The formulation for a translucent soap is normally quite simple and
straightforward, adding the following blend to the chosen base.
Wt%
Perfume 1.0-1.5
Colour q.s.
Preservative q.s.
Experience suggests that the level of perfume should be no higher than 1.5%
to ensure optimum clarity.
Despite the need for optimum translucency, it is possible to incorporate low
levels of natural extracts and natural oils to enable claim validations to be
made for certain soaps. The limitations are normally established by process
experience but, for an acceptable product, a total additive level of 2.5% is a
likely maximum. Although soap bases are normally fully preserved it may be
prudent to add a small quantity of BHT (butylated hydroxy toluene) to ensure
good product stability. The translucent appearance may be exploited further
by the use of solid material or pearl additives, both of which can provide novel
appearances to further enhance the soap tablets.
As with regular toilet soap, it is important to carry out stability tests on
prototype samples over an extended period to ensure that no deterioration
occurs. This is particularly important with perfumes, as any discoloration
effect is readily apparent.
9.2.4 Synthetic detergent/combination bars

The development of modern detergent systems has provided raw materials
that can be used singly or in combination to produce a solid bar with a much
lower pH than regular soap. Indeed some of the undoubted success of
recently introduced cream/ cleansing bars has been the ability to demonstrate
that products mimic the pH of skin.
Although many of the basic raw materials are more expensive than regular
soap the added benefits do allow a higher retail price for such products. When
these products are produced from the most basic raw materials, specialised
equipment is required and indeed many of the processes may be covered by
patent restrictions. However, synthetic detergent!combination bars can be
processed on regular soap-making equipment although it is essential that
the temperature is carefully controlled to ensure that the detergent mass is
maintained in a suitable plastic condition without becoming too mobile.
The product is also difficult to handle on pilot plant equipment.
Formulations for synthetic detergent! combination bars tend to be
relatively simple and because of the less aggressive conditions, it is possible
to use them as vehicles for specific treatment chemicals that would degrade
at higher pH levels. The lower background odour means that perfume levels
can be reduced and, since good colour distribution through the bar is often
difficult to achieve, the products are very often white or off white.
Combinations of synthetic detergent systems and regular soap can offer
the opportunity to reduce cost but on the down side the pH is only reduced
slightly to around 9.0-9.5. These formulations can pose some production
problems and it is again essential to maintain close control of process
temperatures.
9.2.5 Bath salts/bath crystals/bath cubes

Solid bath additives are generally intended to soften the water and produce
a delicate fragranced atmosphere for bathing. It is also possible to include
other additives to further enhance the bathing experience.
9.2.5.1 Bath salts The basic formulation of bath salts is shown below.
Wt%
Sodium sesquicarbonate 97.50
Mineral salt 1.50
Perfume 1.00
Colour q.s.
This product could be produced by simply using a ribbon mixer to blend

together the solid components, after which the perfume and colour would be
dispersed on to the surface to create the desired end result. The most com-
monly used mineral salt is sodium chloride, although combinations of
other salts can be used to simulate seawater.
Starting with the basic outline formulation, it is possible to include solid
detergents to enhance water softening and to create an illusion of foaming.
One of the sodium dodecylbenzenesulphonates would be appropriate. Fatty
acid ethanolamides and fatty esters are also added to improve skin-feel. As
the level of additives is increased, the mass becomes quite sticky. It is necessary,
therefore, to include a suitable drying/flow agent to ensure that the product
remains a free-flowing powder. The process of replacing the sodium sesqui-
carbonate with other components has no real limit apart from cost. In practice,
the total additives could probably account for as much as 40% of the total
formulation; however, the fatty/liquid components would account for no more
than 10%.
The product can be tinted using pigments dispersed on to a suitable extender,
and the product can be further enhanced by the use of a solid, water-soluble
dyestuff, which will colour the bath water. This can be a totally different colour
to the product itself. Although in the laboratory the formulator is able to
approximate process conditions by simple mixing, it is essential to check the
levels of colour dispersion and the amount of drying required for any individual
formulation by means of a full-scale trial. A ribbon mixer with a separate high-
speed mixing blade to ensure good dispersion of all raw materials is ideal, and
equipment for sieving the finished product to remove any large undispersed
particles is advisable.
9.2.5.2 Bath crystals Bath crystals are normally formulated in a similar

manner to bath salts but using raw materials with a definite crystal structure,
which enhances the appearance of the finished product. Sodium sesqui-
carbonate is available as fine, needle-like crystals. Sodium chloride can be
obtained in a number of different crystalline forms, both regular and in lumps.
Sodium thiosulphate has also been used. With these basic constituents it is
only possible to surface coat the crystals, and the formulation requires little
more than the addition of a liquid colour and perfume.
9.2.5.3 Bath cubes Bath cubes are basically bath salts combined with
suitable binders and compressed to form solid tablets. A typical formulation
is as follows.
Wt%
Sodium sesquicarbonate (powder) 92.00
Sodium sesquicarbonate (crystals) 2.50
Maize starch 2.00
Talc 1.50
Mineral oil 1.00
Perfume 1.00
The formulation of bath cubes is very difficult to simulate and is probably
best left to suppliers. As with solid bath additives, all perfumes should be
selected with the end use in mind. One recent innovation has been that of
'fizzing' cubes. These incorporate suitable alkaline and acidic materials into
the cube so that the product dissolves with the formation of carbon dioxide,
and generates bubbles.
9.3 Liquid bathing and showering products
The market for bathing and showering products has seen tremendous growth
in recent years and there has been a significant move away from the solid
bathing products mentioned in the previous section. The range of newer
products includes foam baths, shower gels, bath oils and after-bath preparations.
This section will consider the formulation options available, based on
surfactants materials.
Regular soap is an excellent surfactant that can be produced from readily
available raw materials. Its only major disadvantage is its poor performance
in hard water, and this feature prompted the development, from vegetable oils,
of sulphonated derivatives for use in textile processing. The technology
developed gradually, with the production of the first surfactants from petroleum-
based feedstocks around the time of World War I. The basic technology
for the production of surfactants developed between the two world wars, and
the expansion in the petrochemical industry made available large volumes of
reasonably priced raw material. Today, a wide range of alternative raw
materials are available to the formulator.
9.3.1 Foam baths

Foam baths, in either liquid or gel form, are probably the most widely used
bathing preparations currently available in the marketplace. A bewildering
array of clear and pearlised products, in a rainbow of colours, can be seen on
supermarket shelves.
The principle function of bathing, in the 'western' sense of the word, is the
cleansing of the body, although the therapeutic effect of relaxing in a hot bath
should not be ignored. A foam bath will help to soak off dirt and body oils
and ensure that they are left suspended in the bath water. It will also ensure
that no tell-tale 'bath ring' is deposited, as is the case when soap is used. Al-
though cleansing is the principle function of a foam bath, good perfuming
and a capacity to impart some skin conditioning properties is desirable. As
already mentioned, the total bathing experience should create a pleasant,
relaxed atmosphere.
9.3.1.1Basic formulation requirements When formulating foam baths, a

number of fundamental attributes should be considered.
(i) Good foaming characteristics

(ii) Non-irritant to eyes, mucous membrane and skin
(iii) Reasonable cleansing power without adverse skin effects
(iv) A clean, fresh and attractive effusive perfume.
The selection of the principle raw materials will have a significant bearing on
the final product.
The main ingredient, even in the most basic formulations is the foaming
agent and selection of this surfactant should be made with the basic attributes
in mind. Surfactants are available in four principle types.
(i) Anionic-with the polar group having a negative charge
(ii) Non-ionic-with the polar group having no charge
(iii) Cationic-with the polar group having a positive charge
(iv) Amphoteric-with both positively and negatively charged polar
groups.
Anionic surfactants are probably the most widely used, as they are reasonably
priced and available as very pale coloured/water-white variants, which allows
the formulation of very pale/tinted products. Among of the most popular
forms of anionic surfactant used in foam bath formulations are the fatty al-
cohol ether sulphates. The sodium form based on lauryl/myristyl alcohols
containing either two or three moles of ethylene oxide forms the basic consti-
tuent of many formulations. More recently, the equivalent magnesium forms
of the same basic structure have become available. Although more expensive,
these have a much lower irritancy potential. The formulation for a typical,
moderately priced foam bath is shown below.
Wt%
Sodium lauryl ether sulphate, 28% active 50
Perfume 1
Sodium chloride 1.5
Preservative q.s.
Colour q.s.
Water to 100
Surfactant The combination of the basic anionic agent with the non-ionic
diethanolamide imparts improved foam stability and can help with the creation
of a suitably viscous product. These materials can also assist with the solubili-
sation of perfume and other skin-care ingredients where needed.
Perfume The choice of perfume is crucial to the development of a good
foam bath, and a reasonable amount of time should be spent in the evaluation
and panel testing of this vital component. The selected perfume should mask
any odour from the raw materials and give an impressive initial impact in the
head space of the container-a critical aspect most likely to stimulate
purchase by the consumer. The perfume should have a good 'lift' from hot
water to create the ideal bathing environment, and tenacity for the skin.
The level of perfume in the product will be determined by cost constraints, and
the formulator is under increasing pressure to obtain fragrances with high
impact at minimal cost. Fragrance levels of up to 5% are chemically feasible,
although some additional solubilisation may be necessary. Reasonable shelf-
life is an obvious requirement, and adequate product stability testing is vital
as perfumes can have adverse effects on colour, viscosity, clarity and even
preservative performance.
Sodium chloride This is widely used as a viscosity modifier and the level
of addition will need to be determined at the development stage once the total
formulation is available. The level of salt in the basic surfactant will vary from
batch to batch, therefore the level of viscosity modifier will need to be adjusted
according to analysis of the incoming bulk raw material. On occasions,
reduction in the viscosity of products that have become too thick may be
required. This can be achieved by the addition of alcohol, propylene glycol or
hexylene glycol.
Preservative Preservation of foam-bath formulations is vital to prevent
product degradation by moulds and bacteria. The basic surfactants may
contain preservatives, but addition of a selected preservative will almost
certainly be required. Validation must be carried out by challenge testing with
an approved method, normally involving the use of a range of specified
organisms. It is also essential to use an 'in-house' cocktail of organisms that are
specific to the individual manufacturing location. The choice of preservative
will be determined by the ultimate market for the product, since many
countries-and indeed specific customers-have approved lists of preserva-
tives. The whole question of preservation is highly volatile, since proven
products can be de-listed almost overnight. With increasing demands from
the consumer for 'safer' products, the levels of preservative may well be reduced,
since they can contribute to irritation difficulties for some consumers. In these
situations the importance of good manufacturing practice is essential to ensure
that there is no unnecessary overload on the preservative system by poor
'in-house' techniques.
Colour The selection of the colour system will be determined mainly by
the legislative requirements of the final market, and it is common practice
to use a range of US certified colours to create an appropriate colour palette.
This can prove problematic, since specific colours may be de-listed at any time.
Other markets, such as Japan, can be even more restrictive in the choice
available. Organic colorants may give rise to colour instability problems,
especially when pale-coloured products are required. Light stability must be
carefully tested.
Simple foam baths are relatively easy to manufacture and require no
specialised production equipment other than a suitable vessel equipped with

a large paddle mixer. The ability to control the speed of the mixer is vital if
unnecessary aeration is to be avoided.
9.3.1.2 Variations on the basic formulation The basic outline formulation

for a foam bath can be used by the formulator as the starting point for a
whole series of foam baths. Within reason, the active content can be reduced
to produce inexpensive formulations but these will obviously not have the
performance attributes that were identified earlier in this section. Possibly
of more interest is the addition of other materials to improve both the
appearance and performance of the product; here the only determining factor
will be the final cost objective for the finished product.
Opacifiers One of the most frequently used methods of enhancing the

appearance of the product is to include an opacifier to impart a pearl effect.
This can be achieved by the addition of alcohols (such as stearyl alcohol and
cetyl alcohol), ethylene glycol monostearate or glyceryl stearate. A dis-
advantage of using these particular raw materials is the necessity to heat
the formulation (less perfume) to around 70°C, and then allow the bulk to
cool slowly with stirring to ambient temperature to develop the pearl. An
alternative method not requiring heating is the use of a commercially available
pearl agent (opacifier-detergent blends) incorporated at a level of between
2.5 and 5.0%. In any opacified/pearl formulation it is vital to maintain opti-
mum viscosity to ensure that the pearl remains in suspension. Stability checks
are the only way to establish adequate shelflife and, in particular, to determine
the effect of fragrance on pearl systems.
Amphoteric surfactants Although the sodium lauryl ether sulphates are
reasonably mild products in their own right, the formulator may elect to
substitute a proportion of the ether sulphate with one of the amphoteric
surfactants mentioned earlier. Amphoteric surfactants exhibit excellent
mildness and very good foaming characteristics but, because of their higher
cost, they are normally used in conjunction with anionic surfactants. Typical
amphoterics are alkyl imidazoline betaines or alkyl amino betaines, which,
when incorporated at the appropriate ratio with the selected anionic, can
also be used to enhance formulation viscosity. Amine oxides are often claimed
to have improved foam boosting properties when compared with
alkanolamides and may well be preferred by the formulator.
Emollients Even when carefully formulated, foam baths can possibly
cause harmful effects on the skin, and the addition of emollients can be very
beneficial to product performance, and in helping to leave the skin soft and
smooth. A wide range of emollients is available. Although it may be difficult
to substantiate some of the moisturising claims that are made for many foam
baths, they do have a perceived effect on the skin and are very popular.
Taking all of the preceding comments together, an outline formulation for
an improved milder formulation with good afterfeel can be arrived at.
Wt%
Cocamidopropyl betaine 5
Opacifier~detergent blend 2.5
PEG- 7 glyceryl cocoate 2.5
Cocamidopropylamine oxide 1.5
Perfume 1.5
Sodium chloride
Preservative q.s.
Citric acid q.S. to pH 7
Colour q.s.
Water to 100
Although the comments made in this section are restricted to certain specific
anionic, non-ionic and amphoteric surfactants, the formulator will soon
recognise that there are many other surfactants in each particular category
that offer different properties. All surfactant suppliers will readily provide al-
ternative outline formulations to enable a wide choice of alternatives to be
created.
It is often difficult to describe foam baths as natural products, even though
the prime building blocks for the raw materials do have natural sources.
However, it is not uncommon for similar formulations to be marketed under a
'natural' banner by the addition of small quantities of natural extracts. It is
best left to the individual to make their own decision on the ethics of such
marketing platforms.
9.3.2 Bath oils

It may be appropriate to question whether bath oils should really be included
within the general area of personal hygiene products since they do not
contribute to cleansing. Their principle function is skin lubrication, with a
secondary function of applying fragrance to the skin.
9.3.2.1 Foaming bath oils Many products in the marketplace are described
as foaming bath oils but are best considered as foam baths with increased
levels of emollient oils. They foam well, do not leave any bath ring, and norma-
lly have higher levels of fragrance than regular foam baths. Consequently,
they may require additional materials to sol ubi lise the fragrance.
An outline formulation for such a bath oil is shown below.
Wt%
Cocamidopropyl betaine 7.5
Coconut diethanolamide 2.5
Cocamidopropylamine oxide 2.5

PEG-7 glyceryl coco ate 1.5
PEG-6 caprylic/capric glycerides 1.5
Perfume 1.5
Preservatives/colour q.s.
Water to 100
As with regular foam baths, formulation variants would follow a parallel
route.
9.3.2.2 Soluble bath oils If the level of emollient oils are increased
significantly, the foaming characteristics of these products will be drastically
reduced and they cannot be considered as foaming bath oils. They are more
correctly categorised as a form of soluble bath oil, although they impart a
significant level of skin lubrication, which is not necessarily the case with
regular soluble bath oils.
Soluble bath oils are normally formulated to deliver high levels offragrance
to the bath water but with few additional benefits such as emollient properties.
They are relatively simple formulations, consisting of little more than anhy-
drous mixtures of perfume, surfactant and colour. These products are quite
expensive and water may be included to reduce cost. When choosing the
surfactant, the level of fragrance and the desired viscosity of the final product
must be considered. Perfume solubilisation can be achieved using an
appropriate hydrophilic surfactant. An outline formulation would be as
follows.
Wt%
Perfume 10
Polysorbate 20/polysorbate 80 20
Water to 100
These products are very easy to manufacture and require no heating. The
perfume is mixed with the surfactant prior to dilution and the addition of
minor additives.
This type of formulation can be an ideal vehicle for producing
'aromatherapy' bath oils by the simple substitution of individual or blended
oils for the perfume. The choice of the oils imparts the different mood
conditions that such products are reputed to create.
9.3.2.3 Dispersible bath oils These are designed to be emulsified in the bath
water, creating a milky bloom. The emollient oils are balanced with
appropriate levels of surfactant to create a product that has no significant
oily feel and does not leave a bath ring. In many respects these products are
closely related to the foaming bath oils mentioned earlier, although the latter
products do not create a blooming effect.
Dispersible bath oils are relatively easy to manufacture and, as always,
the cost of the finished formulation will determine the choice ofraw materials.
In its simplest form, the product consists of an oil and perfume with an ap-
propriate surfactant. Mineral oil is a relatively inexpensive oil base, but
vegetable oils can be used for partial substitution. Other emollient oils will
also be required to aid perfume solubilisation and impart greater skin-feel
to the product. Polyethylene glycol ethers are most commonly used as a
surfactant and a reasonably priced formulation is outlined below.
Wt%
Mineral oil 60
Corn oil 5
Isopropyl myristate 15
Oleth-3 12.5
Perfume 7.5
Colour q.s.
Balancing the levels of the various components is required to achieve
adequate solubilisation for the chosen fragrance and to achieve the desired
amount of bloom when the product is added to the bath.
9.3.2.4 N on-dispersible/floating bath oils As their name implies, these are

designed to float on top of the bath water. On emergence from the bath the
bather's skin is coated with a thin oily film. Non-dispersible bath oils provide
a distinctly different after-bath sensation and, as the fragrance in the product
is concentrated in the thin surface layer, the release is greatly enhanced by
hot water-creating an acceptable fragranced atmosphere in the bathroom.
Their disadvantage is the oily ring left around the bath-if the bather is also
using a regular soap in an area of hard water, the effect is even more unsightly
because of the additional soap scum.
The ideal non-dispersible bath oil will cover the surface of the bath
completely and only deposit a light oily film on the skin. This requires a
careful balance between the oily and emollient constituents and the chosen
surfactant to ensure that the oil spreads rapidly across the water surface.
Laboratory trials using water at an appropriate temperature are essential,
since the spreading characteristics of systems are greatly affected by
temperature.
As with the dispersible oils, mineral oil forms a significant part of the
formulation, but its greasy feel may be modified by combination with isopropyl
myristate or one of the newer emollients such as the polypropylene glycol
ethers. These materials also have much greater solubilisation powers. The
choice of other emollient oils is almost limitless, and vegetable oil can also
be used to achieve differing skin-feeling characteristics. Materials such as
the condensation products of oleic acid esters of sorbitol have excellent
solubility and spreading properties. The choice of surfactant is also important
to ensure that emollient additives are soluble in the chosen oils.
Perfume is the most critical cost element in the formulation and the
optimum level will depend on the final cost target for the formulation. A
typical floating bath oil formulation is outlined below.
Wt%
Mineral oil 43.5
PPG-15 stearyl ether 45
Corn oil 5
PEG-40 sorbitan dioleate 1.5
Perfume 5
Colour q.s.
Product stability and performance testing is essential and should include a

careful evaluation of the proposed packaging. Significant proportions of oily
materials can interact with some plastics used in packaging. Although glass
containers may always be preferred, both for appearance and for lack of any
interaction, cost probably excludes their use for all but the most expensive
presentations. Glass is also considered unsuitable for bathroom use because
of the risk of breakage and injury.
These products also serve as excellent vehicles for 'aromatherapy'
products as indicated above in section 9.3.2.2.
9.3.3 Shower gels

Shower gels are, in the most simple terms, higher viscosity variants of foam
baths, often containing higher levels of active materials. The increase in
viscosity may simply be achieved by increasing the active content and/or
electrolyte levels, or by adding an alternative thickening agent to the formulation.
Most of the formulation criteria discussed in section 9.3.1 are relevant for
shower gels. However, as the method of use involves direct application to
the body, some attention needs to be paid to the mildness of the proposed
formulation. Consequently, a higher level of amphoteric surfactant is often
used. With careful adjustment of the levels of the two principal surfactants,
a range of viscosities up to an almost solid gel can be obtained.
An outline formulation for a moderately priced product is given below.
Wt%
Cocamidopropyl betaine 15
Coconut diet hanoi amide 2.5
PEG-7 glyceryl coco ate 2.5
Perfume 1.5
Propylene glycol 1
Water to 100
Recent formulation innovations have included the addition of materials
such as hydro beads to create a more interesting visual appearance and these
beads can contain additional emollient chemicals. Even solid particles such
as loofah can be incorporated into gel formation if the viscosity of the
product is sufficient to prevent separation/ settling.
9.3.4 After-bath and after-shower conditioners

After-bath and after-shower products are intended to replace some of the
natural skin oils that are removed during bathing or showering. Many of
these products are simple oil-based systems and may be considered unsatis-
factory because of their oily nature. More popular are low viscosity body
lotions (see chapter 3).
A more novel approach is to apply a product such as a liquid talc, or
even a body conditioner, which attempts to replicate the well established
effect of hair conditioning.
Liquid talc products are suspensions of talc or starch derivatives suspen-
ded in a light oil or alcohol base. These products are rubbed gently on to the
skin to produce a fresh, cool sensation, and to leave an emollient lubricity
-softening the skin.
10 Antiperspirants and deodorants
R. GIOVANNIELLO
10.1 Introduction
Based on an historical perspective, antiperspirants and deodorants are

relatively new personal care products, covering a 100 year span of develop-
ment and use. One can appreciate the technological advancements of these
compositions, considering that over 300 generations have passed during
which some kind of cosmetology was crudely practiced. Botanically
extracted oils, fragrances and metallic-based ointments were extensively
used for skin care, eye and facial decor.
In the early 20th century the antiperspirant active choices available to
consumers were few. This undeveloped cosmetic science, together with poor
product delivery forms applied to the axillary body region was considered
nothing less than crude in the extreme.
The earliest known marketed deodorant product was a zinc oxide-based
cream composition [1] introduced within the United States in 1888. Through
the years zinc in various salt forms has been evaluated for its antiperspirant
and deodorant properties. The incorporation of zinc halides into basic
aluminum and zirconium chloride complexes has resulted in salt complexes
described as useful antiperspirants possessing good alcohol solubility [2, 3].
Zinc metal complexes however were never adopted into the Category I anti-
perspirant active listing. Other zinc-based compounds known to have
deodorant potential were zinc peroxide, zinc salicylate, zinc sulfocarboxylate
and zinc sulfide.
In the early 1960s zinc phenol sulfonate was introduced in aerosol form and
was coupled with hexachlorophene. The effective antimicrobial action of the
two ingredients quickly led to high consumer acceptance and some
cannibalization of the decade-old roll-on antiperspirants. Today zinc
phenol sulfonate is one of the few clinically accepted zinc salts that can be
found in deodorant compositions. Hexachlorophene however was banned
in the mid-1970s due to potential skin penetration and neurotoxicity.
The earliest antiperspirant was a non-formulated product consisting of a
dilute aqueous solution of aluminum chloride. The application was simply
one of cotton swabbing the axillary area and waiting for the sting and water
to disappear in that order. Aluminum chloride despite its strong acidity is
perhaps the most effective active to this day. It can be found in pharmacies
ANTIPERSPIRANTS AND DEODORANTS 311
in a regulated dosage of not greater than 15% on a hydrated basis in non-
aerosol form.
Since the early 1900s, aluminum salts were primarily the only active
ingredients recognized as effective in reducing sweat and controlling odor.
Efficacy was not quantified until 1916, the first published report appearing
in the Journal of the American Medical Association. At the same time
promotional campaigns were under way leading to national popularity for
aluminum chloride solutions.
Esthetics were clearly lacking from the simple solution forms of anti-
perspirant but by 1930, cream compositions were introduced containing
aluminum sulfate in wax bases. Compared with current standards the
esthetics may appear to have been derived from poor cosmetic science, but
were in fact elegant to the consumer of that era. By 1945, 88% of the US
antiperspirant market was in the form of creams, the greatest share of an
antiperspirant form ever to exist.
In the 1950s hand squeezed aerosol and roll-on antiperspirants made their
way onto the market, representing unique delivery forms. The package
technology was not perfected however, leaving the consumer with convenient
but often faulty delivery systems. The attractive features were the fact that
the antiperspirants could now be applied without the use of fingers.
Popularity grew slowly but as early as the next decade, roll-ons dominated
the market over creams for a short period of time.
During the same era, phenomenal changes occurred in the way aerosols
were designed. Deodorants and antiperspirants were incorporated into
pressurized propellant systems [4] in metal containers leading once again to
high consumer acceptance. Valve perfection coupled with anhydrous
suspension compositions dramatically reduced the rate of clogging. By 1973
aerosol forms achieved greater than 80% market share. The huge success of
aerosols sparked interest in many countries. Currently, approximately two
thirds of the UK antiperspirant and deodorant market is in the form of
aerosols [5].
The mid-1970s in the United States can be remembered as an era of
growing environmental safety awareness which hit hard on aerosol com-
positions. Both fully halogenated chlorofluorocarbon propellants and
aluminum-zirconium complexes were prohibited from use in aerosols and
sprays leading to the fastest market decline in an antiperspirant! deodorant
category ever witnessed.
The greatest formulary ingredient ever recognized for esthetic improve-
ments came about at the same time that aerosols were under fire. The generic
name for this miracle additive was cyclomethicone. It possessed high esthetic
and lubricative properties which led to rapid technological advancements in
suspension roll-ons and sticks. These anhydrous suspension systems have
become consumer favorites and today more than 80% of all antiperspirant
formulations contain cyclomethicone. In Europe and other parts of the
100~--------------------------------------~
30 35 40 45 50 55 60 65 70 75 80 85 90 95
Year
Figure 10.1 A/P-DEO product form market history. US market = 1.8 billion $ = 80%
AP + 20% DEO. Key: ___ semisolids, --+- sprays, --+- liquids,
--8- solids.
world, aqueous based roll-ons and sprays dominate suspensoid stick com-
positions. The existing antiperspirant! deodorant market comprises roll-
ons, sticks, aerosols, gels and creams. Since 1985 consumers have had the
choice of conventional and enhanced performance types. The US market
history of antiperspirant and deodorants is graphically illustrated in
Figure 10.1.
10.2 Regulations
Unlike most cosmetic products, antiperspirants have been regulated more

stringently by the US Food and Drug Administration, both with respect to
the active raw materials and the finished product compositions. Up until
1938 there were no regula tions relative to cosmetic ma terials. The Food Drug
and Cosmetic Act which was enacted in 1938 by the federal government
clearly stipulated that deodorants which did not alter a bodily function were
viewed as cosmetics but antiperspirants which affected the operation of the
sweat glands were considered drugs. This physiological concept is interpreted
in basically the same way today throughout the world, however labeling and
testing requirements for cosmetic drugs do vary from country to country. The
United States has initiated the most specific labeling requirements and
Canada probably leads in the most conservative testing programs.
Antiperspirants are classified as over-the-counter (OTC) drugs and
deodorants are designated as cosmetic products. The regulatory control
tightens specifically when claims are made by the manufacturers of such
products.
The proposed rules for classifying OTC drugs were drawn up in the Federal
Register in 1972 by the FDA. The last final tentative drug monograph
CFR 21 part 350 was published in 1982 and since then it has been regarded
as the only document to spell out rules regarding safety, clinical testing and
active categorization. Labeling of OTC drugs is discussed in CFR 21
part 20l.
In addition to the tentative final document, Category I antiperspirant
actives which were effective in January 1995 were adopted by United States
Pharmacopeia (USP) as drug compounds, assuming identity standards and
test methods consistent with USP requirements. Currently, additions and
modifications are underway to provide full coverage of Category I actives.
The specifications will include the total range of elemental atomic ratios,
solvents and concentrations. The changes are consistent with the industries
use or intended use within the specifications already permitted in CFR 21
part 350. For commercial considerations, only those actives listed in
Category I should be of interest to the formulator as shown in Table 10.1.
Table 10.1 US FDA over-the-counter Category I antiperspirant actives

Atomic ratio range
Active ingredient Metal chloride A1:Zr

Aluminum chlorohydrate 2.1-1.91:1
Aluminum dichlorohydrate 1.25-0.9: 1
Aluminum sesquichlorohydrate 1.9-1.26: 1
Aluminum chlorohydrex PG 2.1-1.91: 1
Aluminum dichlorohydrex PG 1.25-0.9: 1
Aluminum sesquichlorohydrex PG 1.9-1.26: 1
Aluminum chlorohydrex PEG 2.1-1.91:1
Aluminum dichlorohydrex PEG 1.25-0.9: 1
Aluminum sesquichlorohydrex PEG 1.9-1.26: 1
Aluminum-zirconium trichlorohydrate 2.1-1.51:1 2.0-5.99: 1
Aluminum-zirconium tetrachlorohydrate 1.5-0.9: 1 2.0-5.99:1
Aluminum-zirconium pentachlorohydrate 2.1-1.51: 1 6.0-10.0: 1
Aluminum-zirconium octachlorohydrate 1.5-0.9: 1 6.0-10.0: 1
Aluminum-zirconium trichlorohydrex GLY 2.1-1.51: 1 2.0-5.99:1
Aluminum-zirconium tetrachlorohydrex GLY 1.5-0.9: 1 2.0-5.99:1
Aluminum-zirconium pentachlorohydrex GLY 2.1-1.51: 1 6.0-10.0: 1
Aluminum-zirconium octachlorohydrex GLY 1.5-0.9: 1 6.0-10.0:1
Aluminum chloride
Aluminum sulfate buffered
10.3 Mechanism of sweating
Antiperspirants are intended for use in the axilla region of the human
anatomy. This area contains aprocrine, eccrine and sebaceous glands. These
glands generate fluids and chemical substances which lead to the develop-
ment of body odor. The eccrine glands average about 200 per square cm and
produce the majority of sweat. The eccrine secreted fluid is composed of a
hypotonic solution of sodium chloride, urea, lactates and other metabolic
wastes. The sebaceous gland is a sub-surface gland evidenced by a hair
follicle. It excretes lipids and fatty acid substances which are responsible for
the generation of coryneform bacteria. The apocrine gland, also a sub-
surface gland with a protruding hair follicle secretes lipids, cholesterol and
steroids. The biological degradation of certain steroids by coryneform
bacteria is mainly responsible for the development of odiferous compounds.
The total mechanism is still not fully understood.
The production of sweat by the eccrine glands is initiated by both
emotional, thermal and sensory stimuli. The actual mechanism is somewhat
complicated in the sense that water is not just pumped through the sweat duct
to the surface. The transfer of sweat fluid results from the enzymatic
degradation ofN a + /K +-ATPase within the basal membrane. The movement
of Na+ ions across the luminal membrane in the secretory coil causes an
osmotic pressure gradient. The relief of this gradient condition is accom-
plished by the movement of water across the cells of the sweat gland secretory
coil into the lumen. This movement of water continues under either stimuli,
increasing luminal hydrostatic pressure. The excess fluid carries over to the
absorptive duct in the secondary coil and proceeds to the pore opening on
the skin.
There are a number of theories about how antiperspirants affect the sweat
gland to diminish the flow of fluid. One of the earliest investigations by Shelly
and Horvath [6] suggested that protein plugs were created when aluminum
chloride was used to treat the axilla. This was challenged as being more of
an injurious effect causing a cell transformation to restrict flow. Papa and
Kligman [7] theorized that aluminum chloride damaged the sweat duct
causing cell erosion, thus allowing for sweat to leak from the inner duct into
interstitial spaces rather than flow to the skin surface. Others postulated that
the pores swell shut when contacted by antiperspirant materials.
The most respected theory which has been substantiated by much scientific
evidence is the hydroxide plug development by aluminum and other metallic
salts. This theory best coincides with the hydrolysis chemistry of aluminum
chloride and its basic salt complexes. These complexes are polymeric in
nature and possess a high degree of cationic charge relative to the average
molecular weight of the polymer distribution. Aluminum chloride has the
highest charge and lowest molecular weight compared to the lower charges
of higher molecular weight basic aluminum halides. Table 10.2 illustrates
the charge-to-weight relationship in polymer development. One should
Table 10.2 Charge/mass ratios for Al polymers with
formula: [Al n(OHhn_2(H zOhn+4]"+2, where charge/
mass=n+2/3n
n Al Formula n+2/3n
Decreasing
charge/mass
ratios
Straight chains
I AI Al(H 20)3+ 3/3
2AI Al 2(OHhCH zO)g4+ 4/6
3 Al Al 3(OHMH 20) 105+ 5/9
4 AI Al4(OHMH 20) 126+ 6/12
5 Al AI 5(OH)g(H 20) 1/+ 7/15
6AI AI 6 (OH)w(H 20hr 8/18
Cyclic
6AI 6/18
conclude that the smallest polymer size species with high charge will enter the
sweat duct by some migratory movement perhaps assisted by charge attrac-
tion. During this journey in a very diluted state, neutralization followed by
hydrolysis occurs causing the hydroxide plug to form in the intracorneal and
intraepidermal ducts thereby restricting flow. These plugs in fact have been
confirmed using electron microscopy and aluminum fluorescence techniques
to detect the presence of the gel.
Studies by Quatrale [8] have been conducted on the antiperspirant action
of aluminum chloride, aluminum chlorohydrate (ACR) and aluminum
zirconium glycinate (AZG) during application. By performing cellophane
stripping of the applied axilla region it was demonstrated that hydroxide
plugs from aluminum chloride were found to be the deepest and most difficult
to remove. The restoration of the affected sweat glands back to normalcy was
slow. ACR hydroxide plugs were next easiest to restore followed by AZG.
One would have expected AZG hydroxide plugged glands to be deeper and
restore slower than ACR because AZG typically demonstrates 40% relative
higher sweat reduction than ACR. It should also be recognized, however that
under dilute conditions as would be the case in underarm applications,
polymer growth for most AZG compounds exceeds that for ACR. This
faster, more extensive superficial hydrolysis at an earlier stage of migration
into the duct makes AZG an effective antiperspirant.
10.4 Antiperspirant active properties
10.4.1 Basic aluminum chloride

The basic aluminum chlorides (BAC) defined in the FDA-OTC monograph
include aluminum dichlorohydrate (ADC), aluminum sesquichlorohydrate
(ASC) and aluminum chlorohydrate (ACH). Aluminum chlorohydrate is

manufactured from aluminum metal, water, hydrochloric acid and/or
aluminum chloride according to the following chemical equations of
synthesis:
10AI + 2AICl3 + 30H2 0 ~ 6AI2 (OH)sCI + 15H2
2AI + HCI + 5H20 ~ AI 2 (OH)sCI + 3H2
2AI(OH)3 + HCI ~ AI 2 (OH)sCI + H 2 0
4AICl3 + 10H20 ~ 2AI2(OH)sCI + 5Cl2 + 5H2
Quite often ACH will also be referred to as 5/6 basic aluminum chloride
which pertains to the fully basic most polymerized form of the salt.
Synonymous names for ACH that industry has become familiarized with
are aluminum chlorhydrate, aluminum chlorohydroxide and aluminum
hydroxy chloride.
ASC and ADC are more acidic, less polymerized forms of basic aluminum
chloride. They may be prepared by using a stoichiometric excess of acid
according to the following equation:
6AI2(OH)sCI + 2HCI ~ 6AI2(OH)4.666CI1.333 + 2H20
From a commercial perspective, ACH and other basic aluminum salts
prior to 1980 were not polymerically or clinically differentiated. It was
discovered that polymer alterations could boost sweat reduction perfor-
mance. The performance benefits were first disclosed by Gosling in a 1977
Canadian patent application [9].
Currently there are numerous polymeric versions of ACH and AZG with
enhanced or activated properties. Most types of the enhanced salts are
offered in dry powder form, but there are aqueous and propylene glycol
complexes that are stable as well.
It is advisable for the formulator to have a polymer fingerprint for each
particular batch of an active to ensure that the physical properties are
consistent with those used during the developmental stages of formulation.
A chromatographic analysis of an enhanced active is the only means of veri-
fying potential performance. Figure 10.2(a)-(f) illustrates various polymer
distributions of the aluminum complexes. The formulator should also be
familiar with other physical properties of the active found during the research
and development stage so that scale-up can be better understood. Process
variables can impart changes to the active itself.
The hydrolysis of trivalent aluminum is extremely complicated. The
formulator who incorporates these polymer blends should be aware that
solvated forms of BAC will in fact reach a different polymeric equilibrium
under certain conditions of use. Such conditions would include the dilution
of active with polar solvents, freezing, process temperature, time and the use
of pH altering additives. Most marketed forms of concentrated basic
300.00
300.00
200.00 200.00
100.00 100.00
O.OO+-------J O.OO+----J..
0.00 2.00 0.00 2.00

Minutes Minutes
(a) Aluminum Chloride (b) 1/2 Basic Aluminum Dlchlorhydrate
300.00-:: t 3
300.00 3
200.00
200.00-
100.00- 100.00
0.00 L.1J.5 0.00 -t----...J

I
0.00 2.00 0.00 2.00
Minutes Minutes
(c) 3/4 Basic AI Sesquichlorhydrate (d) 5/6 Basic Aluminum Chlorhydrate
300.00 200.00
200.00
100.00
100.00
5
o.oo-:t----~
0.00 1==;:=;==¢:':'~~::":::;::!
0.00 2.00 0.00 2.00
Minutes Minutes
(e) 5/6 Basic AI Chlorhydrate (I) 5/6 Basic AI Chlorhydrale peak 4 enhanced
Figure 10.2 Typical polymer distributions of aluminum antiperspirant actives.
aluminum chlorides will show a shift both in the molecular size distribution
and structural coordinates during the formulation process. This can lead to
reduced efficacy.
Conventional aqueous ACH is the most popular form of BAC, which is
normally supplied as a 50% hydrated salt solution. It is fully miscible with
anhydrous ethanol, propylene glycol, glycerine and most low molecular
weight polyols. The typical polymeric distribution for ACH 50% aqueous
solution shows 35% peak 2 polycations of about 8000 g m -I, 60% peak 3
intermediate polycations of about 5000 g m -I, 3% peak 4 AIl3 polymers of
about 3000 gm- I and 2% peak 5 oligomers and monomers of less than
2000gm- l .
The nominal empirical formula for ACH is AI2(OH)5C1.2~H20 and the
anhydrous active content of a 50% solution is 40.5%. BACs are permitted in
all types offormulations not to exceed a maximum anhydrous dosage of25%.
A formula containing ACH 50% solution should not comprise greater

than 61.6% of the total composition. Aqueous ACH is primarily used in
roll-on emulsions, pumps, creams and gels.
ACH is also marketed as a dry powder that is available in various particle
size distributions. ACH powder corresponds to the same nominal empirical
formula as the aqueous solution except that the anhydrous active content is
81 %. The balance is both free and hydrated water.
Variation in particle properties can impart different characteristics to a
formula. Discretion is often necessary to match the right powder form with
the application.
In an unmicronized state, ACH is basically spherical in nature. This form is
sometimes referred to as crystal, powder or bead. ACH can be used in this
form with some economic advantage because the micronizing process stage
is not exercised. The formulator should make certain that the random
distribution is 100% less than 100 /lm, since this is the critical size at which
the consumer can begin to detect grittiness during application and use. One
advantage of using unmicronized powder is that the particle density can be
readily controlled during manufacturing. This affords the formulator better
control of the suspension characteristics in lower viscosity systems. Apparent
bulk densities can vary between 0.2-0.9 g cm -3 with typical values of about
0.5 g cm -3. The critical particle density in cyclomethicone is about
0.24 gcm- 3 . Unmicronized ACH with higher density and narrower dis-
tribution has some utility in aerosol sprays because it tends to deliver a better
controlled spray pattern. Such distributions contain a smaller fraction of
particles below 10 /lm.
Micronized ACH is available in various particle size distributions
depending on the application. The industry standard grade more often than
not will be found suitable for use in most suspension systems. The standard
particle size specification for controlling distribution is 97% minimum less
than 325 mesh. The mean particle size is about 10 /lm. Extra fine ACH is
sometimes required for ultimate suspension capability. This grade generally
contains 80% minimum less than 10 /lm, and a mean particle size of 5/lm.
The pH of a 15% ACH solution is 4.3 compared with 3.9 and 3.5 for a
nominal metal! chloride ratio ASC and ADC, respectively. Since pH is a
logarithmic function of acidity I basicity, it is likely that ADC and the lower
range of ASC will show more irritation at the same dosage level as ACH. This
is the predominant reason why highly basic ASC and ACH nearly always
have an exclusive presence in the marketplace. A basicity index range for
antiperspirant actives relative to their metal! chloride specifications is shown
in Figure 10.3.
ACH can be polymerically optimized with higher peaks 3 and 4 to impart a
greater efficacy potential over the conventional version. These salts may be
referred to as enhanced or activated because they can reduce sweat by
30-50% relative to the conventional type. As those experienced in the field
ALUMINIUM SALTS AUZR SALTS
0
•
~ 2.2
""iii
CD
~
I
0
1.8
1.4~-.------'------r--~-'------'------r----~--~
ACH ASC ADC TETRA TRI PENTA OCTA
Antiperspirant salts
Figure 10.3 Basicity index (OR/metal ratio). OTe mongraph A/P salts.
of antiperspirants have sometimes recognized, other formula ingredients do

not always behave in the same way in the presence of enhanced salts as they
do with conventional forms. These interactions can impart rheological
changes to the formula as well as diminish the potential difference of the
anticipated clinical result. It is the writers contention that some non-ionic
surfactants, in particular those with strong emulsifying characteristics, will
selectivity seek out the most available coordinated water in anhydrous
formulations. This water can be found in the lower molecular weight bridged
polycations of the enhanced polymer group. Once this bound water is drawn
into phase equilibrium with the emulsifier, migratory movement of the
enhanced species to the sweat duct is impaired.
Solubility restrictions are also encountered by the encapsulating effects of
fatty alcohols, waxes and emulsifiers. A partial or delayed release of active
over time leads to lower efficacy. Ingredient interaction with enhanced salts
has plagued formulators for nearly two decades. It is advisable to conduct an
in-house clinical evaluation first whenever enhanced salts are being
considered for a performance geared project.
Basic aluminum chloride powders demonstrate varying degrees of
solubility in anhydrous ethanol and propylene glycol. The degree of
solubility depends on the amount of hydrated water available in the complex
as well as the temperature of the dissolution step. As a general rule ACH
containing 47% aluminum oxide will dissolve in 180 proof ethanol. ASC and
ADC will dissolve in 190 proof ethanol and 200 proof, respectively. If the salt
is thermally forced into ethanol there is a good possibility that an anhydrous

formula incorporating this salt solution will eventually precipitate out oxides
of aluminum rendering the formula unstable. If propylene glycol or other
hydrophilic ingredients are added, better stability can be achieved.
If an anhydrous alcohol-containing composition is desired, a safe
approach would be to use a basic aluminum chloride propylene glycol
complexed active. These salts contain 50-75% less coordinated water, yet
they will solubilize more readily in anhydrous alcohol. They also demon-
strate better stability in more hydrophobic systems. Propylene glycol
complexed actives are most suitable in mechanical sprays and roll-on
formulas.
For every conventional form of basic aluminum chloride there are
enhanced stoichiometric equivalents containing a normalized lower
molecular weight distribution. The properties of enhanced basic aluminum
chlorides are discussed in numerous patents [28-35].
The most recognized polymeric versions of BAC with enhanced perfor-
mance are the aluminum chi oro hydrates with higher levels of peak 3 and 4.
These salts contain an intermediate polymer distribution with reduced
amounts of peaks 1 and/ or 2 polycations. Higher efficacy has been
associated with smaller polymer size and increasing cationic charge. It is
clearly logical to anticipate that greater amounts of peak 4 species present in
BAC will demonstrate higher sweat reduction performance than peak 2
polymer-enriched conventional actives. It is also logical to assume that
peak 3 enriched BAC will also demonstrate better performance than peak 2
enriched conventional actives although less than peak 4 enriched BAC. Al27
NMR studies reveal that 5/6 basic aluminum chloride containing excess
peak 4 can undergo structural change to diminish the AIl3 polymer-activated
species without changing the polymer content of peak 4. For this reason gel
permeation chromatography techniques are not always adequate for the
evaluation of enhanced active polymer properties. The technique however is
useful as a quality control method to determine if the specified polymers are
present.
Conditions ofvery high basicity, low concentration, high temperature and
extended time can have a degradative effect on the preferred AIl3 polymer
with the subsequent generation oflower charged peak I polymers. In today's
competitive environment, the demand exists for various physical polymeric
forms of antiperspirant compositions.
Enhanced BAC can be manufactured in particle forms similar to those
discussed for conventional BAC. The predominant use of peak 4 enhanced
BAC is in anhydrous formulations. These salts lack peak 4 stability in
aqueous media. Formulas containing glycol solubilized peak 4 enhanced
actives with less than 5% added water will result in substantial peak 4
preservation. Peak 3 enriched actives demonstrate aqueous and hydro-
alcoholic polymer stability. Every cosmetic chemist dedicated to this field
should have a basic understanding of the polymer network of the active raw
material ingredients.
10.4.2 Aluminum zirconium complexes

The aluminum zirconium complexes (AZC) defined in the FDA-OTe mono-
graph include aluminum zirconium tetrachlorohydrate (drex-gly), aluminum
zirconium trichlorohydrate (drex-gly), aluminum zirconium octachloro-
hydrate (drex-gly) and aluminum zirconium pentachlorohydrate (drex-gly).
All AZC are comprised of a basic aluminum chloride and a zirconium
chloride polymer which are combined in aqueous media with or without
glycine to form AI-Zr oxo bridged complex polymer structures.
The following empirical equations represent some starting materials which
when combined in aqueous media form various basic aluminum zirconium
active complexes, ZC is zirconium oxychloride and ZHC is zirconium
hydroxychloride.
2AI 2(OH)sCI + ZrOC1 2 ~ AI4(OH) lO CI 2 . ZrCl2
ZC AljZr tetrachlorohydrate
2AI2(OH)sCI + ZrOC12 NH2CH 2 COOH ~ [AI4(OH) lO CI2 . ZrOCI2 ] NH 2 CH2 COOH

AljZr tetrachlorohydrex-Gly
2AI 2(OH)sCI + Zr(OH)Cl ~ AI4(OH) lO CI 2 . Zr(OH)Cl

ZHC AljZr trichlorohydrate
2AI2 (OHls + Zr(OH)Cl + NH 2 CH 2 COOH ~ [AI 4(OH) lO CI2 . Zr(OH)CI] NH2CH 2COOH
AljZr trichlorohydrex-Gly
4AI2(OH)4.SC1U + Zr(OH)CI ~ AI8(OH)18C16 . Zr(OH)Cl

AljZr octachlorohydrate
4[AI2(OHk sCl u ]' NH 2CH 2 COOH + Zr(OH)CI ~ [A18(OH)18C16 . Zr(OH)CI]· NH2CH 2 COOH
AljZr octachlorohydrex-Gly
4AI2(OH)sCI + Zr(OH)CI ~ AI8(OH)2oCI6 . Zr(OH)Cl

AljZr pentachlorohydrate
4[AI2(OH)sCI]· NH2CH2COOH + Zr(OH)CI ~ [AI8(OH)20CI4 . Zr(OH)Cl]· NH2 CH 2COOH

AljZr pentachlorohydrex-Gly
The incorporation of glycine in any portion of the aqueous synthesis will

form the aluminum zirconium chlorohydrex-gly salt. Aluminum zirconium
polynuclear complexes are extremely complicated in their structure and the
methods of their manufacture playa key role in their physical molecular
makeup.
The most popular aluminum zirconium complexes are the aluminum

zirconium tetra- and tri-chlorohydrex-gly. The industry standard for the
aluminum/zirconium atomic ratio is about 3.5: 1. The metal! chloride atomic
ratios however are significantly different, the tetrachlorodrex-gly being 1.4: 1
and trichlorohydrex-gly being 1.7: 1. The metal! chloride atomic ratio is a
critical stoichiometric characteristic of the formulation because this ratio
dictates the structural properties of the aluminum zirconium oxobridged
coordinates. Overall the higher metal! chloride ratio acti\'es are more
formulator friendly for several reasons. The pH is higher, in this case, 4.0
(l5%w/w aq. at 25°C) for the trichlorohydrex-gly and 3.8 for the tetra-
chlorohydrex -gly.
Chromatographic analysis reveals that the free acid content of
trichlorohydrex-gly is roughly half that of tetrachlorohydrex-gly. Acidity is
an inherent disadvantage for antiperspirant actives in general because it
limits the number of compatible solidification agents, gel stabilizers and
thickeners that can be incorporated into antiperspirant compositions. In
essence the pH window for these products is 3.5-5.0 compared with a
neutral-mildly alkaline environment for deodorant preparations.
Another possible advantage of tri- over tetra-chlorohydrex-gly in
anhydrous formulations is that the amount of coordinated water that is
present under comparable conditions of active manufacture is less for tri-
than for tetra-chlorohydrex-gly. The differences arise from the inverse
proportional relationship between lower coordinated water and increasing
basicity. Greater amounts of glycine introduced into the active followed by
drying also lead to lower coordinated water as a result of direct substitution
by glycine in the complex. It cannot be overemphasized that the active
component in an anhydrous recipe will contribute the greatest amount of
inherent water to the formula. This can make or break the objective stability
goals for anhydrous semi-solid and solid products.
Another consideration when choosing the active type is the effect of
stability on the fragrance in the formula. The amount offree acid whether in
the form of hex a-a quo aluminum or hydrochloric acid will act unfavorably
toward certain unsaturated fragrance compounds. Generally fragrance-
based ketones, esters and nitriles exhibit good stability. Aldehydes and
alcohols with moderate unsaturated components are not as stable in acidic
media and at elevated process temperatures.
Since 1985 aluminum zirconium chlorohydrex-gly powders have been
available in polymerically optimized forms, giving the formulator active
performance options. Analogous to the basic aluminum chlorides, for any
given stoichiometric arrangement of aluminum zirconium glycinate
complex, there are numerous polymeric versions of the salt. Figure 10.4
(a) - (h) illustrates typical polymer variations in Al! Zr complexes.
The conventional aluminum zirconium glycinate typically contains 10%
peak 2 polycations, 65% peak 3 intermediate polycations, 5% peak 4 AI13
3
200.00 3
200.00
4 4
100.00 100.00
0.00 i:::;:::::;:=:':::;::::;~::::::;j 0.00 -1=:::;::::::::;::::::;~~~::"::::;::i

0.00 2.00 0.00 2.00
Minutes Minutes
(a) AIZrTelrachlorhydrale (b) AIZrTelrachlorhydrex Gly Pk3 Enhanced
300.00 200.00
3
200.00
100.00
100.00
0.00 i==;:::::;::~:':';'::'::;:::":::;:::J 0.00 ~:::;:::::;:~~:'::;::::"":::;;::1

0.00 2.00 0.00 2.00
Minutes Minutes
(c) AIZrTetrachlorhydrex Gly (d) AIZrTelrachlorhydrex Gly Pk4 Enhanced
3 200.00
200.00
5 100.00
100.00
0.00 -+-___...J 0.00 +---.......

0.00 2.00 0.00 2.00
Minutes Minutes
(e) AIZrPentachlorhydrate (I) AIZrTelrachlorhydrex Gly Pk4 Enhanced
200.00 4
3
150.00
100.00 100.00
50.00
0.00 -+-___-J.
0.00 -{:=;:=;;:::~¢'~::"~;:1
0.00 2.00 0.00 2.00
Minutes Minutes
(9) AIZrTrichlorhydrex Gly (h) AIZrTrichlorhydrex Gly Pk4 Enhanced
Figure 10.4 Typical polymer distributions of aluminum I zirconium AlP actives.
polymer and about 20% monomer and oligomers. Peak 4 enhanced

aluminum zirconium glycinates typically contain 10% peak 1 large zirconium
polymers, 40% peak 3 species, 40% peak 4 species and 10% peak 5 species.
Peak 3 enhanced aluminum zirconium glycinates typically exhibit 10% peak
1,65% peak 3,5% peak 4 and 20% peak 5.
Abiding by the concept that lower molecular weight polymeric dis-
tributions are increasingly effective given non-interfering effects of other
formula ingredients, one can assume that peak 4 and peak 3 enhanced salts
will significantly outperform conventional salts of equivalent stoichiometry.

The average molecular weight contribution from all metal-containing species
is more significant than a single enhanced peak value. A meaningful example
of misleading single peak evaluation could arise if peak 4 is higher relative to
peak 3 yet large amounts of zirconium polymers exist in peak 1.
Ample data exist in the field to verify that conventional aluminum
zirconium glycinate complexes will outperform conventional aluminum
chlorohydrate by a relative 40% reduction in sweat. It is also generally
recognized that enhanced polymer forms will yield significantly improved
performance over their conventional stoichiometric equivalent under proper
formulation conditions.
The particle size and shape for aluminum zirconium complexes are similar
to those discussed for basic aluminum chlorides. The apparent density of
these salts however is shifted slightly higher due to the heavier atomic weight
of zirconium. In spherical form the range is about 0.3-1.05 gcm- 3 . The
higher density range in spherical form poses some interest because of the
reduced optical light scattering effects exhibited by this form. Improved
lower residue is achievable in anhydrous suspensoid compositions where the
surface area and particle number are reduced.
The aluminum zirconium glycinates have limited solubility in anhydrous
ethanol due to the reduced coordinated water content imparted by glycine.
The incorporation of water, propylene glycol and glycerine will enhance the
rate of solubilization. Propylene glycol solutions of these salts are com-
mercially available for use in clear sticks, gels and creams. The maximum
allowable and anhydrous dose of AZCs is 20% in non-aerosol compositions.
10.5 Clinical assessment
Products labeled as antiperspirant or deodorant-antiperspirant must meet

the FDA-OTC monograph definition for effective sweat reduction. There is
no requirement to meet a controlled odor specification when claims are not
made, but there is a minimum sweat reduction requirement for the privilege
of using the word antiperspirant and other sweat reduction language which
appears on the label.
The term deodorant is an inherent property of antiperspirant products and
it may appear on the label as well. The minimum efficacy requirement for
antiperspirants is 20% sweat reduction in 50% of the users as demonstrated
under specific test guidelines. Sweat rate evaluations dating back to the
1920s were essentially visualization techniques using starch and indicators
to identify the quantity of sweat droplet development. Some sensory
techniques were also developed by researchers such as thermographic and
gravimetric analysis, however this work has remained as a laboratory
curiosity and has not been adopted as a standard clinical procedure.
The modern clinical efficacy test accepted by both government and
industry is the gravimetric measurement technique that was developed after
1950 and has since been perfected. The most recent method which has been
adopted with minimal modifications is described by Majors and Wild [10].
Thorough analytical efficacy assessment is discussed by Murphy and
Levine [11].
The regulatory guidelines set forth by the OTC drug review panel and
adopted into the 1982 tentative final monograph are the current procedural
test requirements used to qualify antiperspirant drug products. These rules
are:
1. Panelist screening to obtain representative subjects.
2. 17 day antiperspirant and deodorant abstinence by test subjects
prior to sweat study.
3. (a) Hot room conditions of 100 ± 2°F, relative humidity of 35-40% or
3. (b) Ambient environment allowing daily routines for subjects during
collection period.
4. Use of control test formula for each subject, equally but randomly
dividing subjects so that they receive equal but opposite axilla
treatment following reversed axilla treatment of the other formula.
5. The application must represent a typical normal dose.
6. A 40 minute warm-up period is required.
7. Two 20 minute collection periods are made using pre-weighed
cotton pads with gravimetric collection during one of the two
periods.
If no pretreatment evaluation is made it is necessary to make a right to left
sweat ratio adjustment by dividing the raw milligram moisture measurement
of the right axilla. The sweat reduction calculation is made using the
Wilcoxon rank sum test method. An error is not allowed in more than 5% of
the cases where a 20% minimum number is not achieved.
Clinical efficacy studies are costly to run and generally are instituted when
new or modified formulas are encountered. It is to a researcher's benefit to
have a budget sufficient to use these studies in developmental screening of
trial and error bench preparations. It is helpful to consult experts in the
industry who administer such tests routinely so that the objectives can be met.
The application of antiperspirant composition to the skin is generally
recognized as safe with few negative side effects. As is the case with any
dermatological product, safety pre-screening new or modified formulas is
essential taking into account normal mode of use and possible misuse.
Potential side effects to consider might be dermal irritancy and contact
sensitivity.
Dermal irritation of aluminum and aluminum zirconium complexes can
vary considerably depending on the basicity of the complex. The maximum
allowable dose defined in the OTC drug monograph is a built-in safety factor
to help prevent adverse reactions. Active complexes with metal: chloride

atomic ratios of greater than 1.3: 1 have a long reputation of being derma-
logically compatible. Unlike the aluminum chloride and aluminum sulfate
precursors, they have less affinity for and reaction with the epidermal keratin
of the skin. Formulations containing Category I actives and cosmetic
ingredients with non-primary irritation scores are generally subjected to a
dermal evaluation on the axillary region of human subjects. A more
conservative approach might involve their backs using an occlusive or semi-
occlusive patch test. In every instance a control sample is used.
Antiperspirants and deodorants are regarded as being non-sensitizing.
Other components in the formula such as perfumes and oils are more likely
to be sensitizing agents and to be photo-sensitizing. Comedogenicity and
irritation of skin-care ingredients is discussed by Fulton [12]. Are-evaluation
is most advisable if ingredient changes are made. It should be noted that there
will always be a fair percentage of consumers who will abstain from anti-
perspirant use entirely because of irritation effects. A safety assessment of
aluminum compounds is described by Lansdown [13].
10.6 Formulary considerations
10.6.1 Performance
Antiperspirant products are strictly designed to control wetness and odor in
the axilla region of the body. Not all finished products will deliver the same
degree of wetness protection, so there should be some target goal before
commencing a project. Odor control is less of a concern because anti-
perspirants are good deodorants. As a conservative measure, sometimes an
anti-microbial agent will be employed in small quantities for insurance
purposes.
In nearly every instance, formulators design the antiperspirant product to
deliver a 25% or better sweat reduction if it is to remain within the
competitive performance arena of current products. Efficacy is diminished
to some extent by hydrophobic non-volatile ingredients. Given proper
selection and quantity used, 25% reduction should be achievable. The active
concentration in the composition should be at least 12% calculated on an
anhydrous non-buffered basis. The customary range of anhydrous active in
non-aerosol compositions is 15-20% and 7-10% for aerosols. The delivery
dose to the axilla under normal application should be between 200-500 mg.
If the dose is too small, performance objectives might not be met. Product
stability also meets a greater challenge due to extended shelf-life.
As a general rule, a conventional active in an aqueous-based formulation
will yield better clinical performance over a silicone-based liquid suspension
which in turn will edge out wax/ silicone-based suspensoid solids. The reason
for this order is solely due to the rate of availability of the active in a
c
o
g ~n-~----------__~--~~--~--~---~~~.~~~E---~
"0
OJ
'-
iii
~
(/J
ACH ACH ACH ACH AZG AZG AZG

AQUEOUS ANIiYDROUS ANHYOROUS AEAOSQL AQUEOUS ,t.,NHYOROUS ANI-tVOFlOUS.
EMULSION liQUID SUSP SOLlD GUSPeN EMULSION LIQUID SUSP SOLID SUSPENSION
~ Conventional ~ PK 3 Enhanced _ PK 4 Enhanced
Figure 10.5 Clinical efficacy expectations of AlP actives in specified drug form.
solubilized state after application. Aerosols are the weakest contender

because of the failure of the spray to deliver the full dose to the axilla.
Enhanced ACH is often employed to boost performance in aerosols to help
offset the delivery problem. Figure 10.5 [26] provides a guide to clinical
expectations for the customary active dosage in specified drug form.
10.6.2 Cost
Antiperspirants can be formulated from hundreds of ingredient choices. It
will be the responsibility of researchers and marketers to weigh the cost
benefit ratio of expensive ingredients in terms of their esthetic or product
integrity contribution.
The esthetic demands of the United States consumer run high and this has
driven the total raw material cost higher. Anhydrous product forms are more
expensive, where water has been replaced by silicones to improve feel. In
other parts of the world, esthetics is also important, but there is greater
tolerance of aqueous compositions. A cost! esthetic balance is also achieved
where oil-in-water or water-in-oil emulsions are used.
The benefits of aqueous emulsions are that they are easy to prepare, they
comprise a less expensive ingredient mix and they generally meet the efficacy
criteria. They will always survive because they provide an economical
alternative to the consumer. If the formulator wants total performance
esthetic benefits, then the anhydrous enhanced active compositions are
preferable.
A large cost of antiperspirant! deodorants can be the package container
itself. Container and ingredient compatibility must be studied carefully to
guarantee chemical resistance and dispensing capability. Be aware that an

economic saving on an organic raw material constituent can sometimes be
defeated by more costly packaging and design requirements.
Antiperspirant active manufacturers constantly research the efficacy
potential of enhanced aluminum zirconium complexes. Reducing the cost
gap between enhanced and conventional active forms will afford the
formulations some economic flexibility without sacrificing performance.
Recent clinical studies have demonstrated that less costly stoichiometric
configurations of aluminum zirconium glycinate complexes are achievable
without diminishing efficacy [14].
10.6.3 Esthetics
Antiperspirants are a difficult group of products with which to satisfy the
consumer esthetically for several reasons. When active ingredients are placed
in a limited hydrodynamic environment such as in the axillary region, the
active will exhibit some degree of tack. Emollients with lasting properties
can easily offset tack, but there are limitations to the amounts that can be
employed in the formula. Excessive amounts will inhibit the solvation rate
of powdered actives, thereby interfering with the pathway of the active into
the viable epidermis region of the sweat duct.
Volatile silicones have tremendously improved the esthetic quality [15]
without negative performance drawbacks. They carry the ingredients to the
skin with a dry feel and good spreadability. Their high vapor pressure allows
them to depart quickly leaving behind the active and smaller amounts ofless
volatile oils. If tack is experienced in an underarm application for more than
several minutes it should be minimized by formula adjustments, as it will
probably have negative consequences for the consumers.
Aqueous-based products will have more pronounced tack profiles than
anhydrous suspension products. With the proper emollient balance, they will
generally not draw strong criticism. Large amounts of humectants such as
glycols and ethoxylated derivatives can also impart a long tackier drying
process.
Good spreadability is an important attribute in antiperspirant appli-
cations because thick films adhering to the skin and hair follicles will give
the perception of greasiness. Smooth glide is another application benefit
because women in particular will associate glide with elegance. Hard, high,
particulate-containing suspensoid sticks sometimes possess more drag due
to the increased levels of stearyl alcohol and suspending agents. Formulas
with poor glide may also have an irritating effect on the skin due to the
frictional effects of solid particulates.
The underarm is a sensitive area and fast evaporation from water and
alcohol can cause an undesired cold sensation during the drying process. In
such cases the cooling rate can be lowered with oil phase ingredients.
An esthetic appearance of the contents is always of interest to the
consumer. Be aware that high levels of alcohol can evaporate faster than
any other ingredient from the system. This could change the product appear-
ance and consistency. Content shrinkage in time is inevitable in solid
products containing large amounts of alcohol. Propylene glycol may in part
be a good substitute for alcohol in formulas where solvent power is not
required.
The color of a formula that can be viewed by the consumer is of
significance. Opaque compositions should be white or off white, while clear
formulas should be as colorless as possible. A yellow appearance,
particularly against a white package, is subconsciously viewed as poor
quality although the functionality of the product could still be the same.
Product clarity is the most recent marketing campaign used by anti-
perspirant deodorant manufacturers. Clear cosmetics express purity and
beauty. Clear gels have been fairly successful in promoting the no product
residue concept. The flaky or after whitening residue is a wide concern
addressed mostly by the female antiperspirant user. Low residue products
are quickly becoming an important segment of most product lines. Several
formulation approaches will lead to reduced residue. These include micro-
emulsion and suspension technology.
A functional esthetic enhancer in anhydrous formulas comes from the use
of encapsulated fragrances that are capable of providing time or demand
release of fragrance. Micro-encapsulation is specialized technology and the
procedure is often sent out to experts in the field who can provide the proper
encapsulate for the formulator. Some common coating materials include
sucrose, polysaccharides, polyurea and maltodextrins. Micro-encapsulation
is thoroughly discussed elsewhere [16, 27].
10.7 Formulations
10.7.1 Roll-on products

The majority of roll-on products in the US and UK markets are anti-
perspirant! deodorants. Both aqueous- and silicone-based preparations are
quite popular. The predominant forms in the US are silicone emulsions and
suspensions whereas aqueous emulsions take precedence throughout Europe
and other countries. Aqueous versions usually contain greater than 50%
water and incorporate a thickening agent such as magnesium aluminum
silicate, carbomer, hydroxypropyl cellulose or hydroxyethyl, cellulose. Other
components might include 2-20% emollients such as myristyl, palmityl or
stearyl esters and emulsifiers such as alkoxylated fatty ethers/esters and
glycerol stearate.
Formulas containing ample quantities of ethyl alcohol are regarded as
hydroalcoholic systems. Clear stable formulas can be achieved using

cellulose polymers. The polymer is often prepared in an aqueous concentrate
and deaerated before adding the active and emollients. A pre-solubilized
fragrance can be added followed by a final dilution with water. When
para ben preservatives are used, some heating will be required to bring them
into solution but the main mix need not be heated.
The general principles of emulsion technology [17] apply to water-in-oil
(w/o) and oil-in-water (o/w) emulsions. This involves separately heating
both phases with miscible surfactant emollients and adding the water phase
to the oil phase with stirring until emulsification at a lower temperature is
achieved. Homogenization is sometimes needed to reduce the internal phase
droplet size to increase emulsion stability. Water-in-oil microemulsion
formulas can be clear and require an experimentally fine-tuned hydrophilic/
lipophilic balance (HLB) to maximize formula stability. Clear emulsions can
also be produced by matching the refractive indices of the two phases at use
temperature. This is sophisticated formulation. Two or more non-ionic
surface active agents are recommended to accomplish this balance. The
viscosity can be regulated by altering the weight ratio of the phases. Oil-in-
water emulsions are more common in lotion formulas. There is a greater
esthetic advantage of w /0 type micro-emulsions because of the dry, lower
tack feel upon application. Fragrances are easy to incorporate in the last
stage of process because of the solvent power of the external phase. Very
stable w / 0 emulsions have been achieved with organosilicone emulsifiers
[18]. The enhanced stability arises from the highly absorptive phase bound-
aries resulting from the alkyl side chains and the polyglycol groups attached
to the silicone polymer.
The recommended emulsification procedure involves adding an ambient
temperature water phase to an 80°C oil phase at a 3: 1 weight ratio with
vigorous mixing. The cooled mixture is lightly homogenized for several
minutes.
Dry suspension roll-on compositions have few hydrophilic characteristics
because they contain no water. They can be thickened with bentonite clays or
high surface area silica to moderate viscosity levels of several thousand
centipoise. Between 20 and 25% of powdered antiperspirants are suspended
in a base of cyclomethicone or other light oils. Emollients might include
diesters, polydecene, dimethicone, alkoxylated ethers and soluble waxes.
Dry suspension roll-ons exhibit an excellent dry, non-greasy esthetic quality
when applied. High levels of sweat reduction can be achieved with enhanced
aluminum zirconium glycinate antiperspirant actives.
Typical formulation of an emulsion roll-on
Part Ingredient Wt%
A Water 48.0
B Lanolin alcohol 0.5

Peg 40 stearate 2.0
Cetyl alcohol 1.5
Lanolin 2.0
C Glycerine 2.0
Mineral oil 3.0
Phenyl trimethicone 3.0
D Fragrance q.s.
E Aluminum chlorohydrate (50% aq.) 36.50
Procedure: Disperse A using high shear mixing. Heat A to 85°C and add B. When
melted add C, reduce heat to 40°C and add D and E.
Typical formulation of a clear micro-emulsion roll-on

Part Ingredient Wt%
A Po1ydecene 364 21.0
Oleth2 12.0
Oleth20 7.0
Cetyl dimethicone copo1yo1 4.0
B Aluminum zirconium
tetrach10rohydrex-gly (35% aq.) 49.0
Dipropy1ene glycol 5.0
PPG 14 butyl ether 2.0
C Fragrance q.s.
Procedure: Heat A and B separately to 85°C. Slowly add A to B while stirring.
Continue stirring until cooled to 45°C. Add C.
Typical formulation of a dry suspension roll-on

Part Ingredient Wt%
A Octamethy1cyc1otetrasiloxane 40.0
Decamethylcyc1opentasi10xane 25.0
Quaternium 18 hectorite 2.5
B Dimethicone (50 cps) 5.2
SDA 40 alcohol 2.0
C Fumed silica 0.3
Aluminum zirconium
tetrach10rohydrex-g1y 25.0
D Fragrance q.s.
Procedure: Mix A with a high speed agitator. Add B and continue mixing. Add C and
D and continue mixing for 15 minutes. Transfer to a homogenizer and homogenize for
3 minutes.
10.7.2 Stick products
A large amount of research time has been dedicated to the solid and semi-
solid antiperspirant! deodorant product forms. The introduction of volatile
silicones as the base solvent and carrier over two decades ago has led to high
consumer loyalty particularly in the United States, Canada and the United
Kingdom.
The solid suspensoid antiperspirants are comprised of a blend of waxes,
silicone, emollients, couplers and antiperspirant powder. The benefits of
solid formulas are those of controlled delivery and good esthetics. They also
have a good reputation for exhibiting long lasting chemical stability. The
packaging components are manufactured from various plastic materials such
as polyethylene, polypropylene or polyethylene terephthalate. It is important
to match the chemical compatibility of the plastic used in barrel construction
to the oils chosen in the formulation. Some emollients can be aggressive
solvents when in contact with plastic particularly on longer term stability.
The distortion temperature of plastic should also be above the process fill
temperature. The general procedure used in preparing suspensoid solid
products is to dissolve the fatty alcohol waxes and couplers in the silicone at
elevated temperature. The melting point of the castor wax will generally
dictate the working process temperature needed to achieve a homogenous
molten state. Sometimes a higher molecular weight wax such as paraffin or
behenyl alcohol is used in small quantities to fine tune stick hardness. The
materials to be suspended such as the active powder, talc, silica or other fillers
are then added. The temperature is lowered to several degrees above the
solidification temperature, fragrance is added and the contents are poured.
A carefully controlled cooling stage is critical to the final physical appearance
of the stick. High viscosity pours will have less cavitation after solidification.
It is sometimes helpful before final cool down to subject the stick to a brief
period of infrared heating to smooth the top and reduce blemishes.
Stick quality is evaluated by a number of procedures 24--48 hours after
solidification. Chemical analysis at various vertical depths is done to assess
active homogeneity. Hardness is measured by taking penetration readings
using a penetrometer. Sticks designed for the male market are generally
harder with readings of 7-10 mm of penetration compared with sticks
designed for the female market which penetrate 10-13 mm. Other speci-
fications might apply to horizontal bond strength, color and posting failures.
With some minor chemical adjustments, suspensoid compositions can be
formulated with lower residue properties without departing from the solid
stick concept. Consumer residue complaints are not all warranted but some-
times are the fault of the user based on how the product was applied. The real
residue issue pertains to the amount of white material that occurs on the skin.
Hours after application white flakes may fall off onto darker garments
without much notice. The residue occurs either from the encapsulating effects
of fatty alcohol on the active and other inert ingredients or from the white
crystalline active after the volatile silicone has evaporated. Certain emulsi-
fiers that impart creaminess can also prevent the solubilization of active
leading to a white protective barrier of residue particulates.
Branched esters and diesters when incorporated into these waxy based
formulas can significantly reduce residue properties. Low surface area anti-
perspirant actives can also reduce residue because of a lower number of
encapsulated particles observed. These actives can exhibit reduced light
scattering characteristics by virtue of special manufacturing techniques.
Softer stick preparations containing C I6 and C I8 alcohols are lower in residue
than more crystalline C I8 by itself based on comparable dosage evaluation.
Semi-solid gels and creams have sparked great consumer interest because
of their low residue properties and esthetic value. The package design is quite
similar in appearance to solid formulas, but delivery through a well designed
applicator head becomes an additional package component necessity.
Controlling dosage is paramount so that the product can be applied without
mess.
Gels are w / 0 or o/w micro-emulsions and they have the advantage of being
very clear if both phases can be combined with matching refractive indices of
less than 5 x 10- 4 units. The w / 0 type has a dryer feel and can be prepared in
a similar fashion to that discussed previously in roll-on preparations. A
thickening agent such as a dimethicone copolyol is useful in bringing the
phase to a high viscosity level of at least 50000 cps. The formulas are quite
stable at high viscosities because the semi-solid characteristics help to
immobilize the dispersed phase in the external phase.
Aluminum zirconium complexes might be the active of choice in w /0
micro-emulsions in order to boost the efficacy while overcoming the encap-
sulating effects of the external oil phase.
Creams can be of the emulsion type containing about 50% water, the
balance consisting of emulsifiers, gel thickeners, emollients and active. They
are similar to lotions to prepare except that a higher level of thickening agent
is required. An esthetically rewarding feel can be achieved from anhydrous
creams that are made by suspending fine particulate active powder in an
organic base of volatile emollients, esters, emulsifiers and surface active
suspending agents. High surface area clays and silica are useful suspending
agents and stabilizers. In anhydrous formulas such as these, very small
amounts of polar additives such as glycerine and propylene carbonate can
assist in charge development of the surface active particulate.
Solid clear gel antiperspirants represent another approach to preparing no
residue products. The composition consists of a gel agent, propylene glycol
complexed active, solvent glycols, emollients and couplers. A useful gellant
is dibenzyl sorbitol which is dissolved in polar glycols at temperatures of
about 80 to l20°C. Some emollients can be added to this phase but care
should be taken to maintain a low enough viscosity to maintain the solubility
of the gellant. The other phase should contain the active and any remaining
ingredients at some lower elevated temperature between 50 and 80°e. A pH
adjusting agent is needed to maintain a formula pH of 4.5-5.0 to prevent the

dibenzyl sorbitol from degrading in an acidic environment. The final phase
blending should be done in a micro-batch or continuous blend sequence with
adequate mixing at a temperature of70-90°C. The solution should be poured
promptly in order to avoid gellation in the process line. Solidification time
can be 1-20 minutes depending on the viscosity and the amount of gellant.
The entire process is more challenging than most, therefore a reliable auto-
mated line is recommended in scaling up for production quantities.
Typical formulation of an antiperspirant stick

Part Ingredient Wt%
A Decamethylcyclopentasiloxane 50.0
Hydrogenated castor oil (70°C mp) 3.5
PPG 14 butyl ether 3.5
trichlorohydrex-gly (80% < IOllm) 24.0
Talc 5.5
C Fragrance q.s.
Procedure: Heat A to 75°C with mixing until clear. Lower temperature to 65°C and
add B and disperse. Lower temperature to 56°C, add C and fill at 54°C.
Typical formulation of a low residue antiperspirant stick

Part Ingredient Wt%
A Decamethylcyclopentasiloxane 41.0
Isocetyl octanoate 3.5
Cetyl alcohol 5.0
Hydrogenated castor oil (80°C mp) 3.0
PEG 8 distearate 1.0
Ceteareth 20 1.0
B Hydroxylated milk glycerides 1.5
C Aluminum zirconium
tetrachlorohydrex-gly (enhanced) 25.0
Talc (90% 325 mesh) 1.0
D Silica 1.0
E Polysaccharide/fragrance q.s.
Procedure: Heat A to 85°C with mixing until clear, lower temperature to 62°C, add B
and dissolve. Add C and disperse. Add D and disperse. Lower temperature to 58°C,
add E and fill at 56°C.
Typical formulation of a clear antiperspirant stick
Part Ingredient Wt%
A Aluminum zirconium
pentachlorohydrex-gly 30% pg soli
with zinc glycinate 44.0
Glycereth 7 benzoate 2.8
Glycereth 4.S1actate 0.9
PPG 2 isodeceth 4 1.0
Myristyllactate 3.3
Diisopropyl adipate 3.S
AlB (30170) Propylene glycol 16.2
AlB (30170) Dipropylene glycol 26.0
C Dibenzyl sorbitol 2.3
D Fragrance q.s.
Procedure: Using a micro-batch process, heat A to 68°C with mixing. Add A portion
of glycols. Separately heat B portion of glycols to 110°C with good mixing and slowly
add C by increments while increasing temperature to l2S0C until dissolved.
Immediately lower to 118°C and add to A. Immediately add D and pour at 78°C
within 3 minutes.
Typical formulation of a clear wlo gel stick

Part Ingredient Wt%
A Cyclomethicone and dimethicone
copolyol (DC 322SC) 8.0
Dimethicone S.O
Decamethylcyclopentasiloxane 7.0
Dioctyl succinate 10.0
tetrachlorohydrate (SO% sol.) SO.O
Alcohol, SDA 40B 9.0
Methyl propanediol 8.0
Glycerine 3.0
C Fragrance q.s.
Procedure: Combine A ingredients and mix. Combine B ingredients and mix. Measure
refractive index (RI) of each phase at 2S°C. Adjust RI of B up or down to match A to
within O.OOOS units by adjusting glycerine or water, respectively. Add B to A with
gentle mixing. Add C. Homogenize briefly to reach desired thickness.
10.7.3 Spray products
Aerosols are a major product category in the UK. They have dramatically
declined in popularity in the US due to an environmental campaign to phase
out volatile organic carbon (VOC) chemicals, the heart of the propellant
system. Due to the lack of suitable non-VOC substitute propellant, research
has remained low key in this area, awaiting the final call by the environmental
regulatory agency. The California Air Resource Board (CAR B) has been
instrumental in developing the rules for reducing VOC emissions, where anti-
perspirant and deodorant products have sustained more criticism than other
aerosol product categories (see section 13.8).
Most antiperspirant aerosol formulations are variants of suspensions of
active salts in different oil and solvent blends. Aluminum chlorohydrate
powders of micronized or controlled particle size grades are predominantly
used in spray systems. Both aluminum zirconium complexes and aluminum
chloride are prohibited from use based on health concerns stemming from
the less controlled delivery form.
Typical ingredients useful in aerosols are isopropyl myristate, isopropyl
palmitate, dibutyl phthlate, volatile silicone, dimethicone, silica, suspension
clays, propylene carbonate and ethyl alcohol. The propellant is liquified
isobutane, or blends ofisobutane and propane.
A thick concentrate is prepared by shearing a bentonite or hectorite clay
with the emollient in the presence of a polar additive such as ethyl alcohol or
propylene carbonate. The active is slowly added and the final blend is
screened to remove any agglomerates. The formula is added to a corrosion
resistant pressure rated aerosol, and propellant is charged at approximately
a 3: 1 weight ratio of propellant: concentrate, to satisfy California require-
ments of 60% maximum high volatility organic compounds (HVOC).
The success behind an antiperspirant aerosol with good delivery character-
istics is based on low viscosity and good valve design. The vapor-tap valve
and mechanical break up buttons are essential for reduced particle size
sprays. The emollient oils used in the formula also act to reduce the bounce
effect of the spray hitting the axilla surface in order to land a greater
percentage of active at the site. A dispensing rate of 0.08 g S-1 for 2 s of active
should be sufficient to exceed the minimum efficacy requirements of 20%
sweat reduction in half the users. The handling of hydrocarbon propellants
is hazardous and special precautions must be taken to avoid fire and
explosion.
Mechanical pump sprays are also available on the market but are less
popular. Pump sprays consist of low viscosity solutions or emulsions of
solubilized basic aluminum chloride, volatile silicones, ethyl alcohol, water
and various emollients and couplers. The mean diameter droplet size for
pump sprays should be between 50-100 jlm. This may require inserts ranging
in dimension of 0.010" to 0.014" x 0.010" shallow. The output per stroke will
be about 120 or 140 jll. The performance of mechanical pump sprays is
largely dependent on the design of the pump mechanics. Exhaustive trial
and error may be needed to optimize the functional components.
Stability testing for pump sprays should be done daily and involves two
sequential strokes per day for multiple units accurately to assess the rate of
failure.
The greatest formulation challenge will arise where VOC restrictions
might apply. It will be necessary to reduce ethyl alcohol to a low percentage
and still maintain low viscosity and a good evaporative drying rate. The
following are typical guide formulations for aerosols and pump sprays:
Typicalformulation of a low VOC wlo antiperspirant pump

Part Ingredient Wt%
A 50% Aluminum chlorohydrate 44.0
Water 27.0
B PPG 10 butanediol 16.0
Lauryl dimethicone copolyol 8.0
Laureth 2 octanoate 5.0
C Fragrance q.s.
Procedure: Combine A, combine B and add to A with propeller mixing. Add C.
Typical formulation of a suspension aerosol

Part Ingredient Wt%
A Aluminum chlorohydrate powder
(enhanced) 11.0
B PPG 3 myristyl ether 2.0
C Isopropyl myristate 11.0
D Alcohol SDA 40 0.8
E Organofunctional clay 0.8
F Isobutane/propane (80/20) 74.4
G Fragrance q.s.
Procedure: Disperse E in Band C with a high shearing homogenizer for 10-15 minutes.
Add D and G with continuous high speed mixing until a viscous gel is obtained. Slowly
add A at reduced shear speed by incremental additions to ensure homogeneity. When
addition is complete continue mixing for at least 15 minutes. Filter concentrate
through a 50 mesh sieve and homogenize at 6000 psi. Fill the concentrate into
corrosion resistant lined aerosol containers and add F at an 80: 20 ratio, F: (A-E).
Typical formulation of a hydroalcoholic antiperspirant pump

Part Ingredient Wt%
A Alcohol (190 proof) 45.0
B Aluminum sesquichlorohydrate powder 20.0
C Water 5.0
D Octamethylcyclotetrasiloxane 2.5
Laureth 2 octanoate 5.0
PPG 15 stearyl ether 12.5
PEG 20 isohexadecyl ether 4.0
Laureth 7 5.5
Laureth23 0.5
E Fragrance q.s.
Procedure: Heat A to 50°C, add B and dissolve. Add C followed by D and E.
10.8 Deodorants
Deodorant products are designed specifically for the control of malodor and
cater in the US more for the male market. In Latin America and Europe,
deodorants dominate market share. Deodorants date back to many centuries
of use when they were most likely to be natural fragrance oils and aromatic
compounds applied to all areas of the body.
Continental Europe and most parts ofthe world favor deodorant products
to control odor in lieu of antiperspirants, however there is a gradual decline of
that ratio every year. In the US, approximately one in every four people use
deodorants instead of antiperspirants. A basic advantage of deodorants is
that they tend to be less irritating than antiperspirants, promoting loyalty
among their users.
10.8.1 Odor control

There are three approaches to odor control:
1. Topical application of anti-microbial agents to suppress the bacterial
degradation of aprocrine sweat secretions.
2. Topical application of antiperspirants to master a dual function of
sweat reduction and odor prevention by the anti-microbial function of
aluminum.
3. Other miscellaneous means such as the systemic administration of anti-
cholinergic agents to diminish perspiration, enzyme inhibition to
prevent odor formation, olfactory competition (fragrance) and
complexation of odoriferous compounds.
This section primarily focuses on antimicrobials incorporated into form-
ulations.
The simplest approach to deodorizing the axilla is in the use of masking
agents applied neat or in formulation. Any fragrance will work as such,
however there is no long term control mechanism in place to maintain a stable
low odor plateau for extended periods.
The best masking agents are deodorant fragrances. These fragrances are
designed to complement the body odor but at the same time not to reinforce
it. According to Sturm [19] it is possible to select certain deofragrances that
not only mask but have some anti-microbial action on bacteria. This may
require considerable evaluation in formula development and perhaps may
not be practical.
Odor absorption is an old concept for malodor control and it has been
revisited within the last several years. Sodium bicarbonate is just starting to
be used in antiperspirant and deodorant products to absorb odors by the
chemical neutralization of odorous short chain fatty acids. The use of sodium
bicarbonate in suspension systems at a pH of 7-8.5 is feasible. Process
temperatures above 50°C should be avoided since sodium bicarbonate begins
to loose carbon dioxide above this temperature.
Sodium bicarbonate is not stable in aqueous antiperspirant deodorant
compositions. It is stable and more effective if it is encapsulated in anhydrous
preparations. Recent innovative technology [20] teaches hydrophilic
polymer encapsulation of bicarbonate compounds. The deodorization of
bicarbonates is discussed by Lamb [21].
Zinc glycinate [22], zinc oxide and metallic carbonates also demonstrate
deodorizing capability.
Antimicrobial agents [23] that are currently being used are very effective in
destroying gram positive and some gram negative micro-organisms. Two
that have withstood extensive safety testing are 3,4,4'-trichlorocarbonilide
(triclocarbon) and 2,4,4' -trichloro-2'-hydroxydiphenyl ether (triclosan).
Cl 0
Their structural formulas are given below.
Cl-b-~-~-~-o-Cl
H H
3,4,4' - Trichlorocarbonilide 2,4,4' - Trichloro-2'-hydroxydiphenyl ether
Triclosan is more readily used in underarm deodorant preparations at

about a 0.05-0.3% level. It is not necessary to exceed these levels because the
contact time in underarm topical applications is hours long. This gives better
protection than deodorant soaps which can be more readily washed away.
The effect oftriclosan on bacteria is discussed by Meinike et al. [24].
10.8.2 Clinical assessment

Deodorants are cosmetic and a deodorant claim by itself is a cosmetic claim.
There are instances where claims are made in relation to an antiperspirant or
an antimicrobial [25] which require that a clinical study be made to
substantiate the claim.
Some in vitro test procedures can be conducted to determine the effect of

compounds in deodorant products but they are not reliable enough to
indicate the true potential for malodor control. The best evaluation should
involve a panel study. There are many rules to follow by the panelists and
the odor judges. Clinical testing houses are best suited to conduct this type
of study. A direct evaluation is performed by several judges who will give a
rank odor score from 0-10. The lowest tabulated scores will indicate the best
deodorant efficacy. A less critical evaluation can be done in house by
volunteers who agree to wear the deodorant and provide a personal assess-
ment.
10.8.3 Formulations
The majority of underarm deodorant products are in the form of aerosols or
sticks. The preparations for deodorants are similar to antiperspirant aerosols
except that the anti-microbial is used in place of the antiperspirant.
Various plant extracts such as lichen and alpine herb offer anti-microbial
benefits. The following formulations can be used as a guide to prepare
deodorant products.
10.8.3.1 Stick products Deodorant stick products are gelled in a different

manner to antiperspirant sticks by using sodium stearate in lieu of C 16 -C 18
fatty alcohols. Deodorant sticks are relatively easy to prepare. The gelling
agent is normally pre-formed by the supplier of the raw material, however
the formulator can prepare it from aqueous sodium hydroxide which is added
to an alcoholic solution containing stearic acid. About 5-8% of sodium
stearate is sufficient to solidify the composition. Varying amounts of ethyl
alcohol and glycols can be used, which will provide a solvent base for
emollients and anti-microbial agents. Propylene glycol is generally preferred
as a substitute for ethyl alcohol in part or whole when low VOC objectives are
being sought. Propylene glycol is quite popular because it can act as a
plasticizer in the stick, yet it will be absorbed and is non-greasy after
application. Most deodorant sticks are translucent in appearance. The clarity
and feel can be improved with branched esters and alkoxylated ethers such as
PPG 3 myristyl ether. Other ingredients might include dimethicone, silicones,
fatty acid amides and plant extracts. Deodorants in the form of micro-emul-
sion clear gels may also be of interest to today's consumer. The technology is
similar to that discussed in the antiperspirant section.
10.8.3.2 Spray products Deodorant sprays can be in the form of an

aerosol or pump. These formulas can be made to contain deofragrances with
or without anti-microbial agents. Iftriclosan is used it must be dissolved in
the organic additives when preparing the concentrate. Since antiperspirant
actives are good deodorants, aluminum chlorohydrate powder can be
utilized at about 3-4% of the level of conventional ACH.ln conjunction with
an anti-microbial, it makes a very effective product. Enhanced aluminum
chlorohydrate can also be utilized in even less quantities to obtain the desired
performance.
Typical formulation of a deodorant stick
Part Ingredient Wt%

A Sodium stearate 7.0
Ethyl alcohol 15.0
Water 5.0
Triclosan 0.2
B Fragrance q.s.
Color q.s.
Procedure: Dissolve the solids in A by heating to 85°C, cool to 80°C, q.s. with B, and fill
into molds.
Typical formulation of a microemulsion deodorant gel

Part Ingredient Wt%
A DEA 0Ieth-3-phosphate 6.8
Oleth3 4.1
Oleth 5 2.7
Light mineral oil 13.6
2-Ethyl-1,3-hexanediol 3.4
B Diazolidinyl urea 1.0
C Fragrance q.s.
Procedure: Heat A to 8SOC. Heat B to 85°C with good mixing add B to A. Add C with
mixing before filling. Fill at 56°C.
Typical formulation of a deodorant aerosol

Part Ingredient Wt%
A Aluminum chlorohydrate powder 4.0
B Dimethicone (50 cps) 5.0
C C 12 -C IS Alcohol benzoate 15.0
D Alcohol, SDA40 1.0
E Organofunctional clay 0.8
F Triclosan 0.1
G Fragrance q.s.
H Isobutane/propane(80/20) 76.1
Procedure: Disperse E in B, C and F with a high shearing homogenizer for 15 minutes.
Add D and G with continuous high speed mixing until a viscous gel is obtained. Slowly
add A in small increments to ensure homogeneity. When addition is complete,
continue mixing for at least 15 minutes. Filter concentrate through a 50 mesh sieve
and homogenize at 6000 psi. Fill the concentrate into corrosion resistant lined aerosol
containers and add H in an 80: 20 ratio.
References
1. Carson, H.C. (1981) Household Personal Products Industry 1833.

2. Jones, J. and Rubino, A. (1968) US Patent 3,405,153.
3. Jones, J. and Rubino, A. (1975) US Patent 3,928,545.
4. Alexander, P. (1987) Refreshing antiperspirant formulation developments. Manufacturing
Chemist. 5851-52 (June).
5. Ross, S. (1994) An overview of the aerosol market in Europe. Spray Techno/. Marketing 4
16-25 (November).
6. Shelley, W.B. and Horvath, P.N. (1950) Experimental miliaria in man, II. Production of
sweat retention anhidrosis and miliara crystallina by various kinds of injury. J. Invest.
Dermato/. 1 9-20.
7. Papa, C.M. and Kligman, A.M. (1967) Mechanisms of eccrine anhidrosis, II. The anti-
perspirant effect of aluminum salts. J. Invest Dermatol. 49 139-145.
8. Quatrale, R.P., Waldman, A.H., Rogers, J.G. and Felger, c.B. (1981) The mechanisms of
antiperspirant action by aluminum salts, I. The effect of cellophane tape stripping on
aluminum salt-inhibited eccrine sweat glands. J. Soc. Cosmet. Chem. 3267-73.
9. Gosling, K., Jackson, N. and Leon, N. (1982) Canadian Patent 1,115,930.
10. Majors, P.A. and Wild, J.E. (1974) The evaluation of antiperspirant efficacy: influence of
certain variable. J. Soc. Cosmet. Chem. 25139.
11. Murphy, T. and Levine, M. (1991) Analysis of antiperspirant efficacy from test results. J.
Soc. Cosmet. Chem. 42 167-197 (May/June).
12. Fulton, J.E. (1989) Comedogenicity and irritancy of commonly used ingredients in skin care
products. J. Soc. Cosmet. Chem. 40321-333 (November/December).
13. Landsdown, A.B.G. (1947) Aluminum compounds in the cosmetic industry. Soap Perfumery
Cosmet. 47(5) 209.
14. Westwood Chemical Corporation, Antiperspirant Study at Hilltop Research Inc.,
unpublished clinical study, January 1994.
15. Abrutyn, E. and Bahr, C (1993) Formulating enhancements for underarm applications.
Cosmet. Toilet. 108(7) 51-54 (July).
16. Kroschwitz, J. (1987) Encyclopedia of Polymer Science and Engineering, Microencapsulation,
2nd Edition. Volume 9, Wiley, NewYork,pp. 724--745.
17. Morey, E. (1991) Emulsification, emulsion preparations and the HLB system facts and
hands-on-tips. For Formulation Chemists Only F2 CO 110-13.
18. Hameyer, P. (1991) Comparative technological investigations of organic and organosilicone
emulsifiers in cosmetic water-in-oil emulsion preparations. H appi. 28(4) 88-94 (April).
19. Sturm, W. (1979) Deosafe fragrances: fragrances with deodorizing properties. Cosmet.
Toilet. 9435-48 (February).
20. Murphy, R. and LuJoie, S. (1994) Antiperspirant-deodorant cosmetic products, US Patent
5,376,362.
21. Lamb, J.H. (1946) Sodium bicarbonate: An excellent deodorant. J. Invest. Dermato/. 7
131-133.
22. Charig, A., Froeke, c., Simone, A. and Eigen, E. (1991) Inhibitor of odor producing axillary
bacterial exoenzymes. J. Soc. Cosmet. Chem. 42133-145 (May/June).
23. Department of Health and Human Services, Food and Drug Administration (1979) OTC
topical antimicrobial products, over-the-counter drugs generally recognized and safe,
effective and not misbranded. Federal Register, part II. January 6.
24. Meinike, B.E., Kranz, R.G. and Lynch, D.L. (1986) Effect of irgasan on bacterial growth
and its adsorption into the cell wall. Microbios 28133-147.
25. Shehadeh, N.H. and Kligman, A.M. (1963) The effect of topical antibacterial agents on the
bacterial flora of the axilla. J. Invest. Dermatol. 4061-71.
26. Reheis Inc. (1990) Antiperspirant efficacy guide, published literature, May.
27. Buttery, H. (1994) Encapsulation of fragrances. Cosmet. Toilet. Manufacture Worldwide
165-171.
Miscellaneous patent literature
28. Fitzgerald, J.J., Phipps, A.M., McClean, J. and Wu, M.S. (1980) Aluminum chlorhydroxide
and preparation thereof. UK Patent Application 2,048,229A.
29. Gosling, K., Mulley, V.J. and Baldock, M.J. (1982) Inhibition of perspiration. UK Patent
2,027,419B.
30. Giovanniello, R. (1994) Method for preparing basic aluminum halides by reacting
aluminum halide with aluminum. US Patent 5,356,609.
31. Giovanniello, R. (1994) Method for preparing basic aluminum halides and product
produced therefrom. US Patent 5,358,694.
32. Murray, R.W., Nelson, R.E. and Rubino, A.M. (1993) Enhanced efficacy aluminum
chlorhydrate antiperspirant and method of making same. US Patent 5,234,677.
33. Callaghan, D., Phipps, A. and Provancal, S. (1992) Antiperspirant composition with
improved efficacy. US Patent 5,114,705.
34. Giovanniello, R. and Howe, S.M. (1989) Antiperspirant composition and method of
preparation. US Patent 4,871,525.
35. Shin, CT, Slade, M.T. and Nersesian, A. (1988) Antiperspirant composition containing
aluminum chlorhydrate, aluminum chloride and an aluminum zirconium polychlorhydrate
complex and method of use. US Patent 4,774,079.
36. Brewster, D.A., Kuznitz, M. and Faryniarz, J.R. (1992) Clear cosmetic sticks. US Patent
5,128,123.
37. Angelone, P., Karassik, N. and Grace, W. (1992) Clear gel composition. WO Patent
9,205,767.
38. McCrea, A.D. and Diulus, M.D. (1994) Stable anhydrous topically active composition and
suspending agent. US Patent 5,292,530.
39. Orr, T.V. (1991) Antiperspirant creams. US Patent 5,069,897.
40. Luebbe, J.P., Tanner, P.R. and Farris, D. (1988) Antiperspirant gel stick. US Patent
4,781,917.
11 Regulation of cosmetic products
E.G. MURPHY and P.J. WILSON
11.1 Historical development
The modern day mass market toiletry and cosmetic industry began in the US
in the early years of the 20th century, and particularly between the two world
wars. Whilst the industry record for in-use safety of its products was good,
this rapid expansion in consumer exposure gave rise to calls for action to
pre-empt possible problems that could arise. Consumer pressure and
advances in the science of toxicology added to the general concern.
In the US, the Pure Food and Drugs Act of 1906 [1], enacted to extend
formal federal controls over foods and drugs, did not include cosmetics,
reportedly as the result of a political compromise [2]. Not until passage of
the Food, Drug and Cosmetic Act in 1938 [3] were cosmetics included in the
general prohibitions against manufacturing and marketing adulterated or
misbranded products. The 1938 Act also made it possible for products
previously unregulated to come under Food and Drug Administration
(FDA) [4] control as drugs if they were intended not only for medicinal and
therapeutic purposes, but also if they were intended to affect the structure or
function of the body. The 1938 Act has since been amended to control the
safety of cosmetic colors. Regulations under both the FDC Act and the Fair
Packaging and Labeling Act (FDCA), administered by FDA, restricted or
prohibited cosmetic ingredients found to be unsafe and required extensive
informative labeling of cosmetic packaging.
Other national and regional governments have likewise sought to govern
cosmetic products. In Japan, cosmetics are included in the Pharmaceutical
Affairs Law administered by the Ministry of Health and Welfare. The law
requires that cosmetic manufacturers and importers be licensed and that each
cosmetic placed on the Japanese market either be in conformance with the
monographs that make up the Comprehensive Licensing Standards of
Cosmetics or have obtained direct individual approval from the Ministry.
In Europe prior to 1976 there was no comprehensive control of cosmetics
and local legislation varied widely. Some countries, e.g. Germany, already
had a highly developed regulatory system, whilst others relied almost solely
on rather antiquated rules for poisons control. With the development of the
then European Economic Community, later the European Community and
now the European Union (EU), with its twin aims offree movement of goods
REGULATION OF COSMETIC PRODUCTS 345
between member states (MS) and consumer safety, this situation was
unacceptable. In 1976 the then MS agreed a Directive on Cosmetic Products
which would be applicable to the Community as a whole. In the pursuit of
adaptation to technical progress, this Directive has, in the meantime, been
amended no less than 24 times.
Other countries have developed their own regulatory styles, but in the main
these are based on those of one of the three major markets: Japan, USA or
Europe.
11.2 Self-regulation
In many areas of the world, and especially in the US, the cosmetic industry
has embarked on voluntary programs aimed at improving the safety and
effectiveness of cosmetics and at the same time, at avoiding more intrusive
government regulation. These activities have included codes of good practice
and self-regulatory programs such as voluntary registration of cosmetic
manufacturing establishments, cosmetic products and ingredients, and
voluntary reporting of adverse reaction experiences. In addition, in the US,
the industry has undertaken a program [the Cosmetic Ingredient Review
(CIR)] to assess the safety of cosmetic ingredients through an independent
panel of scientific experts which meets, deliberates and publishes its findings.
CIR reports on specific cosmetic ingredients are used by industry and govern-
ment to establish the safety of these materials. In addition, the perfumery
industry set up the international organizations IFRA (International
Fragrance Research Association) and RIFM (The Research Institute for
Fragrance Materials) to examine and review perfumery materials, and to
control their use. The aerosol industry published a code of practice for manu-
facture of aerosol products, while the European Chemical Industry set up
ECETOC as a review body to control information on the safety of chemical
substances. COLIPA (Comiti: de Liaison des Associations Europeennes de
l'Industrie de la Perfumerie des Produits Cosmetique et de Toilette), the
representative body for trade associations within the EC, published' Advisory
Notes to Manufacturers' together with a number of other advisory documents
covering the safety of cosmetic and toiletry products. These included the
'Education and Training of Personnel', 'Product Safety Verification During
Marketing' and 'Avoidance of Nitrosamine Formation in Cosmetic Products'.
Although much of the voluntary activity described eventually led to legis-
lation, there still remains a wealth of voluntary activity, and the legislation
imposed has been maintained at realistic levels. Industry continues to adjust
its voluntary controls in the light of consumer pressures, environmental
concerns and legislation in other areas that impinges on the products manu-
factured and sold as cosmetics and toiletries. Constant vigilance and aware-
ness of these issues is imperative for all scientists aspiring to create new
approaches and new products in this area.
11.3 Regulation in the United States
11.3.1 Federal regulation of cosmetics

The Federal Food, Drugs and Cosmetic Act (FDC Act) [1] is the primary
food and drug law in the United States. The FDC Act prohibits [2] the distri-
bution or importation of cosmetic products that are adulterated [3] or
misbranded [4], terms that have been interpreted by Congress, the Food and
Drug Administration (FDA), and the courts to include certain characteris-
tics. However, in general, the term 'adulterated' includes products that are
defective, unsafe, filthy or produced under insanitary conditions. A cosmetic
may be adulterated if it or its container is composed of a deleterious
substance that may render it injurious to users under customary or labeled
conditions. A cosmetic may also be adulterated if it contains any 'filthy,
putrid or decomposed substance' or if it has been produced, packed or held
in insanitary conditions under which it may have become contaminated.
Finally, a cosmetic may also be adulterated if it contains an unapproved color
additive.
The term 'misbranded' refers to statements, designs or pictures in cosmetic
product labeling that are false or misleading or which fail to provide required
information, and to the use of deceptive or improper containers. A cosmetic
may be misbranded if it fails to bear all of the information required under
both the FDC Act and the provisions of the Fair Packaging and Labeling
Act (FPLA) [5], which sets forth the content and placement of information
required on all consumer packages.
The FDC Act also requires that companies maintain certain records [6],
and authorizes FDA to inspect cosmetic products and establishments,
including manufacturing and packaging plants, warehouses and other
storage facilities, vehicles used for transporting cosmetic products and
containers of imported goods held at US ports of entry [7].
The Food and Drug Administration, an agency within the Department of
Health and Human Services, administers and enforces both the FDC Act
and the FPLA. FDA conducts routine and regular inspections of cosmetic
establishments in the United States to determine that products produced,
packed and stored are neither adulterated nor misbranded. The FDA has
not issued good manufacturing practice (GMP) regulations for cosmetics,
although cosmetics that are also drugs are subject to the pharmaceutical
GMPs. In practice, the same inspection team generally conducts inspections
at both over-the-counter drug and cosmetic facilities. In addition to its
routine inspection activities, FDA will also investigate products and
establishments on the basis of consumer complaints or because a company
has filed a trade complaint concerning a possible violation of the law by one
of its competitors.
Persons and firms responsible for violations may be subject to civil and
criminal sanctions. Products found to be in violation may be seized and their
further manufacture or distribution may be enjoined by orders obtained by
FDA in the Federal court [8]. If the offense is egregious, deliberate or
repeated, FDA may bring a criminal suit against the company and its
responsible officials [9]. Imported products that appear to be in violation of
the law may be detained at the port of entry by FDA inspectors and if found
to be in violation, may be destroyed if they cannot be brought into
compliance or are not re-exported [10].
Although FDA brings many formal cases against violators and products
each year, it also works with domestic companies toward voluntary recall or
correction of illegal goods and practices. This in part is due to the scarce
resources of the FDA and because the FDA has the burden of proving that a
product is either adulterated and! or misbranded. The first step in the FDA's
enforcement procedures is therefore usually a warning letter to the
responsible company or individual from the FDA charging a violation of
the Act and regulations and providing a limited time, usually 15 days, for
the company to correct the violation.
Despite the formidable enforcement tools at the disposal of the FDA,
cosmetics remain the most lightly regulated products within the FDA's
jurisdiction, in large part because more stringent restrictions have
not been needed. Cosmetic products may be placed on the US market without
FDA premarket clearance as long as the products do not contain any prohib-
ited or unsafe ingredients (not adulterated) and are properly labeled and
promoted (not misbranded). There exists no Federal requirement for
cosmetic establishment registration or for listing cosmetic products or ingre-
dients with the FDA. The regulations do include procedures for voluntary
registration and listing of cosmetic establishments, products and ingredients
and many industry members participate in this voluntary program [11].
11.3.2 Cosmetic composition
11.3.2.1 Safe ingredients Each cosmetic manufacturer is responsible for

using only safe and suitable ingredients in its products and for substantiating
the safety of the finished product [12]. Products whose safety has not been
substantiated must bear a warning statement on the label [12]. Although to
this author's knowledge, no cosmetic product has ever been so labeled, in
the event that a product is shown to be unsafe and is marketed without such
a warning, FDA could charge the responsible company with failure to warn
under the provision. This use of the 'misbranding' provisions of the statute,
together with the adulteration prohibitions in the statute, encourages volun-
tary testing of cosmetic products and ingredients prior to marketing [13].
The FDA has published a short list of restricted or prohibited substances,
including items such as bithionol [14], hexachlorophene [15], mercury
compounds for all but preservative use in eye area products [16], vinyl
chloride [17], halogenated salicylates [18], zirconium in aerosols [19], chloro-
form [20], methylene chloride [21] and chlorofluorocarbon propellants [22].
11.3.2.2 Color additives The FDA has also published regulations stipu-
lating the color additives that may be used in cosmetic products, including
the product categories in which they may appear, any restrictions in the
concentration level of the colors and any required label warning statements
[23]. The list of color additives is divided into those that must be certified by
the FDA prior to their sale (all 'FD&C' and 'D&C' colors) [24] and so-called
'natural' colors for which no certification is required.
In contrast to some other color additive regulatory schemes, most
synthetic coal tar colors (the colors identified by 'FD&C' and 'D&C' nomen-
clature, such as FD&C Red 6) have not been authorized for use in products
intended for the eye area. The exceptions are FD&C Yellow 5, FD&C Green
5, FD&C Blue 1 and FD&C Red 40.
11.3.2.3 Hair dyes The FDA's prohibition against the use of 'poisonous
or deterious substances' in cosmetic products [25] does not apply to coal tar
hair dyes as long as the statutory warning statement appears on the product
containers. In addition, coal tar hair dye colors are not subject to the
regulatory requirements for cosmetic color additives [26]. The warning state-
ment required by the FDC Act is as follows:
Caution-This product contains ingredients which may cause skin irritation on
certain individuals and a preliminary test according to accompanying
directions should first be made. This product must not be used for dyeing the
eyelashes or eyebrows; to do so may cause blindness. [27]
11.3.3 Cosmetic labeling

The FDA has issued detailed rules for the labeling of cosmetic products*.
These rules are issued under both the FDC Act and the FPLA. Because the
FPLA applies only to the outermost containers of retail cosmetic packages,
some labeling requirements such as the ingredient declarations, product
identity statements and placement and typesize of net content declarations,
only apply to the outermost retail container. Cosmetics must be labeled with
the information detailed in sections 11.3.3.1 to 11.3.3.6.
11.3.3.1 Product identity [28] This statement should appear on the

principal display panel (PDP) of the outer container in bold type and in lines
parallel to the bottom of the package. The law does not require a product
* The term 'labeling' as defmed in the Federal Food, Drug and Cosmetic Act (FDC Act)
includes not only the product label, containers and package inserts, but also material that accom-
panies the product such as booklets, catalogs and even advertising.
identity statement on the inner container of cosmetics that are packaged in
an inner and outer container. However, the inner containers of most products
are labeled with a product identity statement to avoid consumer confusion
and potential misuse that could result in a product liability suit.
The name used may be the common name of the cosmetic, a descriptive
name or fanciful name (if the nature of the cosmetic is otherwise obvious) or
the cosmetic may be identified by an appropriate illustration of the cosmetic's
intended use.
Products sold to beauty salons for professional use by beauticians, gifts or
free samples, testers or demonstrators and theatrical make-up for profes-
sional use only are exempt from product identity labeling requirements.
However, in practice, these products generally are labeled with an identity
statement to avoid user confusion and potential misuse that could result in
user injury.
11.3.3.2 Name and address of the manufacturer, packer or distributor [29]

The name and address of the manufacturer, packer or distributor must
appear on both the inner and outer containers. The street address may be
deleted if the company appears in the local telephone or city directory. If the
name that appears on the container is not the manufacturer, it must be
prefaced by an explanatory phrase such as 'Distributed by', 'Manufactured
for', 'Packaged by' or a similar description. The name and address must be
placed conspicuously on the product, although specific type size and place-
ment are not required. Labeling the bottom panel is not generally considered
to be 'conspicuous'. The actual corporate name of a corporation must be
used. Partnerships, individuals or associations may be identified by the name
under which they do business.
11.3.3.3 The net content in American (ounces/fluid ounces) and metric

measures [30] This statement should appear in American units within the
lower 30% of the PDP in lines parallel to the bottom of the package. If the
PDP is less than 5 inch2 (32 mm 2) , the declaration may appear anywhere on
the PDP. Ifthere is more than one PDP, the declaration must appear on each.
The required type size for the net quantity of contents varies with the size of
the PDP.
If a cosmetic is sold in an inner and outer container, the inner container
must also bear a net quantity of contents statement. However, the typesize
and placement requirements for the net quantity of contents do not apply to
the inner container as long as the statement appears in a conspicuous
location.
11.3.3.4 A statement of ingredients in the product in descending order of

predominance [31] The ingredients are only required on the outer container
and generally are listed in order of predominance in the product. The
minimum required typesize for product ingredient statements is -kinch

b
(1.6 mm), except that inch (0.8 mm) may be used if the total surface area
available for labeling is less than 12 inch 2 . Placement must be on an appro-
priate information panel (bottom panel labeling is not generally considered
'appropriate').
Products sold to beauty salons for professional use by beauticians, gifts or
free samples, testers or demonstrators and theatrical make-up for profes-
sional use are exempt from ingredient labeling requirements. Special ingre-
dient labeling rules exist for certain cosmetic products, such as lines of
shaded products, assortments, products sold by mail order and products
displayed in cases and display units.
11.3.3.5 Any warnings required by regulation [32] (such as the warnings

required for aerosol products [33] and bath foam products [34]) Warning
statements must be conspicuous and prominently displayed on both the inner
and outer containers and in typesize no smaller than -k
inch (1.6 mm).
Warning statements have been prescribed in the US for foaming bath
products, hair dyes, aerosol products, feminine deodorant sprays and for
products without adequate safety substantiation.
11.3.3.6 Country of origin, if imported [35] US Customs Service regula-

tions require that cosmetic product containers be marked with the country
of origin of their contents. Expiration dating and lot or batch codes are not
required by specific regulation. Most companies do include an expiration
date if the product is not likely to be sold and used within its period of
stability. Lot and batch codes are commonly added to cosmetic product
labeling to facilitate recall and identification of products in the marketplace,
when necessary [36].
11.3.4 The relationship of cosmetic products to drugs

The distinction between cosmetic and drug products is based upon the
definitions of these articles in the FDC Act. The FDC Act defines cosmetics
as '(1) Articles intended to be rubbed, poured, sprinkled, or sprayed on,
introduced into, or otherwise applied to the human body or any part thereof
for cleansing, beautifying, promoting attractiveness, or altering the appear-
ance, and (2) articles intended for use as a component of any such articles;
except that such term shall not include soap' [37].
The FDC defines drugs in pertinent part as: '(B) articles intended for use in
the diagnosis, cure, mitigation, treatment or prevention of disease ... ; and
(C) articles ... intended to affect the structure or any function of the
body ... .' [38].
Thus, the representations made for a product in its labeling determine
its legal status. The definitions are not mutually exclusive and a product can
be both a drug and a cosmetic, in which case the product must meet all the
applicable requirements. As drugs may only be marketed if the FDA deter-
mines that they are generally recognized as safe and effective for their labeled
use, classification as a drug will raise the regulatory burden.
11.3.4.1 Cosmetics and anti-aging claims Over the years, the FDA has
regularly challenged representations for cosmetic products it considers either
false and misleading or representations that fall within the FDC Act drug
definition. As most companies faced with misbranding or new drug charges
choose to modify product labeling rather than to develop the data required to
support drug approval, only a few judicial decisions address the cosmetic-
drug distinction in any detail. The chief cases stem from the 1960s, at which
time the FDA initiated civil seizures of three skin care products which were
widely promoted to smooth, reduce or prevent wrinkles.
'Line Away Temporary Wrinkle Smoother' was advertised as being able to
'visibly smooth out fatigue lines, laugh lines, worry lines, frown lines, tiny age
lines and crows feet, while discouraging new lines from forming'. Advertising
for Line Away contained statements that 'Line Away is an amazing protein
liquid. Contains no hormones or harmful drugs. It's the only wrinkle
smoother packaged under biologically aseptic conditions in the pharma-
ceuticallaboratories of (the manufacturer)' (United States v. An Article ...
'Line Away', 283 F. Supp.* 107 (D.De1, 1986), affd, 415 F.2d 369 (3rd Cir.
1969)).
'Sudden Change' was labeled and advertised as the 'new and improved,
dramatically different wrinkle-smoothing cosmetic. By simple, dynamic
contraction, it lifts, firms, tones slack skin ... smooths out wrinkles, lifts the
puffs under the eyes, leaving your contours looking beautifully defined. It
acts noticeably, visibly ... not a hormone or chemical astringent, Sudden
Change is a concentrated purified natural protein ... .' Sudden Change was
also advertised as a 'face lift without surgery! ... (it) is the one cosmetic that
can make you look years younger for hours ... although it cannot eliminate
wrinkles permanently ... Just smooth it on and watch it smooth away crows'
feet, laugh and frown lines-even under-eye puffiness ... Sudden Change ...
does not change the structure or function of your skin in any way' (United
States v. An Article ... 'Sudden Change', 288 F.Supp. 29 (E.D.N.Y. 1968),
rev'd., 409 F.2d 734 (2d Cir. 1969)).
'Magic Secret', the third product, was advertised to 'smooth away wrinkles
in minutes ... keep them away for hours', to 'firm the skin', to 'tighten and
moisturize tired skin', to 'smooth away crows feet, puffy under eye circles,
laugh, frown, and throat lines injust minutes'. Users would 'feel an astringent
* F. Supp., Federal Supplement; D. Del, District of Delaware; 3rd Cir., Third Circuit;
affd, Affirmed; E.D.N.Y., Eastern District of New York; F. 2d, Federal Reporter 2nd Edition;
D. Md., District of Maryland; 2d Cir., Second Circuit.
sensation gently firming and toning the skin' (Unites States v. An

Article ... 'Magic Secret', 331 F.Supp. 912 (D. Md. 1971)).
Only the intended uses for 'Magic Secret' were held to be within the Act's
cosmetic definition [39]. The courts in 'Line Away' and 'Sudden Change'
found these products within the FDC Act's 'drug' definition [38] based upon
their promoted ability to affect the structure and function of the body by
'lifting' the skin, by discouraging new wrinkle lines, and in the case of 'Line
Away', by the therapeutic implications created by statements that the
product was produced in a 'pharmaceutical laboratory' and packed under
'biologically aseptic conditions'.
Since these cases were decided, the FDA has taken administrative action
against products represented for uses the Agency believes are intended to
affect the structure or function of the user's body. In a letter to cosmetic skin
care companies in 1987, the FDA stated that,
We consider a claim that a product will affect the body in some physiological
way to be a drug claim, even if the claim is that the effect is only temporary ... .
Therefore, we consider most of the anti-aging and skin physiology claims ... to
be drug claims. For example, claims that a product "counteracts," "retards."
or "controls" aging or the aging process, as well as claims that a product
"rejuvenates," "repairs," or "renews" the skin, are drug claims because they
can be fairly understood as claims that a function of the body, or that the
structure of the body will be affected by the product.
For this reason, also, all the examples ... (that) allege an effect within the
epidermis as the basis for a temporary beneficial effect on wrinkles, lines or fine
lines are unacceptable. A claim such as 'molecules absorb ... and expand,
exerting upward pressure to lift wrinkles upward' is a claim for an inner, struc-
tural change. [40]
The FDA further stated:

... we would not object to claims that products will temporarily improve the
appearance of ... outward signs of aging. The label of such products should
state that the product is intended to cover up the signs of aging, to improve the
appearance by adding color or luster to skin, or otherwise to affect the appear-
ance through physical means .... We would consider a product that claims to
improve or to maintain temporarily the appearance or the feel ofthe skin to be a
cosmetic. For example, a product that claims to moisturize or soften the skin is a
cosmetic. [40]
In the same letter, the FDA stated that products represented for OTC drug
purposes, such as sun protection or protection from harmful or annoying
stimuli would be regulated as OTC drug sunscreens or OTC drug skin protec-
tants. Other representations that the FDA has considered to be either
misleading cosmetic claims or unapproved new drug claims include anti-
cellulite claims and skin renewal claims for which mode of action is to affect
the structure function of the body. Most recently, the FDA has investigated
the safety and mode of action of IX-hydroxy acids in cosmetic products.
11.3.4.2 Cosmetics and aTC drugs Many products considered to be
cosmetics in other countries are regulated in the US as over-the-counter
(OTC) drugs. These products include antiperspirants, anti-dandruff
shampoos, sunscreen products, skin lighteners, anti-acne products, anti-
cavity and anti-plaque dental products and skin protectants. A product that
is represented as intended for one of these uses will be regulated by the FDA
as a drug. If the product is also labeled for cosmetic uses, such as for cleaning,
beautifying or moisturizing, it will be considered a cosmetic as well as a drug
product, in which case it must bear both cosmetic and drug labeling. Products
that do not comply with FDA monographs (final rules) for OTC drug
products may be considered to be unapproved new drugs that may only be
marketed subject to an approved new drug application.
11.3.4.3 Future cosmetic-drug overlap The 'cosmetic' and 'drug' defini-

tions have not changed since the FDC was enacted in 1938. In the meantime,
cosmetic products have become more sophisticated and the line between
cosmetic and drug product has often blurred. Although the FDA has recog-
nized in the OTC drug review procedures that limits for materials used in
drug products do not apply when used in cosmetic products [41] the presence
of some ingredients in a cosmetic product is likely to cause its regulation as a
drug by the FDA. These ingredients tend to be those for which no cosmetic
use is known (for example, penicillin) or which have been heavily promoted
by the manufacturers for therapeutic purposes (for example, certain UV
absorbers). The response of the FDA to date to technology advances such as
fluoride toothpaste, antiperspirants and sunscreens, has been to designate
and regulate the products as drugs under the more stringent drug premarket
review and approval procedures. It remains unclear whether the FDA will
take similar steps to control the use of ingredients such as the IX-hydroxy
acids, which have been shown to have a physiological effect, or whether the
FDA and industry will find other methods of assuring the safety of these
innovative cosmetic ingredients and products. One solution would be to use
the industry-funded Cosmetic Ingredient Review (CIR) program to assess
the safety of cosmetic ingredients. The CIR, which has a permanent staff
headquartered in Washington, D. c., commissions independent expert panels
of scientists to evaluate the available published and unpublished literature on
the safety of specific cosmetic ingredients. The FDA, industry and consumer
organizations may each appoint a non-voting representative to attend the
expert panel meetings.
11.3.5 Regulation of cosmetics by other federal agencies
11.3.5.1 Federal Trade Commission The Federal Trade Commission

(FTC) and the Food Drug Administration (FDA) have overlapping and
concurrent jurisdiction over the advertising and labeling of foods, drugs,

medical devices and cosmetics. The FTC regulates 'deceptive' or 'unfair'
advertising, including promotional claims that appear on packages or in the
media and is chiefly concerned that the consumer has reliable, substantiated
information upon which to base purchasing decisions.
The FDA regulates 'false or misleading' statements made in product
'labeling' and, although its jurisdiction extends to economic deceptions, the
FDA is primarily concerned that the public health and safety is not
endangered through consumer reliance on unsubstantiated claims to safety
and effectiveness.
Although in regulating product claims, the FTC focuses chiefly on
consumer deception and the FDA chiefly on health and safety concerns, the
responsibilities of the two agencies overlap and nothing in the law would
prevent simultaneous FTC and FDA prosecutions against deceptive, unfair
and misleading labeling and promotional claims. Therefore, to avoid
unwanted duplicative proceedings, the FDA and the FTC have entered into
a liaison agreement (Memorandum of Understanding between the FDA and
FTC, 36 Fed. Reg. 18,539 (1971)), in which the FTC agrees to take primary
responsibility for regulating 'advertising' and the FDA agrees to take
primary responsibility for regulating 'labeling'. In practical terms, this means
that questionable representations made only in advertising are handled by
the FTC, while questionable representations made in labeling or in labeling
and advertising are generally handled by the FDA. As part of the agreement
between the two agencies, the FTC and FDA exchange information about
enforcement proceedings as needed.
The FTC regulates advertising claims through industry-wide rulemakings,
through administratively adjudicated cease-and-desist orders entered
against specific companies, through issuance of FTC Policy Guidelines and
through prosecution of specific cases in the federal courts. An FTC investiga-
tion of advertising claims may be prompted by requests made by consumers,
competitors, state officials or the Commission itself.
Advertising claims may be considered deceptive because they contain a
'material' representation, omission or practice that is likely to mislead
consumers 'acting reasonably under the circumstances'. A representation or
omission is 'material' if it affects the consumer's choice of product, such as
statements about the product's ingredients or the nature of risks involved in
product use. (Cliffdale Associates, Inc. v. FTC, 103 FTC 110 (1984)). In
addition, representations about a product can be considered deceptive if the
advertiser lacks substantiation that demonstrates there is a reasonable basis
for a claim. In fact, inquiries into claim substantiation are the primary basis
for FTC investigations and challenges to advertising.
An FTC request for substantiation is non-public and is 'directed to
individual companies via an informal access letter or, if necessary, a formal
civil investigative demand'. Requests may be directed to one company or to
several companies within the same industry. Unless the claim made in
advertising is substantiated, the advertiser may be held to have violated the
prohibition Section 5 of the Federal Trade Commission Act prohibiting
'unfair or deceptive acts or practices in or affecting commerce' [42].
11.3.6 Cosmetics and the Consumer Product Safety Commission

Cosmetics are explicitly excluded from regulation under the Consumer
Product Safety Commission (CPSC) [43]. However, in the absence of FDA
jurisdiction, the CPSC has regulated such items as soap. The CPSC also has
authority to issue regulations establishing special packaging requirements
under provisions of the Poison Prevention Packaging Act [44].
11.3.7 Regulation of cosmetics by the states

Each state has the authority to regulate products and to impose additional
requirements that do not conflict with federal regulation of cosmetics. Most
states have adopted 'mini FDC Acts' that in general are identical to the
federal statute. Some states, however, go beyond the FDC Act to require
registration of cosmetic establishments and products.
Furthermore, state environmental legislation has tended to include
cosmetic products and ingredients. For example, at the time of this writing,
at least eight states (California, New Jersey, New York, Oregon, Rhode
Island, Connecticut, Massachusetts and Texas) have either proposed or
issued regulations restricting the levels of volatile organic chemicals in
cosmetic products such as deodorants, fragrances, and/ or hair products and
similar regulation by the federal agency, the Environmental Protection
Agency (EPA), is expected. California's Proposition 65 [45] requires a
warning statement on products that contain ingredients known to the state
to be carcinogenic or reproductive toxins. Other states are beginning actively
to regulate the composition and disposal of plastic and other cosmetic
containers.
11.3.8 Conclusion
Cosmetics are the least regulated of the products subject to FDAjurisdiction.
Cosmetics may be placed on the US market without premarket clearance as
long as they are neither adulterated or misbranded and may be distributed in
all the states as long as they comply with individual state regulations,
including environmental legislation affecting cosmetic products. The chief
challenge to regulators in the future will be the control of innovative cosmetic
products and ingredients to protect the public health and safety, while the
chief challenge for industry will be to keep these cosmetics out of the drug
definition and away from regulation as drugs. The other major concern for
the next decade will undoubtedly continue to be regulation of cosmetic

product composition and packaging under state and federal environmental
laws and the subsequent challenge to industry to develop environmentally
safe products.
11.4 Regulation in Europe
Since 1976, the size of the EU has steadily increased, with currently fifteen
members and more applications pending. In each of these, the Cosmetic
Directive (76/768) [46] as amended, now forms the basis oflocallegislation
with dual aims of enabling the free movement of goods between member
states (MS) and ensuring consumer safety. In all, the 1976 Directive has been
adapted on 24 occasions, the most recent major revision being the Sixth
Council Amendment (93/35) [47]. Agreeing changes to the Directive is a long
and tedious process, involving industry, all MS, the Commission, the
European Parliament and the Council of Ministers. As a result of this
complex procedure, the Sixth Amendment was under discussion for no less
than seven years.
Following these changes, the principal features ofEU cosmetic regulation
now include:
1. A definition of a cosmetic product
2. A requirement that cosmetic products should be safe for their intended
purpose under normal and foreseeable conditions of use
3. The establishment of an inventory of cosmetic ingredients
4. Pack labeling to include a full listing of ingredients
5. The requirement for manufacturers to maintain comprehensive
product information, including a formal safety assessment.
In addition, Annexes specify prohibited and controlled materials, as well
as listing the only permitted coloring agents, preservatives and UV -filters.
These latter 'positive lists' may well be extended to other classes of ingredient
in the future. Other proposals will eventually forbid the use of ingredients and
products which have been tested on animals.
National regulations in MS reflect the EU Directive, but manufacturers
should study these carefully in order to identify any local variations. Compli-
ance with the Cosmetics Directive and its national versions is mandatory but
facilitates the free movement of products throughout the EU. Imports from
outside the European Union are subject to similar controls.
Other European countries, outside the EU and particularly in the East, are
rapidly developing their consumer-based industries. It can be expected that
their regulatory regimes for cosmetics will closely parallel those of the
European Union in anticipation of eventual application for membership of
that group.
In addition to the rules specifically governing cosmetics, other more
general Directives exist, which may have some impact on the manufacture
and sale of cosmetics within the EU. These are listed below. It should be
remembered that European legislation is continuously developing and that
any of these may well have been the subject of more recent amendment.
• Medicines Directive (65 I 65 I EEC)
• Prepackaged Products Directive (78/891 IEEC)
• Prescribed Quantities Directive (80/232/EEC)
• Aerosol Directive (75/324/EEC)
• Dangerous Substances: Classification, Packaging and Labelling
(67/548/EEC)
• Solvents Directive (73 I 173 IEEC)
• Product Liability Directive (85/374/EEC)
Other general Directives cover such matters as advertising and health and
safety at work and apply equally to the cosmetics industry as to others.
11.5 Regulation in Japan
Cosmetics are regulated in Japan under the authority of the Pharmaceutical

Affairs Law (PAL) which requires that the manufacturer or importer of
cosmetics be licensed and that all products be either licensed with the facility
or approved individually. A simplified licensing system known as the
Comprehensive Licensing Standards of Cosmetics (CLS) has been instituted
within the past decade to permit easier marketing access to cosmetic products
that are formulated in accordance with the standards. Ingredients that may
be used for cosmetic products in Japan are identified in several sources,
including the CLS monographs, the Japanese Standards of Cosmetic
Ingredients (JSCI), and the industry publication Japanese Cosmetic
I ngredient Dictionary (J CID). Portions of the PAL and implementing regula-
tions have also been published in English in Principles of Cosmetic Licensing
in Japan [48].
11.6 Regulation in other countries
Most countries regulate the content and labeling of cosmetic products and in
many countries, the manufacturer or importer of cosmetics must be licensed
by the national health agency. Therefore, if a product is to be sold in several
markets, the initial formulation must take into consideration the rules
governing permissible cosmetic ingredients in as many potential markets as
possible. Details of individual national laws and regulations are available
from local health authorities and trade associations, local branches of the
Society of Cosmetic Chemists, and in-country Embassy commercial officers.
11. 7 General considerations
Formulating a cosmetic or toiletry product requires not only technical

knowledge, but also familiarity with the formidable array of regulations,
laws, restrictions and consumer preferences in each market. Being aware of
these and other factors will help the cosmetic scientist to advise the marketing
staff on subjects such as product claims, safety, acceptability, and product
liability concerns.
11.7.1 Environmental impact
Laws covering the pollution of air, water and land exist both nationally and
internationally, and are constantly under review. The consumer interest in
environmental issues, together with trend towards green politics and consu-
merism has developed public opinion to a degree where products may be
accepted or rejected according to their environmental performance. Contro-
versy concerning the ozone layer and the use of aerosol products is a particular
example. Marketing edge may be achieved by developing products that can
be shown to be harmless or beneficial to the environment. In this respect,
ingredients must be chosen with due care. Packaging, labeling, natural
materials and use of energy all require careful consideration and, without
doubt, new issues will arise in the future. Vigilance and current awareness is
essential.
11. 7.2 Animal protection and rights

The problems encountered in this area are associated not only with the use of
animals for laboratory testing, but also with the use of materials and
ingredients derived from animal sources. The use of animals for cosmetic
testing has decreased substantially over the past decade and continues to
decline worldwide. However, international regulations still require safety data
based on animal studies, therefore new materials not used for other industries
such as plastics, food, chemicals or pharmaceuticals, would require animal
testing. Fortunately, consumer pressure is now aimed at the regulators of
international law (e.g. the EC Commission) and ultimately these requirements
will be modified to make the situation much clearer and easier to cope with.
Due to the growing pressure from vegetarians, religious groups and animal
rights groups, this area of concern is constantly changing. The labeling of
products as 'non-animal tested,' 'contains no animal ingredients,' 'kosher',
etc. requires careful consideration.
11.7.3 Drug or cosmetic? Borderline products

The description 'borderline' is applied to those products which, by their
composition or claims, may fall within the regulatory regime of either
cosmetics or medicines.
The development of more effective, and in some cases therapeutic,
products based on modern cosmetological research and development makes
a consideration of the borderline area essential. Authorities are vigilant in
ensuring that claims, composition and modes of action of intended cosmetic
products do not place them in the field of drugs. Thus it is essential for the
formulator to be fully aware of where the boundary lies, as the penalties for
straying across it are severe.
Whilst the amount of pre-marketing administration for cosmetics is
generally relatively straightforward in most world markets, the same cannot
be said for medicines. Here, the requirement to demonstrate benefit, efficacy,
safety and quality in order to obtain the necessary licences demands signifi-
cant resources, even for a relatively simple product making modest claims. In
addition, the time delay in bringing a new product to market may be com-
mercially damaging, as may restrictions on advertising or distribution.
The approach to this question varies from one jurisdiction to another. In
the US and Japan there are three categories of product-cosmetics, pre-
scriptions, drugs and an intermediate group (over the counter drugs in the
US; quasi-drugs in Japan). In the EU there is no third category and products
may only be classed as cosmetics or medicines. The producer on the
international scale must therefore be fully aware of the local conditions in
his intended markets.
It is beyond the scope ofthis book to discuss the borderline situation in any
detail. For a fuller description, the reader is referred to the following reviews;
by Wilson and Adams for Europe [49], for Japan [50] and for the US [51].
11.7.4 Product liability

The situation with regard to product liability has always been much more
strict in the US then elsewhere. In Europe the law is under considerable debate
and is moving toward the US situation based on the 'deepest pocket' principle.
However, in Europe it is still necessary to prove that the product was defective
and that it caused the damage complained of, before a successful suit for
damages may be concluded. This situation is under review and remains an
issue of great debate. As a result, change is inevitable, and it is necessary to
keep abreast of current developments when considering ingredients for use
in the products under consideration, the product design and method of
application.
References
1. 21 United States Code (USC) §§ 301 et seq.
2. 21 USC § 321.
3. 21 USC§361.
4. 21 USC§ 362.
5. 15 USC §§ 1451 et seq.
6. 21 USC § 373.
7. 21 USC § 374.
8. 21 USC § 332,334.
9. 21 USC § 333.
10. FDA Investigations Operations Manual (1994) US Department of Health and Human
Services, 265, 270 (October).
11. 21 Code of Federal Regulations (CFR) Parts 710,720,730.
12. 21 CFR § 740.l0(a).
13. O'Reilly, J.T. (1993) Food and Drug Administration. Chapters 17-25, p. 26.
14. 21 CFR § 700.11.
15. 21 CFR §250.250.
16. 21 CFR§700.13.
17. 21 CFR§700.14.
18. 21 CFR§700.15.
19. 21 CFR§700.16.
20. 21 CFR § 700.18.
21. 21 CFR§700.19.
22. 21 CFR § 700.23.
23. 21 CFR pts 73, 74.
24. 21 CFR pts 74, 80.
25. 21 USC § 361.
26. 21 USC § 361(e).
27. 21 USC§361(a).
28. 21 CFR § 701.11.
29. 21 CFR § 701.12.
30. 21 CFR § 701.13.
31. 21 CFR§701.3.
32. 21 CFR pt 740.
33. 21 CFR § 740.11.
34. 21 CFR§740.17.
35. Tariff Act of 1930, as amended (19 USC § 1304).
36. In contrast, FDA requires that non-prescription (OTC) drug products bear expiration
dating unless the drug has no dosage limits and has shown to be stable for at least three years
and that all drugs bear lot or batch codes. 21 CFR §§ 201.17, 201.18 and 211. The National
Drug Code (NDC) may appear, but is not required, on OTC drug product packaging. The
NDC consists of a 10-digit number made up of the labeler code assigned by FDA and the
product code and packaging code assigned by the manufacturer, 21 CFR § 201.2.
37. 21 USC § 321(i). This definition is incorporated in the FPLA at 15 USC §§ 1454, 1456,
1459(a). The soap exemption from regulation under the FDC Act has been interpreted
narrowly in regulations issued by FDA at 21 CFR § 701.20 as applying only to products in
which the bulk of the non-volatile matter consists of an alkali of fatty acids and the detergent
properties are due to the alkali-fatty acid compounds and then only if the product is labeled,
sold, and represented as a soap (without cosmetic representations).
38. 21 USC § 321(g).
39. 21 USC § 321(i).
40. Letter from John. M. Taylor, Associate Commissioner for Regulatory Affairs, to Stuart
Friedel, Davis and Gilbert, re: Cosmetic Regulatory Letters, November 19,1987.
41. Federal Register (FR) 6822 (Feb. 15, 1988).
42. 15 USC § 45(a) (I) (supp. 1987).
43. 15 USC 2051 et seq. The Consumer Product Safety Act provides that 'consumer products' do
not include cosmetic products as defined by the FDC Act.
44. 15 USC 1471 et seq. The Poison Prevention Packaging Act includes 'cosmetic' within the
Act's definition of a 'household substance'.
45. Proposition 65 (1995) The Safe Drinking Water and Toxic Eriforcement Act of 1986, codified
at California Health and Safety Code, section 252495 et seq.
46. (1976) Official Journal of the European Communities.
47. (1993) Official Journal of the European Communities. LtSt 32.
48. The sources of Japanese Cosmetics law referred to are available from YAKUJI Nippo Ltd, 1
Kanda Izumicho. Chiyoda-ku. Tokyo 101, Japan.
49. Wilson, P. and Adams, M. (1995) Cosmetic or drug. The Regulatory Affairs Journal 6(3)
197-201.
50. FDA Investigations Operations Manual (1994) US Department of Health and Human
Services, 265 and 270 (October).
51. O'Reilly, J.T. (1993) Food and Drug Administration. second edition, chapters 17-25 and 26.
12 Quality
W.E. DUPUY
12.1 Introduction to quality
It is likely that readers of this book would expect a chapter on quality to

discuss various analytical techniques (biological, chemical, mathematical,
microbiological, physical, etc.) that are in common use in laboratories today.
Twenty years ago that would probably have been acceptable. However, in
the last two decades, ideas about quality have changed so much that it is
more prudent to advise the reader of the latest philosophy, and of how it
developed.
In the 1990s quality should touch every department in the company and
should not be the sole responsibility of those of scientific specialisation.
Quality as applied to manufacturing industry relates not only to that certain,
customer-winning property of attractive goods, but first and foremost to the
state of mind of those who produce them.
Quality is not just a certain level to be achieved once and for all, but means
constant striving for an ideal goal, an infinity. As far as manufacturers are
concerned, the quality of goods constitutes their signature and image. As for
consumers, quality must provide motivation for the first purchase and, ulti-
mately, complete satisfaction during use, thus providing the impetus for repeat
purchases.
Another very important aspect of quality is that of safety. This seems
obvious but, for that reason, is often not given sufficient attention. Even before
providing attraction and satisfaction, the quality of a product should be a
pledge and guarantee of its safety during use.
12.2 Definition of quality
The industrial meaning of the word quality has changed dramatically over
the years. Modern quality methods are no longer the domain in manufacturing
industry but extend to service industries, government institutions and health
authorities. The word 'quality' comes from the latin 'qua/is' meaning 'of what
kind'. Thus, in its original meaning quality was concerned with the compo-
sition or properties of an object without any implications of value. Today,
however, quality is usually invested with a distinctly positive ideal.
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Among the many definitions of 'quality' published in the technical litera-
ture, the one that is most concise and to the point is probably that of
Juran [IJ-"quality is fitness for use". Juran, however, gives no indication of
how 'fitness for use' could be expressed in concrete terms or even be measured.
The European Organisation for Quality Control [2J gave a more compre-
hensive definition: "Quality is the totality of features and characteristics of a
product or service that bear on its ability to satisfy a given need!" Thus, quality
is seen not as a single factor, but as a concept made up of several criteria.
In the US, the Pharmaceutical Manufacturers Association (PMA) has
published its own quality definition: "Quality is the sum of all factors which
contribute directly or indirectly to the safety, effectiveness and acceptability
of the product!" This is a good definition, but would it fit cosmetics or
toiletries? Providing that the weighting of the judges parameters is correctly
apportioned (acceptability, for example, will require more evaluation criteria
for a drug than for a cosmetic), the answer is yes.
As time has progressed, definitions of quality have become more and more
complex. However, Crosby [3,4J successfully introduced a relatively simple
definition: "Quality means conformance to requirements". In other words, the
definition of quality is very dependent on the intended usage. Quality
department personnel cannot be concerned with the various mystical aspects
of quality-beauty, elegance, value for money, or even fitness for purpose
(unless this means conformance to a defined purpose). The emphasis on
conformance throws the responsibility on to marketing and technical
departments to define the requirement and the product, such that a product
specification is produced. This specification should define the environmental
and reliability characteristics that the product must have, the workman-
ship standards that are applicable, and so on. The quality department are
responsible for checking conformance to this specification.
12.3 Inspection
During its development, quality has moved through three distinct phases.
Initially the concept of quality control-'have we done it right?'-was
developed. Quality control is not wrong, but its basis is inspection and is
therefore questionable. Inspection is an activity that:
(i) verifies that an output is acceptable;

(ii) sorts good from bad; and
(iii) takes place after the output has been produced.
Inspection, although potentially stopping errors from reaching the customer,
cannot be the basis for continuous improvement since:
(i) it does not prevent errors being produced in the first place;
Quantity
\ . / Cost
~ Errors
Time
Figure 12.1 Inspection costs.
(ii) visual inspection is not 100% effective, therefore mistakes or errors will
still reach the customer; and
(iii) it adds cost (Figure 12.1).
Inspection is, however, of use in four situations:
(i) to monitor and audit the process in order to provide necessary feedback
to maintain control of the process;
(ii) to gather data about causes of mistakes or errors in order to take
corrective action;
(iii) as a short-term measure until a permanent solution is implemented-
this should only be done against an agreed time scale to ensure that
inspection does not become the permanent solution; and
(iv) compliance with legal requirements.
12.4 Prevention
The second stage in the development of quality was the concept of quality
assurance- are we doing it right? (see section 12.5.2). This was a strategy for
stopping mistakes or errors from reaching the customer(s). Prevention is an
activity that:
(i) stops mistakes or errors from being generated; and
(ii) takes place before or during the process.
Prevention is the only strategy for continuous improvement since it:
(i) stops mistakes or errors from reaching the customer:
(ii) adds value (Figure 12.2) by preventing defects from being produced
in the first place and
(iii) will achieve customer satisfaction.
A study by IBM has shown that an increase in prevention costs is far
outweighed by the corresponding decrease in inspection and failure costs
(Figure 12.3). IBM found that ifit costs £1 to correct a mistake at the design
QUALITY 365
Quantity
L..-_ _ _ _ _ Time
Figure 12.2 Prevention costs.
r····· ...............
Cost of
quality Failure ~l Gain
............... Failure
Inspection Inspection
......... ,. ..
Prevention Prevention
Figure 12.3 Quality costs. Prevention = investment cost to prevent mistakes or errors from
occurring-what it costs to stop things going wrong; inspection = cost of checking the quality
that has been achieved-what it costs to find the errors before the customer does; failure = cost
of wasted resources due to mistakes or errors that reach the customer-what it costs to fix errors.
stage, then it costs £10 to stop it getting to the customer, and £100 to correct
it after the customer has received it.
12.5 Total quality
In recent years the concept of total quality has developed the idea of assurance
much further. Quality can be applied anywhere in an organisation. If everyone
in the organisation is striving to improve his or her quality and that
contribution is captured effectively, then the organisation is in a better position
to compete for the customer's attention. This is total quality.
Customers are the most important part of a business, yet not all companies
give them exactly what they want. In other words, many companies are not
truly driven by customer needs. In such situations, a thriving organisation
cannot exist. However, if customer requirements are used to drive all the
activities of a business then the business can expect to prosper. A number of

questions must be addressed.
• Who is the customer?
- the consumer?
- the retail trade?
-the internal customer?
• What are the customer's requirements?
• When were the customer's requirements last checked?
• How well are the customer's requirements being met?
The principles of satisfying customer requirements are equally relevant to both
internal and external customers, with all the ensuing business gains.
As with all aspects of quality, it is far from easy to work out customer
preferences, and it would seem to be impossible to anticipate emerging trends.
Many companies get stuck at the point when the customer says in effect 'I
know what I don't want'. Successful companies go beyond this and become
even more prosperous as a result. The customer-focused business, department
or manager:
(i) understands the customer by listening and observing;

(ii) looks ahead to the customer's future needs;
(iii) determines what makes a distinctive service for the customer;
(iv) defines and confirms the requirements to provide that service;
(v) focuses hard on precisely delivering the service;
(vi) sets benchmark standards to 'beat the best' of the competition; and
(vii) informs the customer of progress.
Total quality then is about conformance to the customer's requirements,

and the total service given to the customer. It recognises that in the
manufacturing industry, quality cannot be limited to product design and
quality assurance, but encompasses every aspect of a company's dealings with
its customers: (i) from sales literature through to after-sales service; and (ii) from
response time to customer enquiries through to delivery performance. Total
quality leads inevitably to a process of continuous improvement, even when
the customer's requirements are being satisfied, and achieves on-going
reductions in manufacturing costs. For this reason, it is frequently described
as being about 'the elimination of waste'. Examples might include the
following.
• Scrap
• Rectification and rework
• Downgrading of products
• Production hold-ups due to quality problems
• Warranty claims
• Product recalls
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• Product liability claims
• Lost sales due to poor quality and service
• Redundant stock
Total quality is not a prepackaged formula, a collection of techniques and
systems. No two companies will apply identical total quality, although
most total quality programmes have many common aspects. The approach
must reflect:
(i) the company's internal culture;
(ii) the expectations of the company's customers;
(iii) the company's manufacturing technology; and
(iv) how advanced the company is in terms of quality.
The adoption of total quality is increasingly being seen as the route to
achieving competitive edge. What makes companies distinctive in the market-
place is the difference between customer expectation and supplier achievement
-if positive this defines the competitive edge. Research has indicated conclu-
sively the importance of quality in determining a company's profitability.
Profit impact of market strategy (PIMS), which correlates statistics about
many companies worldwide, has concluded that relative product quality is the
single most important factor that affects a company's long-term financial
performance. Focusing on quality creates a cycle of improvement from which
reduced costs become inevitable. Benefits include:
(i) reducing operating costs, through doing things right first time;
(ii) lowering inventory levels, from improved predictability;
(iii) improving staff motivation and commitment;
(iv) increasing sales, from improved customer satisfaction; and
(v) improving relationships with suppliers.
Total quality aims to improve customer service and reduce costs by harnessing
everyone's commitment.
As stated previously, total quality is not a prepacked formula. However,
certain aspects of quality apply to most manufacturing companies. These are:
(i) product design; (ii) quality assurance; (iii) manufacturing processes and
technology; (iv) cost of quality; and (v) human and organisational aspects.
12.5.1 Product design

There are four important design related aspects of quality: (i) market research;
(ii) quality of design; (iii) design for manufacture; and (iv) product approvals.
12.5.1.1 Market research In many industries the customer's present and

future requirements are established by market research. For consumer
products, attitude and perception surveys are playing an increasingly
important role in identifying the customer's subconscious or latent attitudes-

as well as their more obvious requirements. Continuous improvement
requires:
(i) that the customer defines improvements as well as value;

(ii) that customer requirements are continually changing and customers
are continually demanding higher standards;
(iii) the need to be in a position to participate/influence tomorrow's
customer requirements.
This means anticipating and not reacting to the customer's requirements.

Anticipating the customer's requirements can only be achieved by having a
close relationship with the customer.
12.5.1.2 Quality of design However well products are manufactured their

quality cannot be improved beyond the inherent quality of design. In many
industries up to 60% of quality problems can be traced back to design. In the
cosmetics and toiletries industry this is where the most important aspect,
safety, has to be built in. The following questions must be addressed.
• Are the raw materials legally allowed?
• Are they safe on the skin?
• Are they safe in combination with the other ingredients?
• Is the formulation well designed from a microbiological point of view?
• Will the preservation system be effective during the intended life of the
product?
• Is the product stable in its intended packaging?
• Is the product and its packaging environmentally friendly?
The regulatory matters governing the production and sale of cosmetics will
be discussed later in this chapter (see section 12.7 and chapter 11).
12.5.1.3 Design for manufacture Quality cannot be inspected into a

product, but must be designed for manufacture. This includes:
(i) design with tolerances that can be held with existing machinery, or
formulations that can be handled by available process plant; and
(ii) design so that the product can only be assembled in the correct and
most cost-effective manner.
In many companies the designers do not involve production staff at an early

stage of a product's development.
12.5.1.4 Product approvals An increasing number of industries and

markets require product approvals, which must be taken into account at the
design stage. Techniques available to improve the quality of design include
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the following.
• Value analysis
• Failure mode and effect analysis
• Taguchi
• Competitive benchmarking
• Quality function deployment
• Reliability testing
12.5.2 Quality assurance

As described earlier, quality assurance is the development of systems,
procedures and disciplines that cover the complete manufacturing process-from
the design stage through to final testing and commissioning to ensure that the
products are produced to the correct quality standards. It includes:
(i) metrology-the science of measurement; and
(ii) statistical process control (SPC)-a powerful technique for monitoring
quality during manufacture.
SPC can be used in both process and batch production industries. It has the
added advantage that it can, in many cases, be carried out by the operators-a
very effective way of involving them in the search for quality.
12.5.3 Manufacturing processes and technology

Manufacturing processes clearly affect quality and, together with technology,
they need to be continually developed and improved to ensure that they are
capable of consistent production of the required quality. Analytical techniques
and solutions to problems are numerous. Some examples are listed below.
(i) Problem solving
• Pareto analysis
•Histograms
•Variation research
•Cause and effect analysis
• Scatter diagrams
• Regression analysis
• Taguchi
• Process mapping
• Brainstorming
• Control charts
• Project groups/task forces
(ii) Solutions
•• Operator
Design modifications
training/retraining
• De-skilling
••Improved equipment
Automation
• Better tolerancing
• Improved material specification
• Introducing or extending SPC
• Tighter process control
• Improved materials
• Preparation
• Vendor assessment
12.5.4 Cost of quality

The establishment of quality costs is an essential part of any quality
improvement programme. Various methods are available, and should cover
the following items.
• Type (i.e. prevention, appraisal, failure)
• Product line
• Manufacturing process or department
• Type of cost (material, labour)
• Causes (e.g. design, material, operator, training, etc.)
• Scope for reduction, with timescale and paybacks
These costs should identify where the maximum benefits of the quality
improvement programme can be obtained from. It is important to continually
monitor these costs once the programme is underway, to enable success to be
quantified and to identify what still needs to be done.
12.5.5 Human and organisational aspects
12.5.5.1 Top management commitment The most important contributor to

total quality is top management commitment. For many companies this
requires a wholesale change of attitude-a complete cultural change within
the company. Top management control relies on the top management being
prepared to stop the production line and solve the problems, rather than
letting the production line run for subsequent sorting. In this respect, the top
management must lead by example-quality cannot be delegated. The same
principle must apply at every level throughout the organisation. Various
studies of successful companies show that, without exception, management is
obsessed by quality.
12.5.5.2 Education To extend commitment to quality throughout each

level of the organisation requires a major educational programme, from board
level down to shop-floor or office worker. Although the content of these
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educational courses will also depend on the management level, most will
cover the following aspects.
• The importance of quality to the company in achieving its corporate
objectives
• How the quality performance of a company is perceived in the
marketplace
• The company's own cost of quality
• Training in the quality techniques such as brainstorming, fishbone
charts, pareto analysis, histograms and quality circles
• Ways in which those being trained can contribute to improving quality.
The courses should be supported with exercises and case studies that give
customer focus, evaluate processes, anticipate working for continuous
improvement and look to a leadership role in quality.
12.5.5.3 Participation Participation is an essential part of total quality,

involving everyone within an organisation. The greater the involvement, the
greater the rewards. Management needs to be far more open than they have
been historically.
12.5.5.4 Communication The 'initial customer' concept is a very effective

way to break down barriers and improve communications. Each department
(or division) treats all other departments with which it deals as either customers
or suppliers and:
(i) defines the products or services that it gives or receives;
(ii) agrees performance and quality measures; and
(iii) monitors performance against targets.
The lessons learnt from this approach can be salutary, and the results impressive.
It can do more to transform attitudes than any other single change in a total
quality programme. Internal customer/supplier agreements can be instituted.
As part of the continuing educational process, employees need to know
what the company is doing and why it is doing it, on an on-going basis.
Briefing groups, house magazines and notice boards can all play their part
in heightening awareness ofthe importance of quality, and in reporting successes.
12.5.5.5 Visible quality People must be able to see how good quality is, and
what the first time pass rate (or other measure) is. New measures may need
to be introduced. Where possible, pass rates rather than reject rates should be
stressed; in other words positive policing should be applied.
12.5.5.6 Quality circles Quality circles are voluntary meetings of peer

groups to identify and resolve problems in their immediate working area. They
can be a very effective way of involving the workforce in the search for better
quality. Quality circles tap latent creativity of employees and involve them,
where possible, in implementing the suggested solutions. The right environment,
a commitment from the top and a willingness to listen by top management
are all required.
12.5.5.7 Self-inspection Self-inspection is an integral part of the total quality

philosophy, giving the operators the responsibility for the quality of their own
work-once their attitudes are right. Most operators want to take over their
own inspection, and often set themselves higher standards than inspectors-
so-called, 'pride in the job'.
12.5.5.8 Supplier involvement A company's contacts with its suppliers are

often between the buyers and the sales man. Companies should get much
closer to their suppliers at senior management level, and involve them in their
quality problems. Suppliers can be a very useful source of information and
assistance. Most companies adopting total quality end up dramatically
reducing the number of their suppliers, single sourcing wherever practical and
offering long-term contracts in return for good performance. Supplier involve-
ment is much more than vendor assessment. New relationships with employees
and new partnerships with suppliers, should be developed.
Some companies have sensibly used common training material and
common training sessions with their suppliers. One or two companies have
even taken it upon themselves to train their key suppliers. The benefits of this
are a common language and common understanding. It can provide detailed
insight into processes and invites continuous improvement from which both
parties can benefit. Developing in parallel with these initiatives have been
electronic data interchange (EDI) where customers' and suppliers'
computers interchange requirements directly and vendor managed inven-
tories (VMI) whereby a customer's stock movements can be tracked using
data interchange by the supplier's computer which will then schedule
replenishment production. These initiatives have greatly improved accuracy
and substantially reduced inventories to the benefit of both.
12.5.5.9 Quality improvement projects Quality improvement projects are

undertaken by cross-functional and often multi-disciplinary project teams
working on a problem or series of related problems. Members usually require
training in effective group working and in problem-solving techniques.
12.5.5.10 Organisation As stated previously (section 12.5.5.1), the responsi-

bility for quality must be with top management. In a manufacturing unit, this
means that product quality must be the responsibility of the production
department. It cannot be delegated to the quality assurance department-they
should be facilitators.
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Many companies have reorganised themselves around processes rather
than stay with functional hierarchies. Processes not functions drive the
business. A process view of an organisation illustrates:
• The interdependency of organisational departments,
• The primacy of the customer (consumer),
• The impact of customer requirements and response (e.g. consumer
research),
• Continuous improvement, based on customer requirements and
response,
• The importance of suppliers,
• The network of internal customer / supplier relationships.
This process view can have significant benefits allowing decisions to be
made in the most appropriate place by the best qualified individuals. It also
results in delayering, the removal of unnecessary levels of supervision and
management.
12.5.5.11 The quality plan A quality plan should form part of each company's
corporate plan and its objectives should be included amongst the organization's
strategic business aims. The plan will need to be updated regularly-probably
annually-and should include detailed information on quantifiable quality
improvements and financial benefits, together with the resources required to
realise them.
12.6 The new thinking
A simple way of illustrating the differences between the old and new concepts
of quality is shown in Table 12.1.
Table 12.1 Differences between the old and new concepts of quality
Old New
Quality is about products Quality is about organisations

Quality is technical Quality is strategic
Quality is for inspectors Quality is for everyone
Quality is led by experts Quality is led by management
Good quality is high grade Quality is at the appropriate grade
Quality is about control Quality is about improvement
12.7 Quality standards and guides
As one might expect, there are many quality standards and guides and much
legislation (see section 12.8). All total quality approaches rely on some kind
of underpinning quality system, and a good quality system should cover

common ground no matter what the product or industry. The international
standard for quality systems-ISO 9000-developed from the haphazard
approach described earlier. It laid down internationally agreed criteria, with
inspection from independent assessors (third party assessment) to ensure that
the standard was met. Such systems were engineering-led but are fast gathering
favour within the cosmetic and toiletry industry.
A number of cosmetic manufacturers are owned by pharmaceutical
conglomerates, and their route to a quality system has been through the
manufacture and fill of 'over-the-counter' (OTC) pharmaceutical products.
Companies holding medicinal manufacturing licences are independently
audited by inspectors to maintain minimum standards. In the UK, these
companies must refer to the so-called 'Orange Guide' [5], which, although it
has no statutory force, recommends steps that should be taken as necessary
and appropriate by manufacturers of medicinal products, with the object of
ensuring that their products are of the nature and quality intended. In the US,
OTC review panels set product standards for certain cosmetic products.
Both ISO 9000 and the Orange Guide tend to focus on the manufacturing
or operational side of the business, thus missing an opportunity to exercise
some control over an industry frequently dominated by marketing, sales or
finance. This is where total quality can be very effective-given leadership
from the top, it touches the whole company. Wise companies now adopt a
dual approach, following total quality whilst trying for ISO 9000 accreditation
and/or complying with the requirements of inspectors.
12.7.1 Links between ISO 9000 and total quality

Put simply, ISO 9000 is a recognised and established example of a quality
system, and all total quality approaches rely on an underlying quality system
of some sort. At the same time, total quality pundits say that it is difficult for
an organisation to successfully install ISO 9000 without first creating a
management-led total quality approach. Consequently, it can be seen that
both approaches are independent and the distinction between the two is
blurred. The links between the two can be demonstrated by comparing the
features of both alongside each other (Table 12.2). This brings out their
strengths when linked together.
Companies advocating total quality often demand quality processes in
advance of ISO 9000 requirements from their suppliers, although they still see
ISO 9000 as a positive indicator. However, it is not entirely true to say that
ISO 9000 is short-sighted or short-term focused, as it does require a quality
policy and objectives, and organisation and management review, in addition
to quality systems.
ISO 9000, BS 5750 (the UK quality standard) and the European standard
EN29000 all had similar origins. Recognising the blurring referred to above,
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Table 12.2 Comparison ofISO 9000 with total quality
ISO 9000 Total quality
Standards to ensure that things are Focus on doing things correctly and on doing
done correctly the right things (strategic)
Primarily product/service focused Company-wide, covering all departments
A system Philosophy/management approach
No requirements for employee Emphasis on total employee involvement/
involvement in improvement commitment/attitude change
Goal-meet the standard pass the Goal-continuous improvement
audit
Low visibility Company-wide visibility
together with a wish for uniformity, the three standards have recently been
revised and merged to become BS EN ISO 9000. Such standards are regularly
reviewed and this was the case in 1994. In fact it is a requirement of the Inter-
national Standards Organisation (ISO) that all of its standards are reviewed
and either revised or revalidated every five years. This latest revision is part of
a broader programme resulting from a long term strategy adopted by the
international standards committee responsible for the ISO Series. This
strategy has been published as a document called Vision 2000 [6].
Vision 2000 calls for a two phase programme that addresses the following
issues
Phase one published in 1994:
(i) the need to correct inconsistencies and errors,
(ii) the need to improve the wording so that the standard is now more
applicable to its wider usage, particularly sectors such as service
industries,
and Phase two due to be published in 1998:
(iii) the need to make more significant changes to take account of the move
towards the principles of total quality management.
The 1994 version has added emphasis and clarification. The new standard
is not only updated but improved. Of major importance is the requirement
placed on companies to operate as they see fit. The introduction of the
standard states clearly that 'It is not the purpose to enforce uniformity of
quality systems' and 'The design and implementation of a quality system
has necessarily to be influenced by the varying needs of an organisation'.
Virtually all clauses have a word change of some sort with varying degrees
of impact. Significant changes are made in the following areas:
• Policy. The quality policy now has to 'be relevant to the supplier's
organisational goals and the expectations and needs of its customers',
i.e. it allows a customised approach to quality management. It will
require companies to implement an appropriate level of quality
management and not do anything less than is required to meet the needs
of the customer. It also introduces the concept of management with

executive responsibility for quality. This concept is used several times
and emphasises that top management should be promoting quality and
giving the lead. The greatest challenge remains in being able to
demonstrate that the policy is being implemented and understood by all
employees. Policies are one thing but actions are something else.
• Planning. The 1994 version has extended clause 4.2 to three sub-
clauses:
(i) General-the standard now requires a quality manual
(previously this was not a requirement although most companies
did produce one),
(ii) Quality system procedure-this adds 'the degree of documen-
tation required ... shall be dependent upon the methods used,
skills needed and training required by personnel', i.e. only
procedures that are actually required should be written.
(iii) Quality planning-this includes seven guidance notes amongst
its eight requirements. Additional effort will undoubtedly be
necessary to prove compliance.
• Preventive action. The new standard requires that action be taken
before problems occur to prevent potential non-conformities.
A reassuring clarification within the general paragraph is the
comment 'actions taken shall be to a degree appropriate to the magni-
tude of the problem and commensurate to the risk encountered'.
Companies may well find it advantageous to develop a risk analysis
procedure to demonstrate why, or why not, data is analysed and action
taken.
• Purchasing. Documented procedures are now required for purchasing.
Those procedures need to evaluate the sub-contractor before selection,
and the supplier shall define the type and extent of control exercised over
the sub-contractor. There is no absolute requirement to conduct quality
audits or obtain a questionnaire from sub-contractors, but there must be
evidence of some form of assessment of capability.
12.7.1.1 Bureaucracy versus the paperless approach! Assessment bodies

will frequently cite document and data control as the biggest cause of non-
conformance to ISO 9000. The effort and resource often put in place to
control this can be a burden in itself, without taking into account the asso-
ciated record keeping and the remaining company information. Computers
can help with the creation of documentation but, with networks, documents
can be rapidly proliferated throughout the organisation, working against
those trying to control it. In addition documents created by word processors
and stored on disk are generally invisible unless printed.
However. software now available is specifically designed to address these
issues, designed to act as a framework for building and running the docu-
QUALITY 377
men ted system and managing the associated records. Document control
issues are removed such that the time of the quality manager can be better
spent being proactive towards quality matters, rather than being burdened
with administration.
12.7.1.2 The future One of the great gurus of quality, Dr. Juran, made
some interesting predictions at a conference in late 1994 [7]. It seems
appropriate to close on these predictions:
• Quality competition will intensify with multi-nationals and common
markets.
• There will be intense demands on suppliers.
• ISO 9000 will sweep across the world.
• Awards, e.g. Baldrige, will supply intense stimulus and there will be a
growth in awards worldwide.
References
1. Juran, J.M. (1974) Quality Control Handbook, 3rd edn. McGraw-Hill, New York.
2. European Organisation for Quality Control (1971) Glossary of Terms used in Q.c. Rotterdam.
3. Crosby, P.B. (1979) Quality is Free. Mantor, New American Library, New York.
4. Crosby, P.B. (1984) Quality without Tears. McGraw-Hill, New York.
5. HMSO (1983) Guide to Good Pharmaceutical Manufacturing Practice. HMSO, London.
6. Vision 2000. BSI Standards, refPD6538, BSI, 2 Park Street, London WIA 2BS.
7. Juran, J.M. (1994) The Last Word. 12th Annual Conference on Managing for Total Quality.
Published in Quality World, January 1995,30.
Further reading
CTFA (1991) CTFA International Resource Manual. 3rd edn. CTFA Inc. Washington, D.C.
Imai, M. (1986) Kaizen Random House, New York.
Oakland, J.S. (1989) Total Quality Management Heinemann Professional Publishing, Oxford.
Smith, W.S. (1989) The Delighted Customer Vol. 1- The Quality Revolution Quest Quality
Consulting, London. Unilever Internal Publication.
13 Environmental issues
D.F. WILLIAMS
13.1 Introduction
Environmental regulation is widespread and virtually all embracing

throughout the world, particularly in Europe and the USA. Much of the
legislation in Europe is in a state of flux and still to be resolved into clear
regulations but in the USA the environmental restrictions on industry have
been in place for a long time. The Environmental Protection Agency (EPA)
in the USA is long standing and environmental protection agencies have now
been set up in the UK and in the European Union.
By and large the more draconian measures being put into effect in Europe
and the UK under the Integrated Pollution Prevention and Control (IPPC)
and the Integrated Pollution Control (IPC) bodies do not apply directly to
the formulation or the manufacture of cosmetics and toiletries. The
prescribed processes under these regulations do not include this industry
and are more concerned for the moment at any rate with the heavier industry
polluters of air, water and the land. Of much more concern to the formulator
and manufacturer of cosmetic and toiletry products are the regulations and
proposed tax levies associated with waste and with packaging.
Marketing attention is more and more becoming focused on environ-
mental concerns as the pressure from consumers increases. The result of
pressure from customers and retail outlets on the use of animals and animal-
derived materials as well as ozone-depleting gases is now well known and
established. The attention of the regulators is now turned to packaging waste
and of the consumer to the origin of the raw materials used in the products.
Attention to the use of energy is a significant concern also and formulations
and methods of manufacture will need to take this into account. The use of
water will be important as will all emissions from processing.
Concern is building up over the use and emission of volatile organic
compounds (VOCs). VOCs are precursors in the formation of ground ozone
(photochemical smog) and proposals for regulatory Directives are under
consideration in the European Union (EU). Regulations which directly
influence the formulation of cosmetic and toiletry products are already in
place in a number of the States in the USA.
There are of course many other factors which may affect the environ-
ENVIRONMENTAL ISSUES 379
mental policies of companies and which may well influence the customer in
the choice of products but in this chapter only those aspects concerned
directly with the formulation, development and manufacture of the product
are considered.
13.2 Raw materials
When considering the development of a new product it is common now to

concentrate on materials that have a long history and which have not been
tested on animals for many years. In the ED the 6th amendment to the
cosmetic directive prohibits the use of animals for the testing of cosmetic
products and raw materials from 1998. It is hoped that by the time this regu-
lation comes into force there will be adequate alternatives to animal testing
that will provide protection for the consumer and the manufacturers of the
products from adverse effects. A problem still exists and will continue to exist
in the regulations governing the notification of new substances. The law at
the moment in the EU requires evidence of toxicological data from animal
testing and until this is changed the cosmetic and toiletry industry will face a
dilemma when considering the use of newer materials.
In the USA the state of California has set limits on the level of con-
taminants in raw materials which has resulted in the need for manufacturers
to examine more stringently the levels of contaminants in their products.
Contamination levels above the limits could result in the requirement to label
products with compromising toxicological statements. No doubt the possible
effects of contaminants on the environment will be considered in due course.
The effect on the environment of the raw materials used and the final
product is of increasing importance and regulations requiring the labelling
of chemical substances with an environmental declaration are spreading
through the European Union. The main driving forces are the notification
of new and existing chemicals and the regulations governing the control,
packaging and labelling of hazardous substances both for supply and for
transportation.
13.3 Energy
The conservation of energy is of course a prime concern but may not be the
most significant factor in the manufacture of cosmetic and toiletry items.
The use of heat is normally low and the mixing process does not often require
large energy input. There are opportunities however for reducing these
energy requirements by the careful selection of ingredients for a formula
which may enable cold processing or lower temperatures for the preparation.
In addition the energy for mixing can be minimised by similar considerations.
More efficient emulsifiers, lower melting waxes and fatty materials and more
easily solubilised ingredients offer an approach to these objectives.
13.4 Water
The use of water as an ingredient offers little opportunity for savings since the
formula requirement is often specific. Water for processing does however
present a challenge. If hot processes can be eliminated then obviously the
need for cooling water is removed. Lower temperatures and quicker mixing
time will result in the use of less water for cooling. If water is required for
cooling it may be possible to recycle it or to use the effluent from the cooling
jackets or heat exchangers to heat some other material process. These points
are obvious but can perhaps be built on with ingenuity and perhaps can be
used to advantage in furthering the company's customer image.
13.5 Waste
As far as the cosmetic and toiletries industry is concerned the significant

waste factors can be separated into two major areas; that produced as a result
of the formulation and manufacture of the product and that produced due to
the packaging of the product. Waste produced in the factory has of course
been a traditional area of control from the cost point of view but it has taken
on a greater significance in recent years due to environmental factors. Waste
product from rejected batches of products must be disposed under strict
control. Hazardous materials may be involved. Rejected raw materials fall
into the same category. In Europe disposal must be carried out by registered
waste carriers and of course paid for. The same principles apply to reject
packaging materials and faulty components on line. It is important to ensure
good quality componentry to avoid rejects and down time on the lines but
now the disposal factor assumes greater significance in preventing cost
increases. Preventative quality assurance measures and built in fail safe
considerations at the design stage thus become even more important.
13.6 Packaging waste
It will be necessary as time passes to pay great attention to the way cosmetics
are packaged for sale due to the regulations now being discussed in the EU
and other countries. These regulations will in fact impose a levy on the
packaging industry and allied industries designed specifically to discourage
the use of excessive packaging. The imposition of tax on waste destined for
landfill will also affect the design of future packs. Point of sale and mer-
ENVIRONMENTAL ISSUES 381
chandising units will have to be looked at with environmental considerations
in mind.
Packaging waste provides a challenge and an opportunity particularly in
the product development area. The prime target of most governments
concerned with environmental problems is to minimise waste. The retail
packs of consumer products therefore provide an avenue of approach
towards achieving this aim offering the consumer an environmentally
friendly product. In the USA, California and Oregon are imposing
reductions in weight or minimum levels of recycled material in packs above
8 oz or 240 ml.
Design of packs that will use the minimum of material whilst still
adequately protecting the product will become increasingly more important.
Reusable packs and packs that can be recycled will offer further oppor-
tunities and failing all else packs that can be disposed of with no environ-
mentally deleterious effect or indeed which may provide an environmental
benefit must be considered.
Use of materials from sustainable sources and those which cause little or
no environmental problems or do not use large amounts of energy in their
preparation will increase in significance.
As ever the development of a product must ensure that the product and the
pack are designed together and that all members of the team are aware of the
environmental consequences.
13.7 Eco labelling
Consumer demand for information on the environmental acceptability of the

products they buy has led to the spread of 'Eco labelling' schemes throughout
the world. Individual countries and the EU are devising their own definitions
and specifications required for the award of an 'Eco' label, an important
factor in the development of products for the future.
13.8 Volatile organic compounds
The present situation on the use of VOCs is far more stringent in the USA
where state legislation limits considerably the use of volatile materials in
cosmetic and toiletry formulations. This drastically affects the formulation
of hairsprays and fixatives, mousses and conditioners as well as nail polish
remover, antiperspirants, deodorants and fragrances. These limitations will
lead to new technology since at the moment solutions offered to date have not
gained great consumer support. Elimination of the aerosol as we know it
today seems to be the main target ofthe regulatory bodies.
In Europe at the moment the situation is still developing and is not yet
clear. No overt regulations are aimed specifically at cosmetic and toiletry

products. There is more concern over the sale and storage of petroleum, the
coating, printing and paint industries where great changes have already taken
place in formulations and processes. The forward looking cosmetic and
toiletry formulator will be well advised to watch developments in the USA
and use innovation to lessen the dependence on the use of volatiles.
13.9 Environmental management systems
It is worthy of note that public concern about the environmental perfor-

mance of manufacturers of consumer products is growing. This concern
may well influence the choice of products the consumer may make in the
highly competitive marketplace. Any company that is able to convince the
consumer of its concern and care about the effects of its activities on the
environment may therefore well steal an edge on its competitors. It is also a
distinct possibility that the retailers who place a great deal of emphasis on
their environmental image may well force the pace and insist that their
suppliers show evidence of their commitment to protecting the environment.
Throughout the world therefore a number of schemes are being developed
that will enable companies to demonstrate such commitment through
standards and certified environmental management schemes. The British
Standards Institute have introduced BS 7750 and on the international front
an ISO Scheme (ISO 14000) is being finalised. These schemes set out the
requirements for a management system and structure which if adopted and
accepted by independent accredited assessors enable companies to claim
certified status. EMAS (Eco Management and Audit System) is a regulation
introduced into the EU (Regulation 1836/93) which set up a voluntary
scheme and was launched as a final scheme framework in April 1995. The
above standards compliment this regulation. Other standards relevant to
the Eco Management systems are BS ISO 14001 and 14040 (Life Cycle
Analysis). In January 1995 these were all in draft form and others were under
preparation covering aspects oflife cycle inventory, impact assessment and
improvement assessment. It is essential therefore that workers in the field of
consumer product maintain awareness of the developments in this important
area.
13.10 Sources ofinformation
Environmental protection agencies in the USA, the Environment Protection

Agency (EPA), the EU, the European Environment Agency (EEA) and the
UK, Environment Agency (EA) have been set up to collect and provide
objective and reliable environmental information and to assist governmental
ENVIRONMENT AL ISSUES 383
bodies in the USA, UK and European Union in formulating sound policies to
protect the environment. The EU EEA (European Environment Agency) will
publish a newsletter periodically and other countries throughout the world
will no doubt set up environmental protection bodies in time.
Trade Associations provide regular summaries of the individual state's
regulations and the development of international regulations and an
extremely important source of information on rapidly changing environ-
mental issues.
The Official Journal of the European Community (OJ) provides detailed
information on all Regulations, Directives and proposed Directives oper-
ating within the European Union. Some of the more important and relevant
environmental legislation is listed below.
13.10.1 European Community

• First Environment Action Programme (OJ Cl12 20-12-73).
• Fifth Environment Action Programme. Towards Sustainability (OJ
C138 17-5-93).
• Proposed Directive for The Integrated Pollution Prevention and
Control, a Framework Directive (OJ C311 17-11-93).
• The Directive on Packaging & Packaging Waste 94/62/EC (OJ L365
31-12-94).
• The Directive on Waste (Framework) 75/442/EEC amended by
91 /156/EEC (OJ L194 12-2-75 & OJ L78 26-3-91).
• The Directive on Toxic and Dangerous Waste 78/319/EEC (OJ L84
31-3-78).
• The Directive on Hazardous Waste 91 1689/EEC (OJ L377 31-12-91).
• The Draft Directive on the Landfill of Waste (OJ C212 5-8-93).
• Regulation on the Evaluation and Control of the Risks of Existing
Substances EC Regulation 793/93 (OJ L84 5-4-93).
• EEC Council Regulation implementing the Montreal Protocol on
Substances that deplete the Ozone Layer (OJ L67 14-3-91).
• The Directive on Air Pollution by Ozone 92172/EEC (OJ L297
13-10-92).
• The Directive on the Approximation of the Laws, Regulations and
Administrative Provisions relating to the Classification, Packaging and
Labelling of Dangerous Substances. 67/548 I EEC (OJ L196 16-8-67).
• The above amended and adapted by many Subsequent Directives up to
93/101 IEEC (OJ L13 15-1-94).
• Decision establishing a list of wastes pursuant to Directive 75 1442/EEC
(OJ L5 7-1-94).
• Regulation on the establishment of a European Environment Agency
(OJ L120 11-5-90).
• EEC Council Regulation on a Community Eco- Label Award Scheme

92/880/EEC (OJ L99 11-4-92).
• Working Document for a Draft Marking for Packaging Directive.
1-4-95 (Commission of the European Communities).
13.10.2 USA
• State Regulation of the Volatile Organic Compound content of Personal
Care Products. April 1995 (CTPA).
• The Federal Clean Air Act (CAA) Amendments 1990.
• The State of California Proposition 65 (Contaminants in Raw
Materials).
There are many other regulations governing waste solid and water quality
operating in the various states and details can be obtained from the EPA.
13.10.3 UK
• The Environmental Protection Act 1990.
Appendices
Appendix I: List of suppliers
United States
Akzo Chemicals Inc., 300 South Riverside Plaza, Chicago, Illinois 50505
Allied-Signal Inc., A-C Performance Additives, PO Box 2332R, Morristown,
New Jersey 07962-2332
Alzo Inc., 6 Gulfstream Blvd., Matawan, New Jersey 07747
Amerchol Corporation, 136 Talmadge Road, PO Box 4051, Edison, New
Jersey 10818-4051
Amoco Chemical Company, Mail code 4101, 200 East Randolph Drive,
Chicago, Illinois 50501-7125, 800-621-4567
Aqualon Company, 2711 Centerville Road, PO Box 15417, Wilmington,
Delaware 19850-5417
BASF Corporation, 140 New Dutch Lane, Fairfield, New Jersey 07004
Bernel Chemical Company Inc., 30 Park Place, Englewood, New Jersey 07631
B.F. Goodrich Chemicals, 6100 Oak Tree Boulevard, Cleveland, Ohio 44131
B.F. Goodrich, Specialty Polymers & Chemicals Division, 9911 Brecksville
Road, Cleveland, Ohio 44141-3247,800-331-1144
Cascade Chemical Company, PO Box 438, Park Ridge, New Jersey 07656-0438
Croda Inc., 183 Madison Avenue, New York, New York 10016
Dow Corning Corporation, 2200 W. Salzburg Road, Midland, Michigan
48686
EM Industries Inc., Fine Chemicals Division, 5 Skyline Drive, Hawthorne,
New York 10532
Finetex, PO Box 216, Elmwood Park, New Jersey 07407
GAF Chemicals Corporation, 1361 Alps Road, Wayne, New Jersey 07470
Goldschmidt Chemical Corporation, 914 E. Randolph Road, PO Box 1299,
Hopewell, VA 23860, 800-446-1809
W.R. Grace & Co, Co.-Conn., Davison Chemical Division, PO Box 2117,
Baltimore, Maryland 21203-2117
Henkel Corporation, Emery Group, 300 Brookside Avenue, Ambler, PA
19002
Heterene Chemical, 295 Vreeland Avenue, Paterson, New Jersey 07513,
201-278-2000
Hoechst Celanese, Colorants & Surfactants Div., Route 202-206 North,
Somerville, New Jersey 08876
ICI Americas Inc., ICI Specialty Chemicals Wilmington, Delaware 19897,

800-456-3669
lnolex Chemical Company, Jackson and Swanson Streets, Philadelphia,
Pennsylvania 19148-3497
Kelco, Division of Merck & Co., Inc., 75 Terminal Avenue, Clark, New Jersey
07066
Lonza, Inc., Specialty Chemicals Division, Corporate Headquaters, 17-17
Route 208, Fair Lawn, New Jersey 07410
National Starch & Chemical Corporation, Resins & Specialty Chemicals,
Finderne Avenue, Bridgewater, New Jersey 08807
Reheis Inc., 235 Synder Avenue, Berkley Heights, New Jersey 07922
Rhone-Poulenc Inc., Surfactants & Specialties, 1099 Winterson Road,
Linthicum, Maryland 21090
Rohm & Haas, Independence Mall West, Philadelphia, Pennsylvania 19105
Sandoz Chemicals, 4000 Monroe Road, Charlotte, North Carolina 28205
Scher Chemicals, Inc., Industrial West, Clifton, New Jersey 07012
Sherex Chemical Company, Inc., 5777 Frantz Road, PO Box 646, Dublin, Ohio
43017
Stepan Company, 22 Frontage Road, Northfield, Illinois 60093
Sutton Laboratories, Inc., 116 Summit Avenue, Chatham, New Jersey 07938
Tri-K Industries, Inc., 466 Old Hook Road, PO Box 312, Emerson, New
Jersey 07630
Trivent Chemical Company, Inc., 45 Ridge Road, PO Box 597, South River,
New Jersey 08882
Union Carbide Corporation, Specialty Chemicals Division, 39 Old Ridgebury
Road, Danbury, Connecticut 06817
Van Dyk, Mallinckrodt Specialty Chemicals, Co., Drug & Cosmetic Chemical
Division, 11 William Street, Belleville, New Jersey 07109
Wickhen Products Inc., Big Pond Road, Huguenot, New York 12746-0247
Europe/United Kingdom
Akzo Chemie UK Ltd, 1-5 Queens Road, Herstam, Walton-on-Thames
KT125NL
Albright & Wilson, White Haven, Cumbria CA28 9QQ
BASF (UK) Ltd, PO Box 4, Earl Road, Cheadle Hulme, Cheshire SK8 6QB
B.F. Goodrich, Hounslow, Middlesex
BP Chemicals Ltd, Belgrave House, 76 Buckingham Palace Road, London
SW1W OSU
Croda Chemicals Ltd, Cowick Hall, Snaith, Goole, North Humberside DN14
9AA
Dow Corning Ltd, Avco House, Castle Street, Reading RGI 7DZ
Durham Chemicals Ltd, Birtley, Chester-Le-Street, Durham DH3 lQX
GAF Europe, Rythe House, 2 Littleworth Street, Esher, Surrey KTlO 9PD
Goldschmidt AG, Goldschmidtstrasse 100, D 4300 Essen 1, Germany
APPENDICES 387
Henkel Cospha KGaA, Henkelstrasse 67, Posffach 1100, D4000, Dusseldorf 1,
Germany
Hercules Ltd, 20 Red Lion Street, London WCIR 4PB
Hiils AG, Referat 1122, D 4370 Mari, Germany
Kelco AIL Ltd, 22 Henrietta Street, London WC2E 8NB
Unichema International, PO Box 2, 2800 AA Gouda, The Netherlands
Union Carbide UK Ltd, Union Carbide House, High Street, Rickmans-
worth, Hertfordshire WD3, 1RB
Wick hen Products Inc., Cumberland House, Greenside Lane, Bradford BD8
9TO
Appendix II: Useful addresses
ACOPER, Igancio Chiappe Lemos, Calle 37, No. 7-43, Bogata, Colombia
ASCOPA, Case postale 230, CH-1211 Geneva 3, Switzerland
Associacao Brasileria da Industria de Produtos Limpezae Afins, 1570-8
Andar, San Paulo, Brazil
Associacion de Fabricantes de Articulos de Tocador, Los Laureles 365, San
Isidro, Lima, Peru
Associazione Nazionale dell'lndustria Chimica (ASCHIMICI), Via Fate-
benefratelli 10, 1-20121 Milano, Italy
Camara Argentina de la Industria de Productos de Hygiene y Tocador,
Paraguary 1857, Capital Federal, Buenos Aires (1121), Argentina
Camara de Industria Cosmetica, San Antonio 427, Santiago, Chile
Camara Nacional de la Industria de Perfumeria y Cosmetica, Talsan No. 54
Despacho 6, Mexico 1, D.F., Mexico
Camara Venezolana de la Industria de Cosmeticos y Afines (CAVEINCA),
Edificio 'IASA' Plaza la Castellana, Oficiana 106 Apartado 3577, Caracas,
Venezuela
Canadian Cosmetic, Toiletry and Fragrance Assn. (CCTF A), 24 Merton
Street, Toronto, Ontario M4S 1A1, Canada
Chamber of Cosmetics Industry of the Philippines, PO Box 4541, Manila,
Philippines
COLIPA, Rue de la Loi, 223 (Bte 2), B-1040 Brussels, Belgium
Cosmetic, Toiletry and Fragrance Assn. of Australia, 60 Yark Street, Sydney,
New South Wales 2001, Australia
Cosmetic, Toiletry and Perfumery Assn. Ltd. (CTPA), 35 Dover Street,
London WIX 3RA, England
CUPCAT, Adva. Agraciada 1670 Piso 1, Montevideo, Uruguay
Fachverband der Chemischen Industrie Osterreichs, Gruppe Korperp-
flegemittc1industrie, Schliessfach No. 69, A-lOll Wien, Austria
Federation Francaiso de 1'Industrie des Produits de Parfumerie, de Beaute et
de Toilette, 8, Place du General Catroux, F-75017 Paris, France
Indian Soap and Toiletries Makers Assn., P-ll, Mission Row Extension,
Calcutta 1, India
Industrieverband Korperpflege und Waschmittel e.V. (IKW), Karlstrasse 21,
D- 6000 Frankfurt/M 1, Germany
International Cosmetic Regulations, Allured Publishing Corporation, PO
Box 318, Wheaton, Illinois 60187, USA
International Federation of Society of Cosmetic Chemists, Delaport House,
57, Guildford Street, Luton, Bedfordshire LUI2NL, UK
Japan Cosmetic Industry Assn., 4th Floor Hatsumei Bldg., 9-14, 2-chome
Toranomon, Minato-Ku, Tokyo 105, Japan
Kemisk-tekniska Leverantorforbundet (KTF), Box 1542, S-111, 85 Stock-
holm, Sweden
Korea Cosmetic Industry Assn., 45-1, Pil-Dong, Jung-Ku, Seoul, Korea
Kosmetikkleverandorenes Forening, Boks 6780 St. Olavs PI., Oslo 1, Norway
Malaysian Pharmaceutical Trade and Manufacturers Assn., 3rd Floor, Jaya
Supermarket, Jalan Semangat, Petaling Jaya, Malaysia
Nederlandse Cosmetica Vereniging, Gebouw Trinderborch, Catharijnesingel
53,3511 GC-Utrecht, Netherlands
New Zealand Cosmetic and Toiletry Manufacturers Federation, PO Box
9130, Wellington, New Zealand
PERKOSMI, C/O P.T. Kalbe Farma, 11 Jendral a Yani, Jakarta, Indonesia
Saebo Parfumeri Toilet & Komisktekniske Artikler (SPT), Ostergade 22,1100
Copenhagen, Denmark
Savez Farmaceutiskih Drustave Jugoslavije Sekcija Za Kozmetologiju,
Askercerva 9, 6100 Ljubljana, Yugoslavia
Sindicado da Industria de Perfumaria e Artigos de Toucador; Avenida
Calogeras, 15, 4° an dar, CEP 20030, Rio de Janeiro RJ, Brazil
Sindicado da Industria de Produtos de Perfumarias e Artigos de Toucador, Av.
Paulista, 1319-9 Andar, San Paulo, Brazil
S.T.A.N.P.A., San Bernardo, 23-2, Madrid 8, Spain
Teknokemian Yhdistrys r. yu., Fabianinjatu 7B, SF-00130 Helsinki 13,
Finland
The Cosmetic Manufacturers Assn., 292/37 Lan luang Road, Siyek Mah-
amark, Khet Dusit, Bangkok, Thailand
The Cosmetic, Toiletry and Fragrance Association Inc., Suite 800, 1110
Vermont Avenue N.W., Washington, D.C. 20005
The Proprietary Association of South Africa, PO Box 933, Pretoria 0001,
South Africa
Unione Della Profumeria e Della Cosmesi (UNIPRO), Via Buonarroti, 38-
Milano, Italy
Unione Panhellenique des Industriels et Agents de Produits Cosmetiques et
de Parfumerie, 28 rue Academias, Athens, Greece
Verband der Kosmetik-Industrie, Breitingerstrasse 35, 8002 Zurich,
Switzerland
Index
IX-olefin sulfonates 5-6 Alkyl sulfates 4-5

Acyl amides 8 irritation 4
Aerosol propellants 33 Alkylamido betaines 11-12
dimethyl ether as 33 acylamphocarboxyglycinate 11
hydrocarbons as 33 acylamphocarboxypropionate 12
Afro products 201-24 acylamphoglycinate II
hair groom cream for 217 acylamphopropionate 12
hair pomades for 217 Amine oxides 12
hair structure of 201-2 Amophoteric surfactants 10-12
relaxing products 203-17 Anionic 0 /W emulsifiers 29-30
clear gel permwave for 211 Antiperspirants and deodorants 310-42
comb-out oil for 215 antiperspirants 324-38
conditioning shampoo for 204, 205 acti yes for 313
curl activator gels for 213 aluminum chloride in 317,318,319,
deep pre-conditioner for 206 320
hair conditioner for 212 aluminum chlorohydrate in 316-17
hair groom cream for 217 aluminum zirconium complexes in
hair grooming cream 214 321-4
hair relaxer cream for 210 antiperspirant spray products for
hair softening spray for 214 335-6
hair straightening formulations formulation of 337
hair relaxer creams for 207 antiperspirant stick 334
hair relaxer formula for 208, 209 formulation of 334, 335
hair styling gels for 216 basic aluminum chloride in 315-16
hot oil treatment for 205, 206 clinical assessment of 324-6
moisturizing spray mist for 215 cost of 327
neutralizer 212 esthetics of 328-9
neutralizing shampoo 209 formulation of 326,330-1
thioglycollate relaxation treatment roll-on 330, 331
209 solid clear gel for 333
permanent conditioner for 211 Avocado oil 24
protective shampoo for 204
scalp grease for 215 Baby products 183-99
setting lotion for 216 baby bath products 190-2
skin characteristics of 202-3 baby mousses 191-2
skin products bath oil 191
all-over body creams for 221-2 baby colognes 193-4
general purpose creams for 222 baby creams 186-8
glycerine silicone hand creams for 222 formulation for 186-7
hand and body lotions for 220-1 baby hair conditioner 190
hydroquinone creams for 223 baby lotions 186-8
Alkyl betaines 10 formulation of 188
skin mildness of 11 baby oil 192-3
Alkyl ether sulfates formulation of 193
1,4dioxanein 3 baby powder 184-6
structure of 3-4 formulation of 185
Alkyl phosphates 9-10 liquid talc 185
skin mildness 9-10 formulation of 185-6
390 INDEX
Baby products (contd) foundations 168-70

baby shampoo 189-90 formulation of 168-9
1,3-dioxane in 189 manufacture of 168-9
formulation of 189 lip color 149
baby soaps 188-9 lip glosses 156
baby wipes 192 consumer expectations for 156-7
consumer research for 196 formulation of 157
formulation development for 195 lip liners 157-8
formulation of 190 consumer expectations for 157
laboratory evaluation of 195-6 formulation of 157-8
manufacture of 199-200 manufacture of 158
preservation of 198 lipsticks 149-58
product safety requirements for 197 blooming of 155
quality control for 200 cande1i11a wax in 151
rawmaterialsfor 194-5 castor oil in 153
requirements for 183-4 consumer expectations for 149-50
stability of 198-9 flaming of 154
Bath additives 19-20 formulations of 150-2
thickeners for 19-20 fragrance for 153
Bath products, see Personal hygiene manufacture of 153-4
products microcrystalline wax in 151
Benzyl quaternaries 18 molding of 154
microbial properties of 18 pigments for 153
N-Butyl stearate 25 polybutene for 151
mascara 174--7
Captylic/ capric acid esters 25 consumer expectations for 174
Castor oil 24 formulation of 174
Cationic O/W emulsifiers 30 manufacture of 174
Cationic surfactants 16-19 waterproof formulas 175-7
Cetyl alcohol 28 nail polish 159-62
Cetyl trimethy1 ammonium chloride 16 bentone in 161
Cocoyl isethionates 7-8 butyl and ethyl acetate in 161
bar soap containing 7-8 camphor in 161
skin mildness of 8 consumer expectations for 159
Color cosmetics 149-81 formulation of 159-60
eye make-up manufacture of 161-2
color coating of 180 nitrocellulose in 160-1
consumer expectations for 177 polyesterresinin 161
eyeliners 177 preservation of 179-80
consumer expectations for 177 Conditioning agents 21
formulation of 177-9 dialkyl dimethyl quaternary 16
liquid eyeliners 179 dialkyl quaternaries 16
formulation for 179 fatty alcohols as 21
manufacturer of 177-9 polyquaternized polymers as 21
eyeshadow 171 silicones as 21
consumer expectations for 171 Cosmetic products regulation 344--59
eyeshadow cream 172-3 anti-aging claims 351-2
formulation of 172-4 definition of 352-3
manufacture of 171 drugs 350
pressed powder cakes for 171-2 defmition of 350
face make-up 162-71 labeling 348-50
blushers 170-1 cosmetic products 348,349,350
formulation of 170-1 country of origin 350
manufacture of 170-1 net content in 349
consumer expectations for 162-3 product identity 348-9
face powders 163-7 statement of ingredients in 349-50
formulation of 163-5 regulation of 344
manufacture of 165-7
Scott vo1umeter for 166-7 Dental products 225-69
INDEX 391
American Dental Association 241 humectants for 254-5
biological activity in 225 hydrogen peroxide in 268
claim support of 242 ingredients for 247-8, 250, 266
consumer practices in 237-8 manufacture of 261-2
dental calculus 231 packaging for 262-3
dental caries 226 phosphates in 268
dental floss 238, 240, 245 polymers for 256, 257
dental hypersensitivity 234 quaternary ammonium compounds in
dental pellicle 228 267
dental plaque 228 rheology of 249-50
gum disease 230 silica for 252-3,257-8
structure of 229 sodium dodecylbenzene sulfonate in
dental stain 233-4 259
denture cleansers 240,269 sodium lauroyl sarcosinate in 259
gingivitis 231 sodium lauryl sulfate in (SLS) 259,268
hydroxyapatite 227 stannous salts in 267-8
marketing of 239 surfactants for 258-9
mechanical devices for 237 thickeners for 255-6
mouthwash 264 triclosan in 267
formulation of 264 xanthan gum in 256
ingredients for 264 zinc salts in 268
manufacture of 265 water irrigators 238
packaging of 265-6 Deodorants 338-43
pre-brushing rinse for 265 antimicrobial agents for 339
oral hygiene in 225-6 clinical assessment of 339-40
oral irrigator 245 deodorant spray 340
oral malodor 234 formulation for 341-2
oral rinses 237-9,263-4 deodorant stick 340
periodontal disease 226,232, 233 formulation for 341
definition of 232 formulation for 329,330,331
dental plaque in 232 odor control in 338-9
product evaluation of 242 triclosan for 339
regulation of 240-1 regulations for 312-3
saliva and crevicular fluid 226 sticks for 332
tartar, see Dental products, dental Diisopropyl adipate 26
calculus
teeth 226 EDTA, see Ethylenediamine tetraacetate
tooth diagram 227 Emollients 21
tooth powder 236 Environmental issues 378-84
tooth whiteners 268-9 eco labelling and 381
toothbrush 236-8,240,244 energy and 379-80
design of 245 environmental management systems
formulation of 244 382
plaque removal by 244-5 sources of information 382-3
stain removal by 245 environmental regulation 378-9
toothpaste 235-6,239,260 packaging and 380-1
abrasives for 250,251,252,254 raw materials and 379
alumina trihydrate in 254 volatile organic compounds and 381-2
anti-caries agents for 266 waste and 380
calcium carbonate in 253 water and 380
calcium phosphates in 253 Ester quaternaries 18
carboxymethyl cellulose in 258 fabric softeners from 18-19
chlorhexidine in 267 Ethoxylated surfactants 13-14
dentine abrasion (RDA) of 243 fatty alcohol ethoxylates 13
flavor for 259-60 HLB 14
formulation of 246, 248, 249 Ethylhexyl esters 25
glycerin for 256
herbal compounds in 267 Fatty acids 29
human studies of 243 Fatty alcohols 28
392 INDEX
Foam stabilizers 20 perfume for 76

acyl diethanolamide as 20 plasticizers for 76
acyl monoethanolamide as 20 solvents for 76
alkanolamides as 20 hair structure 37
amine oxides as 20 keratin in 38
betaines as 20 hair thickeners 69
Fragrance, see Perfumery hair tonics 71
formulations of 71
Glycerol monostearate 28 monoethanolamine lauryl sulphate in 42
Glyceryl hydeoxystearate 27 non-aerosol mousse 79
permanent waving 84-9
Hair care products 36-100 chemistry of 85-7
bleaches 89 formulation of 88-9
formulation of 90 pomades 83
formulation of bleach 'booster' 90 sculpting spray 78
hydrogen peroxide in 90 setting lotions 77-8
brilliantines 83 formulation of 77
cocamidopropyl betaine in 43 shampoo
conditioners anti-build-up 56
auxiliary emulsifiers for 66 anti-dandruff 56-7
bodying agents for 66 formulations of 57
cationic polymers for 63 zinc pyridinethione in 56
cationic surfactants for 60-1 baby 56
clear 68 cocamidopropyl betaine in 42
formulation of 69 colour stability of 55-6
colors for 68 conditioning agents 52, 55
formulation of 62-5 formulation for 52-4
hot oils 69-70 foam stabilizers 45
leave-on 69 diethanolamide in 45
formulations of 69 monoethanolamide in 45
manufacture of 68 impurities in 57-8
oil components for 66 1A-dioxane as 58
perfumes for 67 nitrosamines as 57
preservatives for 68 opacifiers for 50
properties of 59 pearlizers for 50-2
raw materials for 59 perfumes for 49
thickeners for 67 preservatives for 49-50
UV absorbers for 72 thickeners 45-7
creams 83 shampoo detergents 40-2
formulation of 84 diethanolamine lauryl sulphate as 42
gloss sprays 79 sodium lauryl ether sulphate as 40
hair dyes 91-9 sodium lauryl sulphate as 41-2
claims for 99 triethanolamine lauryl sulphate as 42
dye removers 97 shampoo formulations 42, 44
permanent hair dyes 93-7 spray gel 78
product evaluation of 98 spritz 78
safety of 99 styling creams! glazes 82
semi-permanent hair dyes 92 styling gels 81
formulation of 93 formulation of 81
stability testing 98 styling waxes 83
temporary dyes 91-2 formulation of 83
hair gels 79-80 volume spray 79
formulation of 80 wet-look
hair oils 83 formulation of 78
hairsprays 72-7 Humectants 33
formulation of 73
ingredients for 74 Isocetyl stearate 26
neutralizers for 76 Isopropyl esters 24
other additives for 77 isopropyl myristate 24
INDEX 393
isopropyl palmitate 24 odor types for 282-3
isopropyl stearate 24 packaging for 277
plant products for 274
Jojoba oil 24 quality control of 286---7
raw materials for 273-5
Linear alkyl benzene sulfonate 6 role of 272-3
safety of 277-8
Magnesium lauryl sulfate 4--5
shave products 285
TEA salts of 4
fragrances for 285
use in toothpastes 4--5
skin creams 283
Magnesium surfactants 9
fragrances for 283
Mineral oil 22
special addi tives for 287-8
Monoalkyl quaternaries 16
stability testing of 285
Natural waxes 26 suncare products 285
beeswax 26-7 fragrances for 285
candelil1a wax 27 talcs 284
carnuba wax 27 fragrances for 284
Non-ionic O/W emulsifiers 30 testing of 278
Non-ionic surfactants 13-15 Personal hygiene products 290-309
after-bath conditioners 309
Octyldodecanol 26 liquid talc 309
Oil-in-water(O/W) stabilizers 30-1 bath crystals 300
Oleic acid esters 25 bath cubes 299-301
Olive oil 24 bath oils 305
dispersible 306---7
Peanut oil 24 floating 307-8
Pearlescent agents 21 formulation of 308
Pentaerythriotol tetraisostearate 26 foaming bath oils 305
Perfumery 272-89 formulation of 305-6, 307
accords for 279,280 soluble 306
aerosols for 283 bath salts 299
antiperspirants 283 foam bath 301-2
fragrances for 283 amphoteric surfactants for 304
aroma chemicals for 274 color for 303-4
assessment of 280-1 emollients for 304
baby-care products 285 formulation of 302, 305
fragrances for 285 opacifiers for 304
bath products 284 perfume for 302-3
fragrances for 284 preservative for 303
compounding of 286 surfactant for 302
costof 277 personal hygiene 290
creative process for 278-9 shower gels 308
definition of 272 formulation of 308
development of 276 soap 290-9
evaluation of 281 abrasives for 294
face powders 285 color for 291-2
fragrances for 285 deodorants for 294
hair products 283-4 extracts for 294
fragrances for 283-4 formulation of 291,296-7
permanent waves 284 fragrance for 292
fragrances for 284 natural oils for 294
shampoos 284 shaving soaps 295
fragrances for 284 superfatting agents for 293-4
lipsticks 285 synthetic detergent bars 299
fragrances for 285 titanium dioxide in 291
market for 281 toilet soaps 290
marketing of 281 translucent soaps 297
natural raw materials for 273-4 transparant formulas 297-8
odor descriptors of 288-9 transparent soaps 295-6,298
394 INDEX
Polyol esters 28 astringents/toners 121

formulation of 121
Quality 362-77 bar soaps 122
animal rights 358 formulation of 122
Consumer Product Safety Commission blood supply of 107
355 cell turnover testing 110
cosmetic products 344--5 cleanser mildness testing III
cost of quality 370 consumer testing of 113
environmental laws 358 efficacy testing of 109
European 356-7 formulations of 112
Federal Trade Commission 353-4 instrumental test for 110
Food and Drug Administration 346-7 liposomes in 144
color additives 348 formulation of 144--5
hair dyes 348 manufacturing trials for 115
inspection of 363-4 microbiological testing of 115
Japan 357 physiology of 104--8
manufacturing processes for 369-70 sebaceous glands of 107
product liability 359 skin color 108
quality assurance 369 sweat glands of 108
quality circles 371-2 sweating, mechanism of 314
quality standards 373-7 skin care products 104-45
ISO 9000 as 374--6 moisturizers 123-8
Sixth Amendment 356 all purpose creams 124
total quality 365-73 formulation of 124, 125
ISO 9000 in 375 facial moisturizer 126
market research in 367-8 formulation of 127
product design in 367 hand and body creams 126-8
self-inspection in 372 formulation of 126
supplier involvement in 372 hand and body lotions 125-7
United States 345-6 formulation of 125
Quaternary ammonium surfactants 17 tests for moisturizers 109
conditioning properties of 17 particulate scrubs 122
formulation of 122
Raw materials 1-35 regulatory requirements of 116-17
safety testing of 116
Sequestering agents 22 sebum testing of 111
Shampoo additives 19-20 skin cleansers 117-23
thickeners for 19 anhydrous oily cleansers 118
Silicone oils 27 classification of 117-18
Skin cleansing milks 119
acne 141-4 formulation of 119
acne grades 142 cold creams 118
sebaceous gland in 141 formulation of 118
treatment of 143-4 mild syndet bars 120
13-cis-retinoic acid in 143 formulation of 120
retinoic acid in 143 super fatted bars 121
anatomy of 104--8 formulation of 121
dermis 106 water-in-oil emulsions 118
epidermis 106 stability testing 114
fibroblasts/ collagen/ elastin 107 sunscreen products 130-40
mast cells 107 sensitivity to UV of 132-3
stratum basale 106 solar radiation and 130-1
stratum corneum 106 sunscreen chemicals for 133
stratum granulosum 106 aerosol spray formulation of
stratum spinosum 106 139
anti-aging products 128-30 burn-block pigmented stick
IX-hydroxy acids for 129 formulation of 140
regulatory factors of 130 formulation of 136-40
retinoids for 129 lip-balm stick formulation of 140
INDEX 395
non-waterproof suntan lotion skin mildness of 7
formulation for 137 syndet bars from 7
spray pump formulation of 139 Surfactants 1-16
sunblock formulation of 138 Synthetic waxes 27
suntan oil formulation of 138
waterproof sunblock cream, Triacetyl methyl ammonium chloride 17
formulation of 137-8 Trialkyl quaternaries 16
testing of 133 Triglycerides 23
UV absorbers for 134-5
UV-Aradiation 131-2 Water-in-oil (JV /0) emulsifiers 31-2
UV-Bradiation 131-2 lanolin derivatives as 32
Soyoil 24 sorbitan monooleate as 31-2
Stearyl alcohol 28 water-in-oil stabilizers 32
Sulfosuccinates 6-7 Wheat germ oil 24

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Chemistry and Technology

BLACKIE ACADEMIC &. PROFESSIONAL

London· Weinhelm . New York· Tokyo· Melbourne· Madras

Chapman & Hall, 2-6 Boundary Row, London SE1 8HN, UK

First edition 1992

ISBN-13 :978-94-0 10-7194-9 e-ISBN-13:978-94-009-1555-8

00 Printed on permanent acid-free text paper, manufactured in accordance

List of Contributors xiii

2.7 Other styling aids in spray form 78

3 Skin-care products 104

3.8.2 Sunscreen chemicals 133

4 Color cosmetics 149

4.1 Introduction 149

5 Baby care 183

5.5 Developmental pathways 195

6 Afro products 201

7 Dental products 225

7.1 Introduction 225

7.6 Oral-care product marketing 239

9 Personal hygiene products 290

9.2.1 Toilet soaps 290

10 Antiperspirants and deodorants 310

11 Regulation of cosmetic products 344

11. 7.2 Animal protection and rights 358

13 Environmental issues 378

Mr J.F.L. Chester Conform Associates, 80 Broadacres, Carlton, Goole,

Mr D.F. Williams Environment and Quality Assurance Manager, Givau-

D.F.W. May 1996

A wide range of chemical and natural materials is used in the formulation

1.2 Basic surfactants

1.2.1 Alkyl ether sulfates

although the foam structure is relatively coarse. Foaming is not affected by

1.2.2 Alkyl sulfates

LS, TEA LE2S, Na LE3SC, Na PFAC, K

1.2.3 a-Olefin sulfonates

a-Olefin sulfonates are a mixture of alkene sulfonates and hydroxy alkane

1.2.4 Other basic surJactants

1.3 Mild anionic surfactants

Compared to the basic surfactants, a much wider group of mild anionic

Sulfosuccinates represent a diverse group of derivatives of sulfosuccinic acid.

1.3.2 Cocoyl isethionates

At room temperature cocoyl isethionate shows only limited solubility in

1.3.3 Acyl amides

1.3.4 Alkyl ether carboxylates

(OCH2 -CH2)-x-OCH2 -COOM

Alkyl ether carboxylates are prepared by reaction of chloroacetic acid with

1.3.5 Magnesium surJactants

It is often stated in literature that magnesium surfactants have significantly

1.3.6 Alkyl phosphates

1.4 Amphoteric surfactants

Amphoteric surfactants are surfactants where the charge changes as a function

1.4.1 Alkyl betaines

1.4.2 Alkylamido betaines

Alkylamido betaines are prepared by condensation of fatty acids with di-

1.4.3 Acylamphoglycinates and acylamphopropionates

CH 2CH 20CH 2COONa Acylamphocarboxyglycinate

RCO-NH-CH 2CH2-N-CH 2 CH 2COONa

RCO-NH-CH 2CH2-N-CH 2CH 2COONa

The most important products of this group are the cocoderivatives-coco-