CA2002702C

CA2002702C - Food acid delivery systems containing polyvinyl acetate

Info

Publication number: CA2002702C
Application number: CA002002702A
Authority: CA
Inventors: Subraman Rao Cherukuri; Gul Mansukhani
Original assignee: Warner Lambert Co LLC
Current assignee: Intercontinental Great Brands LLC
Priority date: 1988-11-14
Filing date: 1989-11-10
Publication date: 1997-03-11
Anticipated expiration: 2009-11-10
Also published as: PH26138A; CA2002702A1; EP0372695A1; PT92296A; MX166482B; ZA898651B; US4931293A; JPH02186944A; AU4459289A

Abstract

A chewing gum composition having prolonged sourness, flavor and juciness duration through the incorporation of a delivery system comprising a food acid encapsulated in a low molecular weight polyvinyl acetate material.

Description

` -Field of the Invention This invention relates to a delivery system for food acids designed to be incorporated into chewing gum and confectionary compositions to impart prolonged tartness, sourness and increased salvation. More particularly this invention relates to a method of protecting food acids from being adversely affected from such factors as moisture, pH, temperature and other reactive chemical ingredients. While the inventive delivery system is particularly useful for delivering food acids and sweeteners, it may also have applications for flavors and drugs and the like.
Background of the Invention In co-pending Application 555,130 (now Canadian Patent No. 1,315,148) the instant delivery system was used to deliver sweeteners. It has now been discovered that the delivery system also has the capability of delivery food acids over an extended chewing period.
The art has disclosed food acids as being added to chewing gum compositions to achieve the desired sourness effect, particularly in citrus fruit flavors. Generally, the acids are added directly to the water-soluble chewing gum portion of the chewing gum composition to ensure the release of the acid during mastication. For example, U.S. Patents 4,088,788 and 4,151,270, both to Ream et al. disclose the addition of at least 3% by weight of one or more organic acids in combination with a sweetener to achieve an alleged synergistic silva stimulating effect. The acids disclosed are added directly to the gum composition in their free form without mention of coating or encapsulation.

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Another example of the use of food acids being added directly in their free form to a chewing gum composition is disclosed in U.S. Patent 4,085,227 to Mackay et al. Thi~ patent disclosed both poorly water-soluble and water soluble food acids being added to the gum ba~e portion of the chewing gum composition.
According to the disclo~ure of this patent, the acids must be in the particle range of less than 150 microns.
Numerous gum base material~ are mentioned, among which i9 polyvinyl acetate. Gum base is disclosed as being present in amounts of about 10-50% by weight. No specific range of molecular weight is mentioned with regard to gum base elastomers in general or specifically to polyvinyl acetate.
Although the art has concentrated on direct addition of food acids to chewing gum rather than encapsulation of the acid, encapsulation is disclosed in U.S. Patent 3,795,744 to Ogawa et al. This patent discloses various "seasonings," among which are included acidifying agents, the "seasonings" being coated or encapsulated with high molecular weight compounds.
Among the encapsulating compounds disclosed are:
starches, cellulose, proteins, gums, polyvinyl alcohol, low molecular weight polyethylene and polyvinyl esters ~uch as polyvinyl acetate, polyvinyl propionate, a graft-copolymer of polyvinyl propionate and polyvinyl acetate, a copolymer of vinyl acetate and ethylene, propylene, acrylic and methacrylic acid, crotonic acid, maleic acid and esters of unsaturated acids thereof.
The polymers are to have a polymerization degree of 200-1500 and their mixtures are disclosed as being useful .
The claims of the Ogawa reference are directed to a method of preparing a chewing gum which can variably release different flavors due to the encapsulated _ 3 "seasoning" particles comprising the steps of:
dissolving about 2-30% by weight polyvinyl ester in a solvent selected from the group consisting of ethanol, ethylaatate and mixtures thereof, and homogeneously dispersing a flavor agent in the amount of 1-20 times the weight of the polyvinyl ester content; adding to this first solution a second solvent which is miscible with said fir9t solvent but is a nonsolvent for said polyvinyl ester, said second solvent being selected from the group consisting of hexane, whereby said polyvinyl ester precipitates out in the form of discrete particles which encapsulate the "seasoning," e.g. food acids.
There encapsulated particles are added to a chewing gum composition.
In addition to the above-mentioned art concerning the addition of food acids, the use of encapsulated sweeteners and flavors in chewing gum compositions i9 well known. Numerous patents have disclosed coatings for sweeteners in an attempt to delay or prolong sweet-ness, as well as to stabilize those sweeteners, such as asparta~e, which are sensitive to moisture, temperature and pH. U.S. Patent 4,384,004 to Cea et al., disclosessolid particles of aspartame encapsulated by a coating material selected from the group consisting of cellu-lose, cellulose derivatives, arabinogalactin, gum arabic, polyolefins, waxes, vinyl polymers, gelatin, zein and mixtures thereof, wherein the amount of saidcoating material to said methyl ester is from 1:1 to 1:10. More particularly, the coating materials include cellulose, methyl cellulose, ethyl cellulose, cellulose nitrate, cellulose acetate phthalate, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, arabinogalactan; polyethylene, polymeth-acrylates, polyamides, ethylenevinyl acetate copolymers, polyvinylpyrrolidone; gum arabic; paraffin wax, carnauba wax, 5permaceti, beeswax; stearic acid, stearyl alcohol, glyceryl stearate; gelatin, zein and mixtures thereof.
The method of coating employed in this reference includes suspending the aspartame particles in a stream of air that passes through a zone of atomized liquid droplets of the coating material, so that the coating material is deposited on the surface of the aspartame.
More than one coating may be used whereby the inner coating is water-soluble and the outer coating is water-insoluble.
U.S. Patent Nos. 4,122,195 and 4,139,939, both to Bahoshy et al., fix aspartame by preparing it with a material such as gum arabic or the reaction product of a compound containing a polyvalent metallic ion, with an ungelatinized starch acid-ester of a substituted dicarboxylic acid, by a spray drying technique, where the aspartame and a film former are prepared in an emulsion.
U.S. 4,374,858, to Glass et al., discloses an aspartame sweetened chewing gum having improved sweetness stability wherein the chewing gum piece has aspartame coated on its surface, as opposed to incorporating it in the chewing gum mix.
EPA 81110320.0, published June 16, 1982 (Publication No. 0053844), to Ajinomoto Co., Inc., discloses a stabilized depeptide-based sweetening composition comprising (a) from 20 to 60% by weight of sold fat, (b) from 10 to 30% by weight emulsifier, (c) from 10 to 30% by weight poly~accharide and (d) not more than 30% by weight of dipeptide sweetener. The composition~ are prepared by heating the mixture of the ingredients, cooling, and pulverizing to obtain powder or granules of the composition to obtain a ASTM mesh size of smaller than 12. Spray drying the mixture i9 also disclosed.

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U.S. 4,105,801 to Degliotti, discloses a confect-ionery comprising a core portion and a shell adheringly enveloping the core portion, whereby the shell is formed by an intimate mixture of microcrystals of xylitol with a solid fatty substance in a proportion of 0.5 to 15 part~ by weight of fatty ~ubstance to each 1~0 parts by weight of xylitol. The fatty substance is preferably a mono-, di- or triglyceride having a melting range of between 20 and 60C.
U.S. 3,389,000 to Toyonaka et al., discloses 1 protective coatings for granular nucleoside-5-phos-phates, the coatings being edible fats melting between 40-100C and derived from plants and animals. Examples of hydrogenated oils used are soybean oil, cottonseed oil, almond oil, castor oil, linseed oil, mustard oil, olive oil, grapefruit seed oil, palm oil, palm kernel oil, rapeseed oil, rice bran oil and the like and mixtures thereof. Thi~ reference discloses a process of preparing the granular product from a liquid mixture of fats and nucleoside-5-phosphates which are sprayed from a pressure nozzle and the resultant granule~ cooked and recovered.
U.S. 4,382,924, to Berling, discloses liquid oral dosage forms for vitamins or pharmaceutical materials comprising an edible oil, a high potency lipid soluble sweetener ~uch as saccharin and a lipid soluble flavorant. The edible oil may be a polyol fatty acid ester having at least four fatty acid ester groups and each fatty acid having from about 8 to about 22 carbon atoms. The oil, sweetener and flavor oil are mixed and heated and then cooled to provide a palatable liquid dosage form.
For a general discussion of spraying fatty materials onto sweeteners and the like see U.S. Patents 3,949,094 and 3,976,794 both to Johnson, and U.S.

3,867,556 to Darragh. U.S. 4,293,572 to Silva et al., disclo~es the application of a dispersion of an emul~i-fied fat with a solution of dextrin, saccharin or a polysaccharide to a food product as a barrier against moi~ture. U.S. patent 3,527,647 discloses a process of agglomerating particle~ by randomly scattering and spraying moi~tened particles to cause them to collide and form agglomerate~.
The problem relating to stabilization of certain core material~ relates to the surface wettability of the material as well as to its morphological configuration.
For example, in the case of certain sweeteners, this is of particular importance. Aspartame is known to be rod-like, needle-like or dendritic in shape. As a result it is very difficult to coat aspartame using ordinary mixing or spray coating techniques. To be effective a~ protective barriers, coating~ mu~t be able to wet and adhere to the crystalline surface, including the needle-like tip~ and other shape variation~ of the aspartame. Additionally, the coating must be capable of being applied in a film with a uniform thickness ~ufficient to provide a barrier against degradative factors quch as moisture, pH change~, temperature changes and reactive chemicals. The coatings, in addition to being protective barrier~, must be flexible enough to conform to the surface irregularities and geometrical configuration without cracking due to mechanical ~treqses which it is subjected to during incorporation of the sweetener into apecific product application~. Attempt~ to coat aspartame using spray technique~ to apply simple mixtures of fat and lecithin have resulted in poor wetting, spotty coating and inadequate protection against moisture and other potentially degradative factor~.

_ 7 It has been discovered that simple mixing of known coating materials such as fats, with certain other core materials such as food acids does not provide adequate protection to keep the core material in a stabilized state. Fat-~ do not provide adequate coating materials, nor do such coating materials as starch, and certain other materials such as waxes. Many of these materials require solvents and moisture for application, which have adverse effects on the stability of hyrophilic instable core materials. For example, simple mixing of 1 food acids in liquid mixtures of traditional coating materials, e.g., fat and lecithin has resulted in poor wetting, spotty coating and inadequate protection against moisture and chemicals. The result was degradation of the aspartame upon exposure to these conditions. Changes in pH and temperature catalyze these degradative conditions.
The process of EPA 81110320.9 (Publication No.
0053844) filed December 10, 1981, discussed above, ic an example of simple admixing of coating materials with aspartame. Thi~ publication discloses the simple melting and admixing of from 20 to 60% of solid fat,10 to 30% of emulsifier, 10 to 30% of polysaccharide and not more than 30% dipeptide sweetener. The mixture is hen cooled and pulverized or spray dried. The pulverizing into fine powder, however, results in rupturing of the coating, leaving the aspartame exposed.
Spray drying is normally associated with the driving off of moisture or qolvents.
U.S. Patent 4,597,970 diccloses a delivery system wherein a sweetener i~ coated with a mixture o fatty acid or wax, lecithin and monoglyceride.
The instant invention seeks to provide coating compositions which eliminate the need for the fatty acid or wax component, yet still provides adequate protection and delayed release of the sweetener, food acid or other active~ contained therein.
The prior art techniques for coating difficult to coat materials such as aspartame, has focused on two methods. The first method involves the formation of a molten mixture of the coating material with the sweetener. The mixture is then solidified by cooling and pulverized. The resultant particles represent a random attempt at completely coating or enrobing the sweetener. In the case of aspartame, this coating does not provide adequate protection against moisture or aldehyde-containing flavor oils and instability of the aspartame results.
The second conventional prior art technique for coating materials involves fluidized bed spray coating.
Thi 8 technique involves suspending a mass of the material to be coated into a stream of atomized drop-lets of coating material. In the case of materials such as aspartame, this method i8 very difficult. Aspartame is a low density material, has a large surface to weight ratio and poor wetting characteristics. For these reasons, spray coating of aspartame in a fluidized bed system is difficult.
The instant process is an improvement over spray congealing techniques and includes additional coating steps. The resultant product exhibits a marked improvement in the effectiveness of the coating as a protective barrier. The result is a significant improvement in the stability of the core material.
Thus, the delivery systems of the invention and 3 process of preparation provide an improved protective coating for core materials. The delivery systems have a variety of other advantages including the controlled release of materials such as sweeteners and flavoring agents. Other advantages will become apparent herein.

Summary of the Invention It has been discovered that a delivery system for food acids can be made using a coating formed from the combination of an emulsifier with low molecular weight polyvinyl acetate. This coating provides an effective barrier against moisture and other conditions such as reactive agents, pH changes and the like. When applied to food acids, these coatings effectuate sustained release of the acid, thereby extending the period of sourness perception, increased salivation and overall enjoyment of the chewing gum or confection.
This invention also concerns chewing gum compositionq having prolonged acid release (sourness) during mastication comprising a gum base and a stable food acid delivery system capable of effecting a controlled release of the acid comprising:
A. At least one food acid selected from the group consisting of citric acid, malic acid, ascorbic acid, tartaric acid, adipic acid, fumaric acid, succinic acid, lactic acid and mixtures thereof;
B. An emulsifier selected from the group consisting of lecithin, stearates, ester derivatives of stearatesj palmitates, ester derivatives of palmitates, oleates, ester derivatives of oleates, glycerides, ester derivatives of glycerides, sucrose polyesters, polyglycerole~ters, and animal waxes, vegetable waxes, synthetic waxes, petroleum wax and mixtures thereof; and C. Polyvinyl acetate present in amounts of about 30% to about 93% by weight of the total composition and having a molecular weight of about 2,000 to about 12,000.
Detailed Description of the Invention and Preferred Embodiments The combination of polyvinyl acetate and the aforementioned emulsifiers produces coatings which form excellent films on the food acids. These coatings are substantially poorly water soluble and protect the food acid or other encapsulated material from hydrolytic degradation. Yet, they possess sufficient hydrophilic character to swell to some degree in the presence of water, thereby slowly releasing the core material.
Glyceryl monostearate is the most preferred emulsifier because it has been found to have the unexpected property of inhibiting the hydrolysis of polyvinyl acetate to acetic acid and polyvinyl alcohol. Other advantages can be enumerated: For example, the coatings are non-cariogenic; no cold flow of polyvinyl acetate is encountered on prolonged storage; the method of making the delivery system does not employ the use of solvents;
and the delivery system can be used in any food, chewing gum, confectionery, personal product or pharmaceutical application where it is desirable to protect a food acid from moisture. Other advantages o the instant invention will become apparent.
The delivery system is prepared by melting the desired ratios of polyvinyl acetate and emulsifier and mixing them at a temperature of about 85C for a short period of time, e.g., 5 minutes or more. Once these materials are sufficiently melted and a homogenous mixture is obtained, the proper amount of solid food acid is added and blended into the molten mass thoroughly for an additional short period of mixing. It is preferred that the food acid particles are milled or ground into a fine powder before encapsulating with the polyvinyl acetate/emulsifier mixture. The resultant mixture is a semi-solid mass which is then cooled to obtain a solid, e.g., at about room temperature, and ground to a U.S. standard mesh size of about 30 to about 200 (600-75 microns).

The instant delivery system can be incorporated in a number of ingestible products such as food products, confection9 and the like, as well as chewing gum compositions, pharmaceutical preparations, denture products, mouthwash and the like.
The resultant product of this invention is in powder or granulated form. The particle size is not critical to the delivery system and can be adjusted to accommodate a particular desired release rate and mouthfeel, depending on the vehicle, e.g., chewing gum or confection, in which it is incorporated. The product can be used "as is" for various applications, e.g., as a topping on baked goods or as an additive in a denture adhesive or mouthwash. The coating matrix is useful for a variety of core materials in addition to food acids, such as sweeteners, spray dried flavors, drug and other particulate materials which require a coating for protection, controlled release or for taste-masking.
These core materials can be used either singly or in combination in either a single or multiple delivery system. That is, one or more of these materials may be present within one coating matrix or coated individually by the matrix and employed alone or in combination in a final product. The food acids can be encapsulated with different amounts or thicknesses of coating such that the acids release sequentially.
The food acids, also commonly referred to as acidulents in the food industry, may be present in amounts of about 0.1% to about 10% by weight of the total chewing gum composition, preferably in amounts of about 0.5% to about 7.5% and most preferably in amounts of about 1% to about 2.5%. In terms of their presence in the delivery system ~ se, the acids are present in amounts of about 1% to about 50% and preferably about 10% to about 35% by weight of the delivery system. The ZOOZ70~

particular amount of acid present must be balanced with the de9ired amount of sourness desired. Too much or too little acid will not achieve the effect of extended flavor, desired tartness and pleasant taste.
The acids may be encapsulated alone or in combination with sweeteners, flavors or similar conventional chewing gum ingredients provided the ingredients are compatible. Alternatively, encapsulated sweetener or flavor can be added separately from the instant food acid delivery system, to provide a unique combination of release properties. The combination of certain flavors, sweeteners and acids have been found to create synergistic effects of longer and more intense flavor, sweetness, sourness and juiciness (saliva stimulation). In particular, the prolongation of acid release gives the chewer the distinct perception of longer taste. Although this phenomenon is not completely understood, it is clear from testing that such taste prolongation exits and can be perceived by the chewer as a substantial improvement over an extended period of mastication.
If an encapsulated sweetener component is to be added, it may be selected from solid natural or synthetic sweeteners capable of imparting high intensity sweetness. A non-limiting list of these sweeteners include amino acid-based sweeteners, dipeptide sweeteners, glycyrrhizin, saccharin and its salts, acesulfame salts, cyclamates, steviosides, talin, dihydrochalcone compour.ds chlorinated sucrose polymers such as sucralose, and mixtures thereof.
The sweeteners which are part of the delivery system may be used in amounts nece~ary to impart sweetness and preferably in amounts of about 0.01 to about 30% by weight of the delivery system. Aspartame, saccharin and its salts are the preferred sweeteners and

2~0Z702 _ 13 may be used in amounts of about 0.01% to about 50% and about 0.01% to 50% respectively, by weight of the delivery system. The preferred amounts of these sweeteners are about 2 to about 10%, most preferably about 4 to about 6% by weight of the delivery system.
Auxiliary sweeteners may be used in the final product, i.e., in a chewing gum composition, in conventional amounts standard in the industry.
A particularly effective combination of sweeteners is aspartame, sodium saccharin and asesulfame K
(potassium acesulfame). Saccharin and its salts and acesulfame salts may be employed in amounts of about 5 to about 50% by weight of the delivery system.
Aspartame is used in amounts up to about 15% by weight when used in this combination. One or more of the sweeteners may be in the encapsulated form prior to incorporation in the delivery system, thus delaying the release of the sweetener and lengthening the perceptible sweetness and/or staggering their release. Thus, the sweeteners may be incorporated such that they release sequentially.
It has also been discovered that the incorporation of the combination of two or more sweeteners used alone or as part of the delivery system improves the sweetness intensity as a result of synergism. Exemplary examples of synergistic combinations are: saccharin/aspartame;
saccharin/potas~ium acesulfame; saccharin/aspartame/
potassium acesulfame. These sweeteners can also be added to the final food confectionery, drug or personal product independently of the delivery system. Thus, a good product may have sweetness imparted thereto attributable to the delivery system sweetness as well as those auxiliary sweeteners independent of the delivery system. These combinations of sweeteners have also been 200Z7G~

_ 14 discovered to impart a long lasting flavor effect to the food product such as chewing gum.
Useful flavoring agents may be chosen from synthetic flavoring liquids and/or liquids derived from plants, leaves, flowers, fruits and so forth, and combinations thereof. Representative flavoring liquids include: spearmint oil, cinnamon oil, oil of wintergreen (methysalicylate) and peppermint oils. Also useful are artificial, natural or synthetic fruit flavors such as citrus oil including lemon, orange, grape, lime and grapefruit and fruit essences including apple, strawberry, cherry, pineapple and so forth.
The amount of flavoring agent employed is normally a matter of preference subject to such factors as flavor type, base type and strength desired. In general, amounts of about 0.05% to about 3.0% by weight of the final chewing gum composition are usable with amounts of about 0.3% to about 1.5% being preferred and about 0.7%
to about 1.2% being most preferred.
With regard to chewing gum formulations in which the novel delivery system is employed, the amount of gum base employed will vary greatly depending on various factors such as the type of base used, consistency desired and other components used to make the final product. In general, amounts of about 5% to about 45%
by weight of the final chewing gum composition are acceptable for use in chewing gum composition with preferred amounts of about 15% to about 25% by weight.
The gum base may be any water-insoluble gum base well known in the art. Illustrative examples of suitable polymers in gum bases include both natural and synthetic elastomers and rubbers. For example, tho~e polymers which are suitable in gum bases, include, without limitation, substances of vegetable origins such as chicle, jelutong, gutta percha and crown gum. Synthetic 200Z7~2 elastomers such as butadiene-styrene copolymers, isobutylene-isoprene copolymers, polyethylene, polyisobutylene and polyvinylacetate and mixtures thereof, are particularly useful.
The gum base composition may contain elastomer solvents to aid in softening the rubber component. Such elastomer solvents may comprise methyl, glycerol or pentaerythritol ester~ of rosins or modified ro~ins, such as hydrogenated, dimerized or polymerized rosins or mixtures thereof. Examples of elastomer solvents suitable for use herein include the pentaerythritol ester of partially hydrogenated wood rosin, pentaerythritol ester of wood rosin, glycerol ester of wood rosin, glycerol ester of partially dimerized rosin, glycerol ester of polymerized rosin, glycerol ester of tall oil rosin, glycerol ester of wood rosin and partially hydrogenated wood rosin and partially hydrogenated methyl ester of rosin, such as polymers of alpha-pinene or beta-pinene; terpene resins including polyterpene and mixtures thereof. The solvent may be employed in an amount ranging from about 10% to about 75% and preferably about 45% to about 70% by weight of the gum base.
Standardly used plasticizers or softeners such as lanolin, stearic acid, sodium stearate, potassium stearate, glyceryl triacetate, glycerine may be used in the gum base compositon. Natural waxes, petroleum waxes, such as polyurethane waxes, paraffin waxes and microcrystalline waxes may also be incorporated into the gum base to obtain a variety of desirable textures and consistency properties. These individual additional materials are generally employed in amounts of up to about 30% by weight and preferably in amounts of from about 3% to about 20% by weight of the final gum base composition.

The chewing gum composition may additionally include the conventional additive~ of flavoring agents, coloring agents such as titanium dioxide; emulsifiers ~uch as lecithin; and additional fillers such as aluminum hydroxide, alumina, aluminum silicates, calcium carbonate, and talc and combinations thereof. These fillers may also be used in the gum base in various amounts. Preferably the amount of fillers when used will vary about 4% to about 30% by weight of the final chewing gum.
In the instance where auxiliary sweeteners are utilized in addition to those in the delivery system, the present invention contemplates the inclusion of those sweeteners well known in the art, including both natural and artificial sweeteners. Thus, additional sweeteners may be chosen from the following non-limiting list: sugars such as sucrose, glucose (corn syrup), dextrose, invert sugar, fructose, and mixtures thereof;
chlorinated sucrose derivatives such as sucralose;
saccharine and its various salt~ such as the sodium or calcium salt; cyclamic acid and its various salts such as the sodium salt; the dipeptide sweeteners such as aspartame; dihydrochalcone compounds; glycyrrhizin;
Stevia Rebaudiana (Stevioside); and sugar alcohols such as sorbitol, sorbitol syrup, mannitol, xylitol, and the like. Also contemplated as an additional sweetener is the nonfermentable sugar substitute (hydrogenated starch hydrolysate) which is described in U.S. Reissue patent 26,959. Alqo useful is the synthetic sweetener

3,6-dihydro-6-methyl-1-1,2,3-oxathiazin-4-one-2,2-dioxide particularly the potassium (Acesulfame-K), sodium and calcium salts thereof as described in Germany patent No. 2,001,017.7.
Suitable flavorings include both natural and artificial flavors. Mints such as peppermint, menthol, 200Z7~)2 _ 17 artificial vanilla, cinnamon, various fruit flavors, used individually or in admixture, are contemplated.
The flavorings are generally utilized in amounts that will vary depending upon the individual flavor, and may, for example, range in amounts of about 0.5% to about 3%
by weight of the final chewing gum composition weight.
The flavorings may be present in the delivery system, in the chewing gum composition itself, or both.
The colorants useful in the present invention, include the pigments such as titanium dioxide, which may be incorporated in amounts of up to about 1% by weight, and preferably up to about 6% by weight. Also, the colorants may include other dyes suitable for food, drug and cosmetic applications, and known as F.D. & C. dyes and the like. The materials acceptable for the foregoing spectrum of use are preferably water-soluble.
A full recitation of all F.D. & C. and D. & C. and their corresponding chemical structure may be found in the Kirk-Othmer Encyclopedia of Chemical Technology, in Volume 5, at Pages 857-884.
The chewing gums of the invention may be in any form known in the art, such as stick gum, slab gum, chunk gum, shredded gum, hard coated gum, tabletted gum, as well as center-filled gum.
The process of preparing the inventive chewing gum compositions i8 as follows. The gum base is melted (about 85 to about 90), cooled to 78C and placed in a pre-warmed (60C) standard mixing kettle equipped with sigma blades. The emulsifier is then added and mixed in. Next, a portion of the bulk sweetener and the softener (e.g. glycerin) is added and mixed in for an additional 3 to 6 minute~. The mixing kettle is cooled and the remainder of the sweetener and softener are then added and mixing is continued. At the time, the unflavored chewing gum temperature is about 39-42C.

_ 18 Flavor oil is then added and incorporated into the base and the mixing is continued. Finally, the delivery system containing the food acid is added and mixed for an additional 1 to 10 minutes. The delivery system is added as the last ingredient, along with artificial high intensity sweeteners, if any. The final gum temperature is about 39~C-43C. The chewing gum composition is then discharged from the ~ettle, rolled, scored and formed into chewing gum pieces.
More generally, this invention relates to a method of preparing a chewing gum composition having improved sustained sweetener release properties which comprises:
(1) Preparing a food acid delivery system wherein the food acid is protected by an encapsulation prepared by the process comprising:
(A) entrapping a particulate food acid in a polyvinyl acetate coating comprising the steps of melting and blending the polyvinyl acetate with an emulsifier and dispersing the food acid uniformly therein; cooling the mixture at ambient temperature while continuing to mix;
(B) grinding the resultant mixture to the desired particle size;
(2) Adding the resultant delivery system to a homogeneous mixture of a gum base and remaining chewing gum ingredients; and (3) Forming the resultant mixture into suitable chewing gum shapes.
Optionally, the delivery system particles can be coated with an additional hydrophobic coating comprising a fat or wax blended with an emulsifier. Conventional, fluidized bed techniques can be used for obtaining these additional coatings.
The following examples serve to provide further appreciation of the invention but are not meant in any zoo27a~

way to restrict the effective scope of the invention.
All percentages throughout the specification are by weight % of the final delivery system unless otherwise indicated.

_ 20 Examples The following compositions A-F are representative of the inventive delivery systems. These compositions were prepared in accordance with the method previously described.
TABLE I
Delivery Systems % by weight Inqredient A B C D E F
Citric acid 5 lO5.00 16.67 24.67 32.67 Fat* _ _ g.oo lO lO lO
Emulsifier** 2 7 2.00 10 10 10 PVA*** 93 83 84.00 63.33 55.33 47.33 * hydrogenated cottonseed oil ** glyceryl monostearate *** polyvinyl acetate M.W. 2,000-14,000 Once the delivery systems were prepared, they were further ground to obtain the desired mesh size, i.e., about 30 to about 200 U.S. standard mesh (600-75 microns~. A second coating of fat or wax and glycerol monostearate blend was applied on some of the above compositions using conventional fluidized bed granulation techniques. This second coating, although not required, is useful in applications where prolonged exposure to acid pH, water or high temperature is likely. The second coating also assures that rod-like or irregularly shaped core materials such as aspartame are adequately coated.
Each of the inventive delivery systems in Table I
were incorporated into the chewing gum compositions of Table II and chewing gum product was produced therefrom using conventional processing techniques common to the art.

Table II, below, shows chewing gum compositions using the Inventive Food Acid Delivery System as well as free, unencapsulated acid (Control IV).

TABLE II
Chewing Gum Compositions % by weight of Total Gum Composition I II III IV _ VI VII
In~redient (Control) Delivery System D 6.00 - - - 9.00 - 6.00 F - - 3.06 - - 1.53 Free acid (citric) - - - 1.00 Gum bflse 19.50 19.50 19.50 19.50 19.50 19.50 23.00 Bulk sweetener*69.1571.10 72.09 74.15 66.15 73.62 Polyol** - - - 50.15 Glycerin 4.00 4.00 4.00 4.00 4.00 4.00 12.00 Flavor 0.90 0.90 0.90 0.90 0.90 0.90 1.00 Emulsifier** 0.25 0.25 0.25 0.25 0.25 0.25 1.60 Color 0.20 0.20 0.20 0.20 0.20 0.20 0.09 High lntensity sweetener - - - - - - 0.16 I-IV: Total acid in each formulation is 1% by weight of the total gum formulation V: Total acid is 1.5% by weight of the total gum formulation VI: Total acid is 0.5% by weight of the total gum formulation * corn syrup and pulverized sugar ** sorbitol/mannitol combination *** lecithin; in VII the emulsifier is a combination of lecithin and vegetable oil Control IV - free acid (unencapsulated acid) Inventive Food Acid Delivery Systems D,E, and F were chosen for use in the final chewing gum compositions as those which were believed to produce the most commercially accepted sourness range.

Figure I graphically demonstrates the results of an expert chew panel which tested Composition I (inventive) and compared it against the control composition IV (free acid). The panel was conducted as a blind study and the panelists were asked to rate the sourness intensity at intervals of 30 seconds, 2 minutes, 6 minutes and 10 minutes. Both compositions contained a total of 1%
citric acid by weight of the total gum composition. As the graph of Figure I indicates the inventive delivery system demonstrated substantialLy higher intensity about 25% higher in the average than the gum containing only free acid through the 10 minute chew. The higher intensity of the sourness indicated a slower release of the encapsulated acid over the free acid. This slower release results in an extension of sourness and concomitant flavor and juiciness without adding a greater amount of acid. Thus, using the inventive food acid delivery system, traditional amounts of acid can be added to achieve greater perceived effects.
Figure II graphically demonstrates the results of analytical chewout studies. Panelist were asked to chew separate samples of composition I (Inventive) and IV
(Control, free acid) for intervals of 2, 7, and 15 minutes. At the end of each interval the panelists submitted that particular sample, now in gum bolus orm, to be analyzed for citric acid content. The graph plots the results of the amount of acid released during mastication at the various time intervals. The amount released was determined from subtracting the amount of acid left in the bolus from the amount originally incorporated in the chewing gum composition. At the 2 minute interval, the Control Sample had released 64% of the acid originally present, whereas the Inventive Food Acid Delivery System released only 42%. Thus, the amount of acid still available for later release in the Inventive Sample is 58%, 22% more acid than the Control.
This demonstrates that the Inventive Food Acid Delivery System delayed the release of its acid.
Between the 2 and 7 minute intervals, the Control Sample released an additional 29% of its acid. The Inventive Sample, however, released 41% additional acid during this interval, which is 12% more acid released than the Control Sample. This demonstrates that the encapsulation of the Inventive Food Acid Delivery System continued to hold back the release of the food acid until later in the chew period.
Between the 7 and 15 minute intervals, the Control Sample released only an additional 6% of its acid as compared to 13% released by the Inventive Sample. The Inventive Food Acid Delivery System delivered more than double the amount of acid during the 7 to 15 minute interval as compared to the Control Sample. Once again, this demonstrates the ability of the encapsulating systems of this invention to prolong acid release during mastication, thereby allowing for the perception of longer lasting sourness and acid flavor as well as increased juiciness.

Claims

We claim:

1. A chewing gum composition having prolonged sourness flavor and juciness duration comprising a gum base and a stable food acid delivery system capable of effecting a controlled release of the acid comprising:
A. At least one particulate food acid selected from the group consisting of citric acid, malic acid, tartaric acid, adipic acid, fumaric acid, succinic acid, ascorbic acid, lactic acid and mixtures thereof;
and B. An emulsifier selected from the group consisting of lecithin, stearates, esters derivatives of stearates, palmitates, ester derivative of palmitates, oleates, ester derivatives of oleates, glycerides, ester derivatives of glycerides, sucrose polyesters, polyglycerol esters, animal waxes, vegetable waxes, synthetic waxes, petroleum wax and mixtures thereof; and C. Polyvinyl acetate present in amounts of about 30% to about 93% by weight of the total composition of the delivery system and having a molecular weight of about 2,000 to about 14,000.

2. The chewing gum composition of Claim 1 wherein the food acid is present in amounts of about 0.1% to about 10% by weight of the chewing gum composition.

3. The chewing gum composition of Claim 1 wherein the food acid comprises citric acid in the amount of about 1.0% to about 7.5% by weight of the chewing gum composition.

4. The chewing gum composition of Claim 1 wherein the food acid is combined with an artificial sweetener prior to encapsulation in the delivery system.

5. The chewing gum composition of Claim 5 wherein the sweetener is present in amounts of about 0.01% to about 50% by weight of the delivery system and is selected from the group consisting of artificial high intensity sweeteners and natural sweeteners and mixtures thereof.

6. The chewing gum composition of Claim 1 wherein emulsifier is present in amounts of about 0.5% to about 20% by weight of the delivery system.

7. The chewing gum composition of Claim 7 wherein the emulsifier is glyceryl monostearate present in amounts of about 2% to about 15% by weight of the delivery system.

8. The chewing gum composition of Claim 1 wherein the polyvinyl acetate has a molecular weight rage of about 2,000 to about 12,000.

9. The chewing gum composition of Claim 9 wherein the polyvinyl acetate is blended with a material selected from the group consisting of resins, rosins, terpenes, elastomers, waxes and mixtures thereof.

10. The chewing gum composition of Claim 1 wherein the gum base comprises an elastomer selected from the group consisting of resins, rosins, terpenes, elastomers, waxes and mixtures thereof.

11. The chewing gum composition of Claim 11 wherein the gum base elastomer is selected from the group consisting of chicle, jetutong, balata, gutta-percha, lechi-capsi, sorva, butadient-styrene copolymers, polyisobutylene, isobutylene-isoprene copolymers, polyethylene, polyvinylacetate, and mixtures thereof.

12. The chewing gum composition of Claim 12 wherein the gum base is present in amounts of about 5%
to about 45% by weight of the final chewing gum composition.

13. The chewing gum composition of Claim 1 wherein there is additionally included fillers, coloring agents, flavoring agents, softeners, plasticizers, elastomers, elastomer solvents, sweetening agents and mixtures thereof.

14. A method of preparing a chewing gum composition having improved sustained sourness, flavor and juiciness release properties which comprises:
(1) Preparing a food acid delivery system wherein the food acid is protected by a matrix coating prepared by the process comprising:
(A) entrapping a particulate food acid in a polyvinyl acetate coating comprising the steps of melting and blending the polyvinyl acetate with an emulsifier and dispersing the food acid uniformly therein; cooling the mixture at ambient temperature while continuing to mix;
(B) grinding the resultant mixture to the desired particle size;
(2) Adding the resultant delivery system to a homogeneous mixture of a gum base and remaining chewing gum ingredients; and (3) Forming the resultant mixture into suitable chewing gum shapes.

15. A method of preparing a delivery system useful for delivering food acids comprising the steps of:
(A) entrapping a food acid in a polyvinyl acetate coating comprising the steps of melting and blending the polyvinyl acetate with an emulsifier and dispersing the food acid uniformly therein; cooling the mixture at ambient temperature while continuing to mix; and (B) grinding the resultant mixture to the desired particle size.

16. A method of preparing a delivery system useful for delivering food acids comprising the steps of:
(A) entrapping a food acid in a polyvinyl acetate coating comprising the steps of melting and blending the polyvinyl acetate with an emulsifier and dispersing the food acid uniformly therein; cooling the mixture at ambient temperature while continuing to mix; and (B) grinding the resultant mixture to the desired particle size; and (C) optionally coating the particles formed in (B) with a hydrophobic mixture comprising a fat or wax blended with an emulsifier to form an additional protective layer on the delivery system particles.

17. A stable food acid delivery system useful in edible products and capable of effecting a controlled release of the acid comprising:
(A) At least one solid food acid selected from the group consisting of citric acid, malic acid, tartaric acid, adipic acid, fumaric acid, succinic acid, ascorbic acid, lactic acid and mixtures thereof;
(B) An emulsifier selected from the group consisting of lecithin, stearates, esters derivatives of stearates, palmitates, ester derivative of palmitates, oleates, ester derivatives of oleates, glycerides, ester derivatives of glycerides, sucrose polyesters, polyglycerol esters, animal waxes, vegetable waxes, synthetic waxes, petroleum wax and mixtures thereof; and (C) Polyvinyl acetate present in amounts of about 30% to about 93% by weight of the total composition of the delivery system and having a molecular weight of about 2,000 to about 14,000.