United States Patent (19) 11 Patent Number: 5,047,234

Dickerson et al. (45) Date of Patent: Sep. 10, 1991

(54) AIR FRESHENER COMPOSITION FOREIGN PATENT DOCUMENTS
11a. 31485 7/1981 Europe ............................ C1)/00
75) Inventors: Lyndel D. Dickerson, Centerville; 164818 12/1985 Europe .......................... A61/914
John A. Ferguson;i, Donald
both of Cinci
Cashman,
all of Ohi 231084 8/1987 Europe .......................... A61 L/901
oth of Cincinnati, all of Ohio 305561 3/1989 Europe ......................... A62D
73) Assignee: Drackett Company, Cincinnati, Ohio 2032959 2/1987 Japan .................................. 424/76.2
s Primary Examiner-Thurman Page
(21) Appl. No.: 397,806 Assistant Examiner-James M. Spear
22 Filed: Aug. 23, 1989 Attorney, Agent, or Firm-Sandra Nolan; Charles Zeller
51) Int. Cl. ........................ A61L 9/015; A61L 9/04; (57) ABSTRACT
m A61L 9/12 The useful life-i.e., emulsion stability and weight loss
52 U.S. C. .................................. 424/76.2; 424/76.3; control-of aqueous air freshener composition can be
w 424/76.4; 512/2; 512/3; 239/44 enhanced via the use therein of small amounts of certain
(58) Field of Search .............................. 424/76.2, 76.3 inorganic metal salts.
56) References Cited
U.S. PATENT DOCUMENTS
4,261,849 4/1981 Benjaminson ..................... 252/106
4,285,905 8/981 Feit ................................... 422/239 18 Claims, 1 Drawing Sheet

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U.S. Patent Sep. 10, 1991 5,047,234

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FIGURE
 5,047,234
1. 2
AIR FRESHENER COMPOSITION DESCRIPTION OF THE INVENTION
The invention is based upon the discovery that cer
BACKGROUND tain inorganic salts, when added to aqueous emulsion air
Air freshener compositions containing substantial fresheners, produce stabilizing effects-that is, the
amounts of water, i.e., aqueous air fresheners, are emulsion is more stable (phase separation is inhibited)
known compositions. and the useful life is extended (the amount of time
Air freshening compositions may be disseminated needed for loss of volatile fragrance components in
into the environment by controlled volatilization of the creases).
composition from a reservoir via an emanating source. The compositions of the invention may contain eight
components:
Any number of emanator designs may be utilized so A. A salt
long as sufficient surface area and pore size is main B. Avolatile solvent
tained to permit an effective mass transport of the com C. An emulsifier, with optional neutralizer
position to the emanator for volatilization into the envi 15 D. An optional co-solvent
ronment. In practice, the emanator serves as the meter E. A fragrance
ing device or rate determining mechanism step for the F. Water
evaporation of the disclosed composition. As the com G. A colorant
position volatilizes, the low volatile and/or nonvolatile H. Other excipients.
materials collect on the emanator surface. Generally the 20
evaporations rate is significantly affected when the pore DRAWING
volume (pore volume defined as the void area in the The Figure is a plot of three curves, showing percent
emanator surface) decreases below 50%. In some ex age weight loss over a period of days using the samples
treme cases, build up of nonvolatile or low volatile and testing methods described in the Example. It could
materials will actually clog the emanator surface and 25 be entitled "Air Freshener Weight Loss vs. Time'.
render the product nonfunctional. Thus, a desirable A. SALTS
feature of an aqueous air freshening composition would
be the maintenance of a uniform rate of volatilization The salts useful to produce the beneficial results de
over the product life. scribed herein are generally inorganic metal salts. They
THE INVENTION
30 usually contain Group IA (alkali metal) or Group II A
(alkaline earth metal) cations. The preferred metals are:
It has been found that the addition of a small amount Li, Na, K, Be, Mg, Ca, Sr, and Be. Na and Mg are
of an inorganic salt to an aqueous air freshener composi highly preferred.
tion, which composition is disseminated into the atmo 35 The anionic portion of the salt molecules will gener
sphere by a controlled volatilization from an emanator ally be a halide, sulfate, phosphate, nitrate, carbonate or
pad, lengthens the useful life of the air freshener. bicarbonate. Halides and sulfates are preferred.
In other words, applicant has found that the inclusion Magnesium and sodium chloride and sodium sulfate
of 0.002 to 0.010 M of a nonvolatile, weakly solvated are highly preferred. Sodium chloride is most preferred.
salt in the perfumed composition produces a more uni Mixtures are operable.
form evaporation rate of an effective quantity of the B. SOLVENT
organoleptic perfume. This is measured by an increase The principal solvent in the compositions of the in
in the time it takes for the total composition to volatilize vention contains at least one alcohol material. By "alco
from the emanator pad without losing effectiveness as hol' is meant mono-hydric alkanols containing from
an air freshener.
The inorganic additive(s) inhibit or retard weight
45 about 2 to about 12 carbon atoms and having straight,
loss, so that the evaporation rate of the freshener is cyclic or branched character. C3-5 monoalcohols are
slowed. In a preferred embodiment, from about 0.1 to preferred. Propyl alcohols are more preferred. Isopro
about 0.2 wt.% of sodium chloride is added to an aque pyl alcohol is highly preferred. Mixtures are operable.
ous air freshener compositions. The resultant composi 50 The solvent component solubilizes the fragrance and
tions evaporate at slower rates, so that their useful lives is believed to aid in controlling the formulation's evapo
ration.
are extended for about one to about three weeks.
Accordingly, the invention is concerned with the C. EMULSIFIER
methods for extending the useful life of air fresheners. The emulsifier component is at least one of a group of
such as those described above and to novel composi 55 phosphate ester emulsifiers. Also termed "hydroxy
tions which employ same. phosphoric acids", these compounds conform to the
ADVANTAGES general formula:
The compositions and methods of the invention have
several advantages over known formulations and meth
ods. The compositions of the invention have signifi wherein R is an alkylphenol moiety, preferably nonyl
cantly longer useful life due to the presence of the salts phenol, and x is an integer between about 3 and about
described herein, 15, preferably about 8 to about 11.
In addition, the salts assist in inhibiting phase separa One highly preferred material is Monafax. 785 TM a
tion in the formulations. 65 product of Mona Industries, Inc. of Paterson, N.J.) the
Other aspects and advantages of the invention will exact formula of which is proprietary. It is believed to
become apparent from a consideration of the following be a poly-(oxy-1,2-ethandiyl) alpha-nonylphenol
description and claims. omega-hydroxy phosphoric acid, typically referred to
 3
5,047,234 4.
as a phosphate ester emulsifier (see McCutcheon's Emul hols and their esters, aldehydes and ketones. Some of
sifiers and Detergents, North American Edition, 1984, the more important of these are geraniol, citronellol and
page 198). terpineol, citral and citronellal, and camphor. Other
Monafax 786 TM (from Mona Industries) is also constituents include aliphatic aldehydes and also aro
highly preferred. It is a nonoxynol-6 phosphate and is matic compounds including phenols such as eugenol.
described at page 55 of the CTFA Cosmetic Ingredient In some instances, specific compounds may be iso
Dictionary, J. M. Whelan, ed., 3rd ed. Supp. (1985) lated from the essential oils, usually by distillation in a
Another commercial phosphate ester emulsifier suit commercially pure state, for example, geraniol and
able for use in this invention is available as Phosphor citronellal from citronella oil; citral from lemon-grass
ester 610 from the Sandoz Chemicals Corporation of O oil; eugenol from clove oil; linalool from rosewood oil;
Charlotte, N.C. In Sandoz bulletin #7-477/83, it is de and safrole from sassafras oil. The natural isolates may
scribed as having exceptional solubility and as being an also be chemically modified as in the case of citronellal
excellent emulsifier, even in high concentrations of to hydroxy citronellal, citral to ionone, eugenol to van
alkali and salts. The manufacturer described it as a solu illin, linalool to linallyl acetate, and safrol to heliotropin.
bilizer of nonionic surfactants and as an emulsifier for 15 Animal products used in perfumes include musk,
aromatic and chlorinated solvents. ambergris, civet and castoreum, and are generally pro
The emulsifier components of the inventive composi vided as alcoholic tinctures.
tions may contain optional neutralizers, e.g., aqueous or The synthetic chemicals include not only the synthet
non-aqueous base(s), to bring them to about pH 7. ically made and the naturally occurring isolates men
D. FRAGRANCE
20 tioned above, but also include their derivatives and
compounds unknown in nature, e.g., isoamylsalicylate,
It is well known that the fragrant materials of air amylcinnamic aldehyde, cyclamen aldehyde, heliotro
fresheners include a significant amount of one or more pin, ionone, phenylethyl alcohol, terpineol, undecallac
volatile perfume ingredient(s) in various proportions. tone, and gamma nonyl lactone.
Typically, the perfumes incorporated in the composi 25 Perfume compositions as received from the perfum
tions used in air fresheners are mixtures of organic com ery house may be provided as an aqueous or organically
pounds admixed so that the combined odors of the indi solvated composition, and may include as a hydrotrope
vidual components produce a pleasant or desired fra or emulsifier a surface active agent, typically an anionic
grance. While perfumes are generally mixtures of vari or nonionic surfactant, in minor amount. The perfume
ous materials, individual compounds maay also be used 30 compositions are quite usually proprietary blends of
as the perfume ingredient. Typical compounds for use, many different fragrance compounds to achieve a par
in mixtures or individually, include methyl salicylate, ticular odoriferous effect.
d-limonene and the like. Typically, perfume compositions contain an effective
The perfume compositions generally contain several fragrancing amount of 0 to 100% by weight of the fra
"notes," each having different volatility rates and there 35 grance ingredient. Generally, perfume ingredient(s) are
fore being subject to the process of chromatography used in air fresheners at concentrations of about 0.01 to
which may result in a differential distribution of the 75 wt.%, with solvents, emulsifiers, water, etc. making
notes at various times. The various notes include a main up the balance.
note or the “bouquet" of the perfume composition, E. WATER
modifiers which round off and accompany the main
note, fixatives including odorous substances that lend a The water component used herein may be commer
particular note to the perfume throughout each of the cially available, or laboratory-prepared, deionized or
stages of evaporation, substances which retard evapora demineralized water. Deionized water is preferred.
tion, and top notes which are usually low-boiling, fresh Softened water can be used. If softened water is used,
smelling materials. 45 the presence of the softening salts must be considered
Perfumery raw materials may be divided into three and the quantity of additional salt appropriately re
main groups: (1) the essential oils and products isolated duced.
from these oils; (2) products of animal origin; and (3) In Table I, the term "q.s. to 100%" means a quantity
synthetic chemicals. Many of these materials include of water sufficient to yield 100% by weight of the total
such substituent groups as the carbonyl group in alde 50 composition.
hydes and ketones; the hydroxyl groups in alcohols; the
acyl group in esters; the C-0 groups in lactones; nitrile F. CO-SOLVENT
groups, and the oxy moiety in ethers. The co-solvent is an optional ingredient. When used,
The essential oils consist of complex mixtures of vola the co-solvents are generally polyalkylene glycol
tile liquid and solid chemicals found in various parts of 55 monoalkyl ethers.
plants. Mention may be made of oils found in flowers, Dialkylene glycol monoalkyl ethers are preferred.
e.g., jasmine, rose, mimosa, and orange blossom; flow Diethylene glycol monoethyl ether, ie., "Carbitol' is
ers and leaves, e.g., lavender and rosemary; leaves and highly preferred. Mixtures can be used.
stems, e.g., geranium, patchouli, and petitgrain; barks, One particularly useful material of this type is the
e.g., cinnamon; woods, e.g., sandalwood and rosewood; ethoxydiglycol product sold as Dowanol DETM by
roots, e.g., angelica; rhizomes, e.g., ginger; fruits, e.g., Dow Chemical (Midland, Mich.) or Carbitol, Low
orange, lemon, and bergamot; seeds, e.g., aniseed and Gravity TM, as sold by Union Carbide Corp. of Dan
nutmeg; and resinous exudations, e.g., myrrh. These bury, Conn. The latter compound can also be called
essential oils consist of a complex mixture of chemicals, 2-(2-ethoxyethoxy)ethanol.
the major portion thereof being terpenes, including 65 This component of the composition functions as an
hydrocarbons of the formula (C5H8) and their oxygen auxiliary solubilizer and also as a volatile non
ated derivatives. Hydrocarbons such as these give rise organoleptic diluent which attenuates fragrance inten
to a large number of oxygenated derivatives, e.g., alco sity.
 5,047,234 6
5
G. COLORANT
Monafax 785, ispropyl alcohol, and fragrance oil are
mixed until a clear solution is obtained. The water is
The colorants used in the formulations herein are added to this solution slowly with stirring. This results
commercially available dyes, preferably water soluble in a clear microemulsion. Dowanol DE (cosolvent) is
dyes. then added with stirring followed by the sodium chlo
Useful colorants include, but are not limited to, ride. The following formulae were prepared.
Azure Blue (Hilton-Davis Chemical), Erio Orange Dye Each of these formulations is the same except for the
(Ciba-Giegy), Rhodamine EB, and E-2CL from Sandoz quantity of sodium chloride and water. Levels of so
Corporation. Mixtures may be used. dium chloride shown here are 0.0, 0.1 and 0.2% respec
10 tively.
H. OTHER EXCIPIENTS
The air freshener compositions of the invention may RAW MATERIAL % WEIGHT
contain a wide variety of excipients. Along with water, FORMULATIONA
co-solvents, and other diluents, they may also contain at
least one other conventional ingredient, in addition to 15 Deionized Water 76.279
Isopopropyl Alcohol 8,000
the fragrances, colorants, neutralizers, and the like de Dowano DE 5.000
scribed herein. The use of fillers, thickeners, and the Monafax 785 6,000
like, in suitable quantities appropriate to their functions, Fragrance Oil 4.000
is contemplated. NaOH (50% solution)
NaCl
0.720
0.000
AMOUNTS OF INGREDIENTS
20 Dye (Sandoz E-2CL) 0.001
100,000
Table I gives approximate weight percentage ranges FORMULATION B
for the ingredients used in the compositions of the in Deionized Water 76.179
vention. A skilled artisan can extrapolate from the val Ispopropyl Alcohol 8,000
ues given in order to tailor a composition to his specific 25 Dowanol DE
Monafax 785
5.000
6.000
needs. Fragrance Oil 4.000
The ingredients in Section H are optional, and are not NaOH (50% solution) 0.720
shown in Table I. NaCl 0.100
Unless otherwise stated, all percentages recited in the Dye (Sandoz E-2CL) 0.001
specification are weight percentages based on total 30
FORMULATION C
00,000
composition weight. The terms "wt.%," "weight %," Deionized Water 76,079
and "wt present" are used interchangeably herein. Ispopropyl Alcohol 8.000
TABLE I Dowarlo DE S.000
Monafax 785 6,000
Amounts of Ingredients 35 Fragrance Oil 4.000
WEIGHT PERCENT NaOH (50% solution) 0.720
COM- HIGHLY NaCl 0.200
PONENT BROAD PREFERRED PREFERRED Dye (Sandoz E-2CL) 0.00
Salt 0.01-0.50 0.01-0,03 0.1-0.2 100,000
Solvent 3.0-15.0 ...O-O.O 8.0
(principal) 40
Emulsifier 2.0-15.0 4.0-7.5 6.0 Five samples were prepared from each formulation
Neutralizer 0.01-2.0 0.48-0.84 0.72 and each delivery system contained 65.0 grams of for
Fragrance
Co-Solvent
1.0-20.0
0-15.0
3.5-6.0
0-7.5
6.0
5.0
mula. Each liquid samples was then placed in a con
Colorant 0.0001-0,005 0.000-0003 0.0024
tainer in an environment which had air flow between
Water qs, to 100% q.s. to 100% q.s. to 100% 45 8-20 linear feet/minute, temperature 72+3 F., and
"The example shows compositions containing 50% aqueous solution of NaOH. relative humidity of 50-10%
Samples were removed from this environment once
As used herein the phrases "suitable amount", "useful each week and weighed on an analytical balance. The
amount', 'suitable quantity', and the like refer to samples were weighed each week until there was no
amounts of an ingredient which are appropriate to its SO visible liquid left in the container. The percent weight
function in the final composition, Thus, a 'suitable sta loss was calculated by the following formula:
bilizing quantity' or "stabilizing amount' of a salt %wt, loss=1-(fw-(ow-cw))/fw
would be an amount sufficient to produce the stabilizing fw=fill weight
effects, i.e., inhibition of phase separation and/or exten ow = original weight of the package with formula
sion of the useful life of the air freshener via decrease of 55 cw = weight at some time t (t was measured in days)
the rate of evaporation. As FIG. 1 shows, the composition of the example
produced significantly slower cooperation rates when
EXAMPLES 0.1% and 0.2% NaCl were added.
The following example illustrates the invention. Table II sets out the fragrance weight loss of Formu
Preparation of formula: lations A-C when tested as described above. The com
positions tested are the same lemon air fresheners
shown in the Figure.
TABLE II
FRAGRANCE WEIGHT LOSS, WITH TIME, OF FORMULATIONS A-C
(0.0, 0.1, AND 0.2) 9% NaCl
Week O 2 3 4 s 6 7 8 9 O 11 2 13 4. 15
Day O 14 21 28 3S 42 49 56 63 70 77 84 9. 98 05
0% NaCl O 35.54 49.92 58.69 65.62 70.62 74.69 78.38 81.23 83.23 85.46 87.54
 5,047,234
7
TABLE II-continued
FRAGRANCE WEIGHT LOSS, WITH TIME, OF FORMULATIONS A-C
(0.0, 0.1, AND 0.2) 7% NaCl
0.1% NaCl. 0 32.26 45.38 53.54 60.21 65.23 69.44 73.38 76.56 78.87 8.54 84.46 86.31
0.2% NaCl 0 30.8 43.5 51.35 57.88 62.74 66.83, 70.71 73.72 75.94 78.49 81.2 83.4 84.95 86.22 86.92

9. The method of claim 7 wherein the halide is so

It should be understood that reasonable variations, dium chloride,
modifications and improvements, may be made by those 10. The method of claim 7 wherein the sulfate is
skilled in the art in the invention disclosed herein with sodium sulfate.
out departing from the spirit and scope thereof. 11. The method of claim 7 wherein the halide is mag
We cairn: nesium chloride.
1. An aqueous air freshener composition consisting 12. A method of inhibiting the weight loss of an emul
essentially of: sified aqueous air freshener composition, consisting
(a) about 1 to about 20 wt.% of a fragrance compo essentially of about 1 to about 20 wt.% of a fragrance
nent, component, about 3 to about 14 wt.% of a monohydric
(b) about 2 to about 15 wt.% of an emulsifier, alcohol having 2 to about 12 carbon atoms and about 2
(c) about 0.01 to about 0.5 wt. % of at least one to about 15 wt.% of an emulsifier, which comprises the
weight loss inhibitor which is an alkali metal or 20 step of adding thereto about 0.01 to about 0.5 wt.% of
alkaline earth metal halide, sulfate, nirate, carbon at least one weight loss inhibitor which is an alkali metal
ate, bicarbonate or phosphate, and or alkaline earth metal halide, sulfate, nitrate, carbonate,
(d) about 3 to about 15 wt.% of a monohydric alco bicarbonate, or phosphate.
hol having 2 to about 12 carbon atoms. 13. The method of claim 12 wherein a halide or sul
2. The composition of claim 1 wherein the composi 25 fate inhibitor is used.
tion contains a halide or a sulfate inhibitor. 14. The method of claim 12 wherein the halide is
3. The composition of claim 2 wherein the alcohol is sodium chloride.
ethyl or isopropyl alcohol. 15. The method of claim 12 wherein the sulfate is
4. The composition of claim 2 further containing from sodium sulfate.
about 0.0001 to about 0.005 wt.% of a colorant. 30 16. The method of claim 12 wherein the halide is
5. The composition of claim 3 wherein the stabilizing magnesium chloride.
agent is sodium chloride. 17. In an air freshener device comprising an air fresh
6. The composition of claim 3 wherein the stabilizing ener composition containing about 1 to about 20 wt.%
agent is magnesium sulfate, of a fragrance component, about 2 to about 15 wt.% of
7. A method of stabilizing a hydroalcoholic air fresh 35 about 3 to about 15 wt.% of a monohydric alcohol
ener composition consisting essentially of about 1 to having 2 to about 12 carbon atoms a reservoir for said
about 20 wt.% of a fragrance component, about 3 to composition, and an emanator for volatilization of said
about 15 wt.% of a monohydric alcohol having 2 to composition, the improvement comprising incorporat
about 12 carbon atoms and about 2 to about 15 wt.% an ing in the composition about 0.01 to about 0.5 wt.% of
emulsifier against phase separation which comprises the 40 a weight loss inhibitor which is an alkali metal or alka
step of adding thereto about 0.01 to about 0.5 wt.% of line earth metal halide, sulfate, nitrate, carbonate, bicar
at least one weight loss inhibitor, which is an alkali metal bonate or phosphate.
or alkaline earth metal halide, sulfate, nitrate, carbonate, 18. The device of claim 16 wherein the inhibitor is
bicarbonate or phosphate. selected from the group consisting of sodium chloride,
8. The method of claim 6 wherein a halide or a sulfate 45 sodium sulfate and magnesium chloride.
inhibitor is used. k k k k is

50

55

65