(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

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(19) World Intellectual Property Organization
International Bureau 11111111111111 II 11111111111 IIIII II Ill IIIII IIIII 1111111111 11111111111 1111 11111111

(43) International Publication Date (10) International Publication Number

25 May 2001 (25.05.2001) PCT WO 01/35764 Al
(51) International Patent Classification7 : A23L 1/22, (74) Agents: JORRITSMA, Ruurd et al.; Nederlandsch
A61K 47/26 Octrooibureau, Scheveningseweg 82, P.O. Box 29720,
NL-2502 LS The Hague (NL).
(21) International Application Number: PCT/NL00/00840
(81) Designated States (national): AE, AG, AL, AM, AT, AU,
(22) International Filing Date: AZ, BA, BB, BG, BR, BY, BZ, CA, CH, CN, CR, CU, CZ,
17 November 2000 (17.11.2000) DE, DK, DM, DZ, EE, ES, Fl, GB, GD, GE, GH, GM, HR,
HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR,
LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ,
(25) Filing Language: English NO, NZ, PL, PT, RO, RU, SD, SE, SG, Sl, SK, SL, TJ, TM,
TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW.
(26) Publication Language: English
(84) Designated States (regional): ARIPO patent (GH, GM,
(30) Priority Data: KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW), Eurasian
99203854.7 18 November 1999 (18.11.1999) EP patent(AM,AZ,BY,KG,KZ,MD,RU, TJ, TM),European
99203981.8 26 November 1999 (26.11.1999) EP patent (AT, BE, CH, CY, DE, DK, ES, Fl, FR, GB, GR, IE,
IT, LU, MC, NL, PT, SE, TR), OAPI patent (BF, BJ, CF,
(71) Applicant (for all designated States except US): QUEST CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG).
INTERNATIONAL B.V. [NL/NL]; Huizerstraatweg 28,
NL-1411 GP Naarden (NL). Published:
With international search report.
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(72) Inventors; and Before the expiration of the time limit for amending the
iiiiiiiii claims and to be republished in the event of receipt of
iiiiiiiii (75) Inventors/Applicants (for US only): WITTEVEEN,
iiiiiiiii amendments.
iiiiiiiii Frans [NL/NL]; Vlasland 18, NL-3833 CM Leusden
iiiiiiiii (NL). ORSEL, Roelof [NL/NL]; Hagedis 33, NL-1275

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BP Huizen (NL). BURGER, Jack [NL/NL]; Bakboord
7, NL-1316 VA Almere (NL). DOORN, Louis [NLINL];
Zonnehoven 4, NL-3893 CB Zeewolde (NL).
For two-letter codes and other abbreviations, refor to the "Guid-
ance Notes on Codes and Abbreviations" appearing at the begin-
ning of each regular issue of the PCT Gazette.

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t"'-- (54) Title: STABLE, SPRAY-DRIED COMPOSffiON IN A CARBOHYDRATE SUBSTRATE AND PROCESS FOR OBTAIN-
ln lNG SAID COMPOSffiON
~
S (57) Abstract: The invention relates to a moisture and oxygen stable spray-dried composition comprising at least one active com-
pound encapsulated in a carbohydrate matrix, which matrix is characterised by 40 to 80 wt. % high molecular weight film forming
0 carbohydrate; 10 to 30 wt. % mono, di and trisaccharides; and 10 to 30 wt. % maltodextrin based on the total weight of the carbo-
> hydrate matrix. The active compound to be encapsulated in the carbohydrate matrix can be selected from the group consisting of
~ flavourants, fragrances, pharmaceuticals and wash-active components.
 wo 01135764 PCT/NL00/00840

Description

STABLE, SPRAY-DRIED COMPOSITION IN A CARBOHYDRATE SUBSTRATE AND PROCESS FOR

OBTAINING SAID COMPOSITION

5
The invention relates to a moisture and oxygen stable spray-dried composition
comprising at least one active compound like a moisture or oxygen sensitive flavourant~

a fragrance or another type of a moisture or oxygen sensitive compound e.g. a

pharmaceutical. Further, the invention relates to a process for fixing volatile
10 flavourants, fragrances or other volatile and moisture or oxygen sensitive compounds in
an amorphous matrix.
With regard to the field of flavours it is noted that for instance efforts have been
made to give the consumer a fresher tasting reconstitutable beverage mix by using
certain natural, natural identical or artificial volatile compounds for improving the
15 consumer's taste perception. Unlike liquid systems which usually retain flavourants
without adverse stability problems, dry comestible beverage mixes are often lacking in
flavour or have off-flavours due to poor storage stability. A fresh tasting, reconstituted
beverage would increase the consumer's perception of freshness which is of paramount
importance.
20 Such compounds as coffee aroma, esters, acetaldehyde, various essential oils and
sulphur compounds, augment or enhance the taste perception of convenience foods.
Dry comestible mix systems present special problems when one tries to introduce
volatile or aromatic flavourants therein. For example, such materials escape through
and from the mix, or react so as to degrade or oxidize into compounds which are
25 recognized to be less desirable. Therefore, there has been a long-standing need to fix by
encapsulation, and prevent the escape of volatiles within a "powdered-mix" comestible
and prevent oxidation thereof. Moreover, the process for fixing a volatile must produce
a product which is easily reconstitutable and is capable of holding the fix over
prolonged periods and under adverse storage conditions.
30 A major problem inherent in fixing aromatics in food allowed substrates is the
fact that those fixation substrates display idiosyncratic fixation characteristics. The
substrate media may be sensitive to moisture, react with the entrained volatile or
produce flavour off-notes. Carbohydrates as a class offer a food-acceptable substrate in
 wo 01135764 PCT/NL00/00840

2
which volatiles and aromatics have been fixed. However, most water-soluble
carbohydrate substrates are hygroscopic and will not reliably hold the fix for long
periods. In view of the foregoing, there is a recognized need for an amorphous
moisture-stable, water-soluble, food-approved substrate to encapsulate aromatic or
5 volatile flavourants.
Where flavours, such as essential oils, are not protected by an antioxidant, even
further problems of off-flavour development are encountered due to oxidation caused
by the inability of the carbohydrate matrix to protect the flavour from oxygen.
EP 0,550,067 B1 relates to a method for encapsulating oils such as fragrance and
10 flavouring oils in a water-sensitive cellular solid matrix, comprising drying an aqueous
emulsion containing (a) the oil to be encapsulated, (b) a non-crosslinked lipophilically
modified starch that undergoes crosslinking under the drying conditions and (c) a
polyhydroxy compound that forms with the polysaccharide material a continuous
aqueous phase in which the oil is dispersible as a discontinuous phase. The oil (a)
15 which typically contains a conventional antioxidant like butylated hydroxy toluene is
typically encapsulated in the dried carbohydrate matrix in an amount from 5 to 80%,
preferably at least 65% by weight of the oil and matrix combination. The modified
starch (b) is in principle an ungelatinised starch acid ester of a substituted dicarboxylic
acid, and the polyhydroxy compound (c) are polyalcohols like glycerol, mannitol etc.,
20 and sugars including mono, di and trisaccharides like glucose, fructose, maltose,
sucrose, and raffinose.
US 5,102,682 A relates to a dry flavoured powdered food mix comprising at feast
20% crystalline sucrose, at least 10% crystalline fructose, 1-8% crystalline food acid,
flavour and anti-caking agent, wherein all components are present in a free, unbound
25 state and wherein the crystalline fructose compound contains less than 10% by weight
of particles smaller than 150 J.lm. As indicated in said US 5,102,682 the fructose and
sucrose content of the food mix can range from 10-60% and 20-80% respectively, and
the combined weight of fructose and sucrose will usually be at least 40%, and for soft
drink mixes such as fruit-flavoured beverage mixes will typically be at least 90%,
30 usually about 95% or more of the mix.
The flavours suitable for use in the food mix can be spray-dried flavours fixed in
a carbohydrate matrix consisting of either maltodextrin or a combination of malta-
dextrin and a modified starch. According to said US 5,102,682 typical spray-dried
 wo 01/35764 PCT/NL00/00840

3
flavours contain 30-60% modified food starch and 30-60% maltodextrin and
flavourant.
EP 0,426,428 B 1 relates to a delivery system for flavours and sweeteners and to ·a
process for its preparation, which system has use in a variety of products including
5 comestibles such as chewing gum, food products etc. More in particular EP 0,426,428
B 1 relates to a process for producing a flavour delivery system prepared from a spray-
dried emulsion of
(a) from 0.1 to 40 wt.% of a flavour oil,
(b) from 0.5 to 30 wt.% of a sweetener and
10 (c) from 30 to 80 wt.% of a film-forming polymer coating component, all amounts are
based on the total weight of the delivery system.
Suitable sweeteners to be encapsulated in the delivery system include natural and
artificial high intensity sweeteners selected from amino acid-based sweeteners,
dipeptide sweeteners, glycyrrhizin, saccharin and its salts, acesulfame salts, cyclamates,
15 steviosides, talin, sucralose, dihydrochalcone compounds and mixtures thereof. As
disclosed therein it is believed that the invention is predicated in part on the discovery
that an interaction exists between flavours and particularly flavour oils and certain
intense sweeteners such as aspartame and acesulfame-K when presented in the
hydrocolloid coatings hereof, such that the sweeteners mask the bitterness of the
20 flavour component. Further, the sequential admixture and emulsification of the
ingredients with each other is believed to contribute both to the masking effect exerted
on the flavour oil and the improved uniformity and extension of the release ·and
perception of both actives. According to EP 0,426,428 B 1 it is further possible to use
sweeteners in addition to those already included in the delivery system. Such additional
25 sweeteners, merely used as excipients, may be selected from e.g. sucrose, glucose,
dextrose, invert sugar, fructose etc.
US 5, 124, 162 A is directed to a moisture and oxygen stable spray-dried fixed
flavour comprising a flavourant encapsulated in a carbohydrate matrix consisting of 22
to 50%, preferably 22 to 45% mono and disaccharides, wherein at least 50% of the
30 mono and disaccharides is maltose, 25 to 60%, preferably 25 to 50% maltodextrin, and
10 to 40%, preferably 10 to 35% high molecular weight film forming carbohydrate.
With regard to the field of perfumes and perfumed products it is referred to WO
94/19449 indicating the detrimental impact of high humidity conditions on products
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4
based on a water sensitive matrix e.g. a starch matrix and a fragrance or a wash-active
component encapsulated therein. This type of encapsulates may be added to a number
of articles to be perfumed including laundry powder, soap and machine dishwash
powder. Apparently the problem encountered in WO 94/19449 is solved by a
5 composition comprising (a) a substance encapsulated within a water-sensitive matrix so
as to be releasable upon contact with water or aqueous solutions, mixed with (b)
particles of inorganic carrier material carrying a poorly water-soluble oil, such that the
composition is stable at high relative humidity. Examples of substances encapsulated in
the water-sensitive matrix are a perfume, flavour, a cosmetic ingredient or
10 organometallic complexes e.g. a bleaching agent, bleach activator or bleach catalyst.
Summarizing the prior art it is noted that the most familiar reference IS

considered US 5,124,162 A. Therein, it is stated that a moisture and oxygen stable

spray-dried composition can be obtained if -next to the other two components of the
carbohydrate matrix- at least 50% of the mono and disaccharide component is maltose.
15 Further, it is indicated in US 5,124,162 A (column 4, lines 19-23) that certain film
forming carbohydrates like gum arabic and waxy starches present "leaky" substrates,
which will not retain entrapped volatile flavourants.
Surprisingly, it has now been found that in spite of the above-mentioned
prejudice stated in the most familiar reference US 5,124,162 A, a moisture and oxygel?-
20 stable spray-dried composition could be obtained by using a carbohydrate matrix
comprising a rather high amount of 40 to 80 wt.% high molecular weight film forming
carbohydrate in combination with 10 to 30 wt.% mono, di and trisaccharides and ro to
30 wt.% maltodextrin, based on the total weight of the carbohydrate matrix.
Therefore, the invention relates to a moisture and oxygen stable spray-dried
25 composition comprising at least one active compound encapsulated in a carbohydrate
matrix which matrix is characterized by
40 to 80 wt.% high molecular weight film forming carbohydrate;
10 to 30 wt.% mono, di and trisaccharides; and
10 to 30 wt.% maltodextrin
30 based on the total weight ofthe carbohydrate matrix.
In view of the above discussed US 5,124,162 A, it is stated that the maltose
percentage of the saccharide component in the spray-dried composition according to
 wo 01/35764 PCT/NL00/00840

5
the invention may be less than 50% and even nihil in case for instance sucrose is used
as the only saccharide component therein.
More in particular the carbohydrate matrix includes from 45 to 70 wt.o/o,
preferably from 50 to 60 wt.% high molecular weight film forming carbohydrate.
5 Suitable film forming carbohydrates are film forming gums, pectins, alginates,
mucilages and mixtures thereof. Preferably the film forming carbohydrates are selected
from gum arabic, gum acacia, tragacanth, karaya, ghatti, agar, alginates, carrageenans,
fucellan, psyllium and mixtures thereof or from gelatin, dextran, xanthan, curdlan,
cellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropyl
10 cellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose, low methoxy
pectin, propylene glycol alginate and mixtures thereof.
Most preferably the film forming agents are film forming gums, hydrocolloids
and lipophilically modified starches. Examples of gums are gum arabic and gum
acacia. Examples of suitably chemically modified starches are Capsul® and N-Lok
15 (National Starch). Of course, also mixtures of film forming carbohydrates can be used
in the spray-dried compositions according to the invention.
Another component of the carbohydrate matrix according to the invention are the
mono, di and trisaccharides, which are used in an amount of 10 to 30 wt.%, preferably
15-25 wt.%, based on the total weight of the carbohydrate matrix. Illustrative examples
20 of mono, di and trisaccharides are glucose, fructose, maltose, sucrose, raffinose and
materials, having a high content of such sugars like fruit juice solids. Preferably, at
least 50 wt.% of the mono, di and trisaccharide material is a disaccharide as a high
amount of monosaccharide may result in a somewhat sticky product whereas a high
amount of trisaccharide may lead to a product more prone to oxidation. In a preferred
25 embodiment according to the invention the mono, di and trisaccharide material is
sucrose.
The carbohydrate matrix according to the invention further includes 10 to 30
wt.%, preferably 10 to 25 wt.% maltodextrin. The maltodextrin will preferably have a
dextrose equivalent (DE) in the range of 1 to 25, most preferably in the range of 10 to
30 20. A variety of maltodextrins meeting the above requirements are readily available
commercially, including maltodextrins from e.g. tapioca, maize and potato ..
The carbohydrate matrix may be softened by the incorporation of up to 5 wt.% of
an edible polyol such as glycerol, preferably 1 to 3 wt. %, based on the carbohydrate
 wo 01/35764 PCT/NL00/00840

6
matrix. Also other components like anti-foam agents in an amount of up to 0.2 %o may
be added.
The active compound to be encapsulated in the carbohydrate matrix can be
selected from the group consisting of flavourants, fragrances, pharmaceuticals and
5 wash-active components.
Flavourants are well-known in the art and are mentioned, e.g., in S. Arctander,
Perfume and Flavor Materials of Natural Origin (Elisabeth, N.J., USA, 1996), in T.E.
Furia et al, CRC Fenaroli's Handbook of Flavor Ingredients, 2nd Ed. (Cleveland, CRC
Press Inc., 1975), and in H.B. Heath, Source Book of Flavors (The Avi Publishing
10 Company Inc., Westport, Connecticut, 1981).
Fragrances and mixtures thereof which can be used for the preparation of
perfumed articles are e.g. naturally occurring products such as essential oils, absolutes,
resinoids, resins, concretes etc., natural, nature identical and artificial fragrances, such
as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals,
15 nitriles etc., covering saturated and unsaturated compounds, aliphatic, carbocyclic and
heterocyclic compounds, for instance as disclosed in S.Arctander (loc.cit.).
Examples of fragrances which may be used within the scope of the invention are:
geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalool, citronellol,
citronellyl acetate, dihydro myrcenol, dihydro myrcenyl acetate, tetrahydro myrcenol;
20 terpineol, terpinyl acetate, nopol, nopyl acetate, 2-phenylethanol, 2-phenylethyl acetate,
benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate,
amyl salicylate, dimethylbenzyl carbinol, trichloromethylphenylcarbinyl acetate, p..:tert.
butylcyclohexyl acetate, isononyl acetate, vetiveryl acetate, vetiverol, a-hexyl-
cinnamaldehyde, 2-methyl-3-(p-tert.butylphenyl)-propanal, 2-methyl-3-(p-isopropyl
25 phenyl)-propanal, 3-(p-tert.butylphenyl)-propanal, tricyclodecenyl acetate, tricyclo-
decenyl propionate, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene carbaldehyde, 4-(4-
methyl-3-penteny1)-3-cyclohexene carbaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran,
3-carboxymethyl-2-pentyl-cyclopentane, 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-
2-cyclopentanone, n-decanal, n-dodecanal, dec-9-en-1-ol, phenoxy-ethyl isobyutyrate,
30 phenylacetaldehyde dimethylacetal, phenylacetaldehyde diethylacetal, geranyl nitrile,
citronellyl nitrile, cedryl acetate, 3-isocamphyl cyclohexanol, cedrylmethyl ether,
isolongifolanone, aubepine nitrile, aubepine, heliotropine, coumarin, eugenol, vanillin,
diphenyl oxide, hydroxy citronellal, ionones, methyl ionones, isomethyl wnones,
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7
irones, cis-3-hexenol and esters thereof, indan musk fragrances, tetralin musk
fragrances, isochroman musk frangrances, macrocyclic ketones, macrolactone musk
fragrances, ethylene brassylate, aromatic nutri-musk frangrances.
The fragrance comprising spray-dried products according to the invention may be
5 used successfully in perfumed articles. Examples of such perfumed articles are: soap,
bath products, washing agents, dish washing and cleaning agents, pommanders,
candles, cosmetics such as creams, ointments, body deodorant sticks and antiperspirant
sticks.
Also pharmaceuticals and wash-active components which are prone to humidity
10 or oxygen can be used as active compound to be encapsulated in the carbohydrate
matrix according to the invention.
A major application of the invention is related to the field of flavours. In this
respect it 1s noted that the final spray-dried product according to the invention is
capable of protecting and retaining 5 to 40 wt.% or even more, preferably 20 to 30
15 wt.% flavourant as active compound, depending on the type of flavourant and based on
the total weight of the flavour. Examples of flavourants, in particular aromatic or
volatile flavourants, to be encapsulated in the carbohydrate matrix according to the
invention are for instance essential oils, like citrus oil, e.g. lemon oil, orange oil,
grapefruit oil and other volatile flavourants, like bakery and savoury flavourants. Also
20 other types of active compounds as indicated above can be encapsulated in the
carbohydrate matrix according to the invention in an amount of 5-40 wt.% or more,
preferably 20-30 wt.%, based on the total weight ofthe composition.
A further aspect of the invention is embodied by a process for producing the
moisture and oxygen stable composition, comprising the steps of
25 a) forming an aqueous carbohydrate solution containing a carbohydrate mixture
consisting of 40 to 80 wt.% high molecular weight film forming carbohydrate(s), 10
to 30 wt.% mono, di and trisaccharide(s), and 10 to 30 wt.% maltodextrin(s),
b) incorporating at least one active compound defined above into the solution of step
(a), and
30 c) spray-drying the aqueous solution of step (b) using an outlet temperature of 1oooc
or less to obtain a stable product encapsulated therein the active compound.
In general, the procedure of spray-drying involves the following. At first a solution of
the product one wishes to make is prepared. The term solution is understood to mean
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mixtures of solutes and solvents encompassing such mixtures as emulsions or
dispersions. The solution is fed into an atomizer which creates a fine mist, composed of
regular-sized droplets. The misted solution is introduced, usually through the top ofa
drying tower or chamber into the spraydryer. Heated air is fed into the chamber so that
5 as the droplets fall from the top of the chamber evaporation and drying of the aqueous
liquid phase respectfully occurs. The product is collected from an outlet port. Examples
of spray-drying apparatus are the Anhydro Dryers (manufactured by Anhydro Corp. of
Attleboro Falls, Mass. U.S.A.) or the Niro Dryer (manufactured by Niro Atomizer Ltd,
Copenhagen, Denmark).
10 More in particular the combination of carbohydrate materials is dissolved in
water to form an aqueous solution with the temperature being maintained at around
1ooc to 90°C. In the case of a highly volatile substance the solution is allowed to cool
to about the boiling point of the substance or below. The active compound, for instance
a volatile or aromatic flavourant is then added to the solution, the solution being
15 preferably maintained at from l0°C to 50°C. The solution is then spray-dried in an
atmospheric spraydryer wherein the inlet temperature is typically about 140°C to
21 ooc and the outlet temperature typically 70°C to 100°C. The resultant moisture-
stable product has an excellent retention of volatiles over time and a prolonged shelf
life without unacceptable oxidation. No antioxidant is added or made part of the final
20 product.
The invention is elucidated by means of the following examples and the storage
properties of the spray-dried products are illustrated by means ofthe Figures 1 and 2.

Fig. 1 illustrates the accelerated shelf life test of

25 • a product according to the prior art based on 25 wt.% orange flavourant (QL
06830 marketed by Quest International, the Netherlands) and 75 wt.% of a
carbohydrate matrix consisting of 50 wt.% Capsul® and 50 wt.% maltodextrin
(DE 20), and

+ a product according to the invention based on 25 wt.% orange flavourant (QL

30 06830) and 75 wt.% of a carbohydrate matrix consisting of 50 wt.% Capsul®,
23 wt.% maltodextrin (DE 20), 25 wt.% sucrose and 2 wt.% glycerol.
 wo 01135764 PCT/NL00/00840

9
More in particular the X -axis represents the time in weeks, and the Y -axis
represents the amount of carvone in wt.%, formed from the spray-dried products
due to oxidation of the limonene component of the used orange flavouraiit
during the accelerated shelf life test at 40°C and at a relative humidity (RH) of
5 30%.

Fig. 2 illustrates the accelerated shelf life test of

• the product according to the prior art shown in Fig. 1, and

10 * a product according to the invention based on 25 wt.% orange flavourant (QL

06830) and 75 wt.% of a carbohydrate matrix consisting of 60 wt.% gum acacia,

20 wt.% maltodextrin (DE 10) and 20 wt.% sucrose.

More in particular the X -axis represents the time in weeks, and the Y -axis
15 represents the amount of carvone in wt.%, formed from the spray-dried products
due to oxidation of the limonene component of the used orange flavourant
during the accelerated shelf life test at 40°C and at a relative humidity (RH) of
50%.

20 Fig. 3 illustrates the accelerated shelf life test of

• the product according to the prior art shown in Fig. 1, and

+ a product according to the invention based on 25 wt.% orange flavourant (QL

06830) and 75 wt.% of a carbohydrate matrix consisting of 50 wt.% Capsul®,
30 wt.% maltodextrin (DE 20) and 20 wt.% glucose.
25
More in particular the X-axis represents the equivalent ambient shelf-life in
months, and the Y -axis represents the amount of carvone in wt. %, formed from
the spray-dried products due to oxidation of the limonene component of the
used orange flavourant during the accelerated shelf life test at 40°C and at a
30 relative humidity (RH) of 30%.
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Fig. 4 illustrates the accelerated shelf-life test of

• the product according to the prior art shown in Fig. 1, and

+ a product according to the invention based on 25 wt.% mandarin flavourant (DF

39467) and 75 wt.% of a carbohydrate matrix consisting of 60 wt.% gum acacia,
5 20 wt.% maltodextrin (DE 10), 9 wt.% mandarin juice solids and 11 wt.%
sucrose (total sugar content: 19 wt.%).

More in particular the X-axis represents the equivalent ambient shelf-life in

months, and the Y-axis represents the amount of p-cymene in wt. %, formed
10 from the spray-dried products due to oxidation of the terpene compounds in the
used mandarin flavourant during the accelerated shelf life test at 40°C and at a
relative humidity (RH) of 50%.

Example 1
15 The following two formulations were prepared by dissolving or dispersing the
components indicated below
(a) 500 g of a carbohydrate matrix comprising 50 wt.% (250 g) Capsul® and 50
wt.% (250 g) maltodextrin (DE 20) being a carbohydrate matrix used for
marketed products; and
20 (b) 500 g of a carbohydrate matrix consisting of 50 wt.% (250 g) Capsul®, 23 wt.%
(115 g) maltodextrin (DE 20), 25 wt.% (125 g) sucrose and 2 wt.% (1_0 g)
glycerol being a carbohydrate matrix according to the invention
under stirring in 600 g warm water of 80°C for 30 minutes. Then the mixture was
cooled to 20°C. An orange flavourant (QL 06830) without any antioxidant preservative
25 was added in an amount of25 wt.% on total dry solids (166 g) under stirring and the
prepared feed was homogenised using a Ultra Turrax T50 at 10,000 rpm for about 3
minutes. The homogenised feed was spray-dried in a NIRO MOBIL MINOR SPRAY
DRYER using a rotary wheel atomiser at 20,000 rpm. Inlet air temperature was kept at
190°C, resulting in an outlet temperature in the range of 90°C.
30
As apparent from Fig. 1, the product according to the invention had an excellent
stability and a desired long storage life compared to the prior art product. More in
particular the storage time of 8 weeks in the accelerated shelf life test at 40°C and a RH
 wo 01/35764 PCT/NL00/00840

11
of 30% corresponds to a storage time of about one year at room temperature (20°C) and
aRH of30%.

Example 2
5 The following two formulations were prepared by dissolving or dispersing the
components indicated below
(a) 500 g of a carbohydrate matrix consisting of 50 wt.% (250 g) Capsul® and 50
wt.% (250 g) maltodextrin (DE 20) being a carbohydrate matrix used for
marketed products; and
10 (b) 316 g of a carbohydrate matrix consisting of 60 wt.% ( 190 g) gum acacia, 20
wt.% (63 g) maltodextrin (DE 10) and 20 wt.% (63 g) sucrose being a
carbohydrate matrix according to the invention
under stirring in 600 g warm water of 60°C for 30 minutes. Then the mixture was
cooled to 20°C. An orange flavourant (QL 06830) without any antioxidant preservative
15 was added in an amount of 25 wt.% on total dry solids (166 g for formulation (a) and
105 g for formulation (b)) under stirring and the prepared feed was homogenised using
a Ultra Turrax T50 at 10,000 rpm for about 3 minutes. The homogenised feed was
spray-dried in a NIRO MOBIL MINOR SPRAY DRYER using a rotary wheel
atomiser at 20,000 rpm. Inlet air temperature was kept at 190°C, resulting in an outlet
20 temperature in the range of 90°C.

As apparent from Fig. 2, the product according to the invention had an excellent
stability and a desired long storage life compared to the prior art product. More in
particular the storage time of 8 weeks in the accelerated shelf life test at 40°C and a RH
25 of 50% corresponds to a storage time of about one year at room temperature (20°C) and
aRHof50%.

Example 3
The following two formulations were prepared by dissolving or dispersing the
30 components indicated below
(a) 500 g of a carbohydrate matrix comprising 50 wt.% (250 g) Capsul® and 50
wt.% (250 g) maltodextrin (DE 20) being a carbohydrate matrix used for
marketed products; and
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12
(b) 500 g of a carbohydrate matrix consisting of 50 wt.% (250 g) Capsul®, 30 wt.%
(150 g) maltodextrin (DE 20), and 20 wt.% (100 g) glucose being a carbohydrate
matrix according to the invention
under stirring in 600 g warm water of 80°C for 30 minutes. Then the mixture was
5 cooled to 20°C. An orange flavourant (QL 06830) without any antioxidant preservative
was added in an amount of 25 wt.% on total dry solids ( 166 g) under stirring and the
prepared feed was homogenised using a Ultra Turrax T50 at 10,000 rpm for about 3
minutes. The homogenised feed was spray-dried in a NIRO MOBIL MINOR SPRAY
DRYER using a rotary wheel atomiser at 20,000 rpm. Inlet air temperature was kept at
10 190°C, resulting in an outlet temperature in the range of 90°C.

As apparent from Fig. 3, the product according to the invention had an excellent
stability and a desired long storage life compared to the prior art product. More in
particular the storage time of 8 weeks in the accelerated shelf life test at 40°C and a RH
15 of 30% corresponds to an ambient shelf-life of about one year at room temperature
(20°C) and a RH of 30%.

Example 4
The following two formulations were prepared by dissolving or dispersing the
20 components indicated below
(a) 500 g of a carbohydrate matrix comprising 50 wt.% (250 g) Capsul® and 50
wt.% (250 g) maltodextrin (DE 20) being a carbohydrate matrix used for
marketed products; and
(b) 316 g of a carbohydrate matrix consisting of 60 wt.% ( 190 g) gum acacia, 20
25 wt.% (63 g) maltodextrin (DE 10), 9 wt.% (28.5 g) mandarin juice
solids (90-95 %of juice solids (D.S.) is a sugar mixture consisting of glucose and
fructose) and 11 wt.% (34.5 g) sucrose being a carbohydrate matrix according to
the invention (the resulting sugar content originating from the sum of the sucrose
and the sugars present in the fruit juice concentrate is 19 wt.% of sugars)
30 under stirring in 600 g warm water of 80°C for 30 minutes. Then the mixture was
cooled to 20°C. A mandarin flavourant (DF 39467) without any antioxidant preserv-
ative was added in an amount of25 wt.% on total dry solids (166 g) under stirring and
the prepared feed was homogenised using a Ultra Turrax T50 at 10,000 rpm for about 3
 wo 01135764 PCT/NL00/00840

13
minutes. The homogenised feed was spray-dried in a NIRO MOBIL MINOR SPRAY
DRYER using a rotary wheel atomiser at 20,000 rpm. Inlet air temperature was kept a~
190°C, resulting in an outlet temperature in the range of 90°C.

5 As apparent from Fig. 4, the product according to the invention had an excellent
stability and a desired long storage life compared to the prior art product. More in
particular the storage time of 8 weeks in the accelerated shelf life test at 40°C and a RH
of 30% corresponds to an ambient shelf-life of about one year at room temperature
(20°C) and a RH of 30%.
 wo 01/35764 PCT/NL00/00840

14
CLAIMS

1. A moisture and oxygen stable spray-dried composition comprising at least one

active compound encapsulated in a carbohydrate matrix, which matrix is characterised
5 by
40 to 80 wt.% high molecular weight film forming carbohydrate;
10 to 30 wt.% mono, di and trisaccharides; and
10 to 30 wt.% maltodextrin
based on the total weight of the carbohydrate matrix.
10
2. The spray-dried composition according to claim 1, characterised in that the
film forming carbohydrate is present in an amount of 45 to 70 wt.%, preferably 50-60
wt.% based on the total weight of the carbohydrate matrix.

15 3. The spray-dried composition according to claim 1 or 2, characterised in that

the film forming carbohydrate is selected from the group consisting of gum arabic, gum
acacia, lipophilically modified starches and mixtures thereof.

4. The spray-dried composition according to any of claims 1-3, characterised it:

20 that the mono, di and trisaccharides are present in an amount of 15-25 wt.% based on
the total weight of the carbohydrate matrix.

5. The spray-dried composition according to any of claims 1-4, characterised in

that at least 50 wt.% of the mono, di and trisaccharide material is a disaccharide.
25
6. The spray-dried composition according to claim 5, characterised in that the
disaccharide is sucrose.

7. The spray-dried composition according to claims 5 or 6, characterised in that

30 100 wt.% of the mono, di and trisaccharide material is sucrose.
 wo 01/35764 PCT/NL00/00840

15
8. The spray-dried composition according to any of claims 1-7, characterised in
that the maltodextrin has a dextrose equivalent (DE) in the range of 1 to 25, preferably
10 to 20.

5 9. The spray-dried composition according to any of claims 1-8, characterised in

that the active component encapsulated in the carbohydrate matrix is selected from the
group consisting of flavourants, fragrances, pharmaceuticals and wash-active
components.

10 10. The spray-dried composition according to any of claims 1-9, characterised in

that the encapsulated active compound is at least one flavourant selected from the
group consisting of essential oils, like citrus oil, e.g. lemon oil, orange oil, grapefruit
oil, bakery flavourants and savoury flavourants.

15 11. The spray-dried composition according to any of claims 1-10, characterised

m that the encapsulated active compound is present in an amount of 5-40 wt.%,
preferably 20-30 wt.%, based on the total weight ofthe composition.

12. A process for producing a moisture and oxygen stable compositio~

20 comprising the steps of

(a) forming an aqueous carbohydrate solution containing a carbohydrate mixture
consisting of 40 to 80 wt.% high molecular weight film forming carbohydrate(s),
10 to 30 wt.% mono, di and trisaccharide(s), and 10 to 30 wt.% maltodextrin(s);
(b) incorporating at least one active compound into the solution of step (a); and
25 (c) spray-drying the aqueous solution of step (b) using an outlet air temperature of
1oooc or less, to obtain a stable product encapsulated therein the active
compound.

13. The process according to claim 12, characterised in that the active
30 compound is selected from the group consisting of flavourants, fragrances,
pharmaceuticals and wash-active components.
wo 01135764 PCT/NL00/00840

16

14. Products comprising the spray-dried composition according to any of claims

1-11 or prepared by the process according to claim 12 or 13.
WOOl/35764 PCf/NL00/00840

113

Fig 1
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Time (weeks)

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cu 0.4
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0~
0.2

0.1

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0 2 4 6 8 10
Time (weeks)
wo 01135764 PCT/NL00/0084.0

213

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wo 01135764 PCT/NL00/00840

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3N3li'JA:J-d 38'1.LN38CJ3d
 INTERNATIONAL SEARCH REPORT lnte. onal Application No

PCT/NL 00/00840
A. CLASSIFICATION O~UBJECT MATTER
IPC 7 A23L1 22 A61K47/26

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
IPC 7 A23L A61K

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practical, search terms used)

EPO-Internal, WPI Data, PAJ

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category o Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

y EP 0 545 632 A (GEN FOODS INC) 1-14

9 June 1993 (1993-06-09)
cited in the application
claims
---
y EP 0 426 428 A (WARNER LAMBERT CO) 1-14
8 May 1991 (1991-05-08)
cited in the application
page 4, 1 i ne 7-13
page 5, 1 i ne 46-53
page 6, 1 i ne 1-6
-----

D Further documents are listed in the continuation of box C.

[] Patent family members are listed in annex.

o Special categories of cited documents :

'T' later document published after the international filing date
or priority date and not in conflict with the application but
'A' document defining the general state of the art which is not cited to understand the principle or theory underlying the
considered to be of particular relevance invention
'E' earlier document but published on or after the international ·x· document of particular relevance; the claimed invention
filing date cannot be considered novel or cannot be considered to
'L' document which may throw doubts on priority claim(s) or involve an inventive step when the document is taken alone
which is cited to establish the publication date of another •y• document of particular relevance; the claimed invention
citation or other special reason (as specified) cannot be considered to involve an inventive step when the
'0' document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu-
other means ments, such combination being obvious to a person skilled
•p• document published prior to the international filing date but in !heart.
later than the priority date claimed '&' document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

19 March 2001 27/03/2001

Name and mailing address of the ISA Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
NL- 2280 HV Rijswijk
1
Tel. (+31-70) 340-2040, Tx. 31 651 epo nl,
Fax: (+31-70)340-3016 Herrera, s
Form PCT/ISA/210 (second shee1) (July 1992)
 INTE RNATIONAL SEARCH REPORT lnte ,onal Application No
Information on patent family members
PCT/NL 00/00840
Patent document Publication Patent family Publication
cited in search report date member(s) date
I I I
EP 0545632 A 09-06-1993 us 5124162 A 23-06-1992
AT 133538 T 15-02-1996
AU 648208 B 14-04-1994
AU 2859392 A 27-05-1993
BR 9204879 A 01-06-1993
CA 2083444 A 27-05-1993
CN 1074933 A,B 04-08-1993
DE 69208058 D 14-03-1996
DE 69208058 T 22-08-1996
ES 2084952 T 16-05-1996
HK 151996 A 16-08-1996
JP 6220485 A 09-08-1994
MX 9206804 A 01-07-1993
NZ 245237 A 25-11-1993
-----------------------------------------------------------------------
EP 0426428 A 08-05-1991 AU 6565990 A 09-05-1991
CA 2028934 A 01-05-1991
CN 1051290 A 15-05-1991
DE 69002730 D 16-09-1993
DE 69002730 T 09-12-1993
ES 2042220 T 01-12-1993
IE 903898 A 08-05-1991
JP 3160969 A 10-07-1991
NO 904693 A 02-05-1991
PT 95734 A 13-09-1991
ZA 9008693 A 25-09-1991
-----------------------------------------------------------------------

Form PCT/ISA/210 (patent family annex) (July 1992)