NZ214424A

NZ214424A - Chewing gum containing an l-aspartic acid derivative sweetening agent

Info

Publication number: NZ214424A
Application number: NZ214424A
Authority: NZ
Inventors: D R Friello; J E Beam; W J Puglia; R L Roy
Original assignee: Nabisco Brands Inc
Priority date: 1984-12-04
Filing date: 1985-12-03
Publication date: 1988-04-29
Also published as: CA1272066A; GB2167641B; GB2167641A; DE3542905A1; CA1272066C; AU5077785A; AU576917B2; FR2573963A1; GB8529498D0

Description

New Zealand Paient Spedficaiion for Paient Number £14424 2 1442 ■y o Priority Date(s): .... ^.Yr. tt-.rlZr.ZY;.

Complete Specification Filed: Cfass: ^Z^L.l/22- Publication Date: ....?,?' j???. P.O. Journal, No: NO DRAWINGS" PATENTS FORM NC.

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NEW ZEALAND PATENTS ACT 195 2 COMPLETE SPECIFICATION "COMESTIBLE CONTAINING MOISTURE AND SHELF STORAGE STABILIZED L-ASPARTIC ACID DERIVATIVE" -£» WE NABISCO BRANDS, INC. a Corporation of the State of Delaware U.S.A. of Nabisco Brands Plaza, Parsippany New Jersey U.S.A.

O hereby declare the invention, for which Ir we prav that a patent nay be granted to ae-us, and the method by which it is to be performed, to be particularly described in and by the following statement ■',feJlow«»d ^y page ' A.1 2 14424 COMESTIBLE CONTAINING MOISTURE AND SHELF STORAGE STABILIZED L-ASPARTIC ACID DERIVATIVE The present invention relates to comestible products which have been sweetened in whole or in part with L-aspartic acid derivative sweetening agents, in the presence of moisture, and more particularly to such comestible products wherein the L-aspartic acid derivatives are stabilized against decomposition during storage.

Aspartame (L-aspartyl-L-phenylalanine methyl ester) is the preferred L-aspartic acid derivative for the purposes of the present invention, and the description of the prior art, and of the present invention, will be discussed primarily based on the use of aspartame, with the understanding that the use of the other L-aspartic acid derivatives listed below is considered to be within the scope of the present invention.

Although aspartame is known to be useful as an intense or concentrated sweetening agent in various types of comestible products, its use in such products has been seriously hampered where such comestible products contain moisture, and/or where such products are manufactured in such a way as to expose the aspartame to an adverse heat history.

It is believed that the presence of water in the products and/or such heat histories leads to the rapid decomposition of thev- aspartame into components such as diketopiperazine which do not provide for, or detract from, the desired sweetening effect. See for example in this regard U.S. 4,122,195, 4,139,639, 4,384,004, and Food Engineering, B.E. Homier, May 1984, pages 127-128. / rr 2144Q' In an effort!to overcome this potential decomposition problem, when using aspartame in comestible products, various solutions to the problem have been proposed. One solution is to endeavor to make the comestible products under anhydrous conditions. See in this regard, for example, International Patent Application W084/01693.

This procedure, of course, requires the use of stringent processing conditions in order to minimize the chances of adding moisture to the product, and it also results in severe restrictions with respect to the types and forms of raw materials that may be used. That is, it precludes the use of aqueous forms of materials such as aqueous sorbitol solutions that have been used in such C o comestible products with sweetening agents other than aspartame.

Another solution to the decomposition problem is to endeavor to use the aspartame in the presence of moisture but in a manner which keeps the aspartame separate and apart from the moisture. This may be done by either using the aspartame on the exterior of the comestible product, as a Coating, for example, see in this regard U.S. 4,374,858, or by using the aspartame within the interior or bulk of the comestible product but in an encapsulated, separated, or admixed form which precludes having a significant, if any, amount of the aspartame from coming into contact with the moisture and/or an adverse heat history during the manufacture and storage of the comestible product and prior to its being ingested by the user thereof. See in this regard, for example, U.S. Patents, Re 29,682; 3,928,633; 4,122,195; 4,139,639 and 4 , 384 ,004. i&Rd-Japanooo Patent Application Publi&aLion J-58-175470, f 'w' S / XT' 2144.2 ftpm soi loon).

This latter solution to the problem, of course, requires the expenditure of significant amounts of effort and expense in pretreating the aspartame in order to effectuate the desired long term separation of the aspartame form the moisture in, and/or heat history of, the product. The encapsulating agents or other means used to effectuate this separation must also be physically and organoleptically compatible with the formulation and utility of the comestible products in which they are used. compensate for the potential loss of the aspartame during storage, even when used in conjunction with one or more of the above noted prior art solutions to the decomposition problem, it is apparently still necessary to use the aspartame at relatively high concentration levels. not been thought readily possible to provide for the use of freely dispersed aspartame, and particularly at relatively low levels thereof, in a comestible product having a relatively high moisture content and with an adverse heat history without encountering a loss of most, if not all, of its sweetening effect due to the relatively rapid decomposition of the aspartame during the storage of the comestible product under the commonly encountered shelf life conditions for such product.

Further, in many, if not all cases, in order to Prior to the present invention, therefore, it has n r f 4 2 1442 4 The present invention provides a means for stabilizing aspartame against decomposition during the long term storage of comestible products containing moisture and freely dispersed aspartame, and having a heat history normally adverse to aspartame.

It has now been found, according to the present invention, that aspartame, when employed freely dispersed, and in relatively low concentrations, in a comestible product containing destabilizing amounts of moisture and, optionally, having a manufacturing heat history of 115 to 130°F for at least 10 to 20 minutes, can be stabilized against decomposition so as to allow for the recovery of at-least 70 to 80%, and preferably at least 80 to 90%, of the initially formulated amount of aspartame after the comestible product has been stored for long periods of time if the comestible product is also formulated with stabilizing amounts of hydrogenated starch hydrolysate.

The hydrogenated starch hydrolysate which may be used in the compositions of the present invention may be a hydrogenated corn syrup or hydrogenated starch hydrolysates of varying dextrose equivalents (DE), such as are disclosed in U.S. Pat. Re. No. 26,959 and U.S. Pat. Nos. 3,556,811, 4,279,931 and 4,382,962, as well as various hydrogenated glucose syrups and/or reconstituted powders which contain sorbitol, hydrogenated disaccharides, tri- to hexa-hydrogenated saccharides, and hydrogenated higher polysaccharides, or mixtures of any two or more of the above.

The hydrogenated glucose syrups or hydrogenated starch hydrolysates and/or powders thereof may be produced by catalytic hydrogenation of standard glucose syrups (acid ^ 15 21442 and/or enzyme converted) to the point where all the glucose end groups of the saccharides are reduced to alcohols, that is, dextrose to sorbitol. In the case of hydrogenated glucose syrups, the total solids contents will usually range from about 65 to about 80%, which solids are made of from about 4 to about 70%, and preferably about 4 to about 20% sorbitol, from about 8 to 65%, and preferably from about 20 to about 65% hydrogenated disaccharides (that is, maltitol), and 20 to 80% of the higher (.2: tri to hepta) © 1Q hydrogenated saccharides. The preferred of the hydrogenated starch hydrolysates contain from about 8 to about 45%, and preferably about 15 to 45%, tri-to hepta-hydrogenated saccharides, and from about 10 to about 35%, and preferably about 15 to 25%, hydrogenated saccharides higher than hepta.

The hydrogenated starch hydrolysate is also referred to in the literature as hydrogenated glucose syrup, or by the trademark or tradename Lycasin polyol or Lonza polyol. The term hydrogenated starch hydrolysate will be used herein to designate such material. The hydrogenated starch hydrolysate is usually sold commercially in the form of an aqueous solution thereof having a moisture content of about 20 to 35%.

The preferred L-aspartic acid derivative to be used in the compositions of the present invention is, as noted above, L-aspartyl-L-phenylalanine methyl ester, known as aspartame. Other L-aspartic acid sweetening derivatives may also be used. Such derivatives are disclosed in U.S. Patent 3,955,000 at column 3, line 63 to column 4, line 35, the disclosure of which is incorporated herein by reference. The following description will be directed to aspartame with the understanding that the other L-aspartic acid sweetening derivatives may be used in lieu of and/or in addition to the aspartame. These compounds are also known as dipeptides. 2 1442 The comestible products of the present invention are sugarless products employing aspartame alone, or in combination with one or more other non-caloric sweetening agents. The compositions of the present invention contain amounts of water which, in the absence of the hydrogenated starch hydrolysate stabilizer of the present invention, would have a destabilizing effect on the aspartame used in such compositions. These destabilizing amounts of water will vary from product to product depending on the amount of aspartame being used and on the presence or absence of an adverse heat history for the product. The comestible products of the present invention, therefore, as contrasted to those made with some prior art technology, may have a relatively wide range of moisture contents, in the range of from about 0.5%, up to about 95% or more. Chewing gum products, for example, made according to the present invention may have a moisture content in the range of about 1 to 8% and preferably of about 3 to 7%, and beverages may have up to 95% or more of water, and other comestibles will have intermediate moisture contents. 90 The comestible products of the present invention may employ a calcium carbonate component as a filler and/or as a pigmenting agent. It is used, therefore, in such amounts as to accomplish such functions. Such amounts may vary from about 1 to about 50, and preferably from about 5 to about 25, weight percent based on the weight of the entire composition. When used as a filler in chewing gum compositions, the calcium carbonate is preferably used in the gum base, and is preferably used in amounts of about 2 to 35, and preferably of about 3 to 10, weight percent, based on the total weight of the chewing gum composition. * 7 21442 4 The comestible products of the present invention may also include those having an adverse heat history, in combination with moisture. A deleterious heat history, in this regard, is a manufacturing heat history which in and of itself and/or in combination with moisture is adapted to cause or accelerate a decomposition of the aspartame during the storage of the comestible product in question after being subject to such manufacturing heat history. Such adverse heat history is one of at least 10 to 20 minutes at a temperature of 115 to 130°F or more.

The comestible products of the present invention, may have a pH, either in the form of the product itself, or in the form of an aqueous extract thereof, in the range of about 5.0 to 7.0. Chewing gum products, made according to the present invention, for example, may have, as such, or as a water extract thereof, a pH in the range of about 4.9 to 7.4, and more preferably of about 6.4 to 6.8.

The comestible products of the present invention will have an aspartame content in the range of about 0.05 to 1.5, and preferably of about 0.1 to 0.3, and most preferably of about 0.20 ± 0.05, percent by weight.

The stabilizing agent to be used with the aspartame is, as noted above, the hydrogenated starch hydrolysate.

This stabilizer component of the compositions of the present invention is used in a stabilizingly effective amount which may vary depending on the amount of aspartame being used, the amount of moisture present in the composition, and the desired shelf life. This stabilizing amount is usually in the range of from >0 to about 30%, and preferably of about 5 to 20%, and most preferably, about 7 to 15%, by weight, on a wet basis, of the product in which the stabilizer is used. © ' 2 1442 On a dry basis, the amount of the stabilizer to be used is usually in the range of from about > 0 to about 21%, and preferably of about 3.5 to 18.5%, by weight of the total composition. The water content of the hydrogenated starch hydrolysate may be the primary source of the moisture present in the comestible products of the present invention, such as the chewing gum products.

The aspartame and hydrogenated starch hydrolysate are freely blended into the comestible products of the £7^ ^ present invention without the need for keeping them separate and apart from each other or from any of the other components of such products during the manufacture and/or storage thereof,and prior to the consumption thereof by the user thereof.

Thus all of the moisture, L-aspartic acid sweetening agent, hydrogenated starch hydrolysate and calcium carbonate (when present) are each freely dispersed in the body of the comestible product. The moisture is not usually added as such but as a component of, for example, the hydrogenated starch hydrolysate, or the glycerine, or of one or more of the other components of the comestible product. Based on the findings of the present inventors there is no need to attempt to keep the moisture, L-aspartic acid sweetening agent and hydrogenated starch hydrolysate, or optional calcium carbonate, in any form thereof, separate and apart from each other. Thus, there is no need to restrict the moisture content of the product to, say below 1 or 2%, nor is there any need to encapsulate, or otherwise modify in any way, nor to use any other means, to avoid having any of these components, in any freely formulated form thereof, from contacting any of other components. None of the formulated 2 1442 amount of the L-aspartic acid sweetening agent is sacrificed by the use of the stabilizing concept of the present invention. All of the formulated amount of the L-aspartic sweetening agent is taken into consideration in assessing the amount of recoverable L-aspartic acid sweetening agent provided in accordance with the teachings of the present invention.

The actual amounts of each of the aspartame and hydrogenated starch hydrolysate to be used in the various comestible products of the present invention will depend on the type of product, the amount of moisture therein, the heat history thereof and the desired level of aspartame usage desired. The amount of the hydrogenated starch hydrolysate used, preferably, should be adequate to provide for a recovery of at least 70% of the initial amount of the aspartame formulated into the product, after the product has been manufactured, packaged and stored, under accelerated storage conditions, for at least 24 days, and preferably at least 35 or more days. Based on experience it is believed that each day of accelerated storage, i.e., at 105°F and at 30% relative humidity, is equivalent to about 7.0 to 7.5 days normal storage time for a product such as chewing gum in stick form. These tests thus indicate that the comestible products of the present invention would be storage stable under their normally encountered ambient storage conditions for at least 6, and preferably at least 9 to 12, months.

Based on the experience of the present inventors it has been found that when used according to the teachings of the present invention, and particularly in chewing gum products, aspartame can be stabilized against decomposition into decomposition products such as diketopiperazine for © ^35 2 1442 4 i ^ extended periods of shelf storage time to such an extent as to allow for the use, over the normal shelf life of such products, about 20 to 50%, and preferably about 30 to 40%, less of the aspartame that would be needed, in the absence of the hydrogenated starch hydrolysate stabilizer of the o present invention, in order to provide for the desired levels of sweetness attainable from the aspartame during the course of such shelf life. The recoverable amounts of aspartame, as reported herein, are analytically determined ^ by the high performance liquid chromatography method. From w a commercial point of view the recovery of the aspartame is achieved in the mouth of the user of the comestible product in which it is' employed.

The comestible products of the present invention include confectionary products such as chewing gum, including the regular non-bubble gum as well as the bubble gum types, hard candy, liquid filled chewing gum and candy; medicinals, such as cough drops, antacids, and breath fresheners; bakery goods such as cookies; and others such as dietetic pack fruits, preserves, jelly, salad dressing, syrups, puddings, ketsup, dry gelatin mixes, beverages, and dry beverage mixes.

The preferred of the comestible products of the present invention are chewing gum products.

The chewing gum compositions contemplated by the present invention comprise all types of sugar and sugarless chewing gums and chewing gum formulations known to those skilled in the art, including the regular gum and the bubble gum types. Typical chewing gum compositions ^ comprise a chewing gum base, a modifier, a bulking agent or W sweetener, and one or more other additives such as, flavoring agents, colorants and antioxidants. The v,:< •* ^ •,,,v ^" 2 14424 modifying agents are used to soften, plasticize and/or compatibilize one or more of the components of the gum base and/or of the formulation as a whole.

A preferred softening agent for use in the chewing gilm products of the present invention is glycerine, which may be used to provide soft, pliable products over extended shelf life conditions, see in this regard European Patent Application 82670 and International Patent Application W084/01693. Unlike the compositions of such European and ^ International Patent Applications, however, the compositions of the present invention need not be made under anhydrous conditions and they may contain moisture in amounts of more than the 1-2% moisture limits imposed by the technology of these other patent applications. The chewing gum i compositions of the present invention may thus contain 0 to t 30, and preferably about 5 to 15, and most preferably about f 16 to 24 weight % of the glycerine, as a softening agent.

The glycerine itself may contain about 1 to 5% moisture.

The chewing gum products of the present invention would have the following formulation: • ~ »!~iw -.Ui,-.. nv'.'-oj « 2 14424 COMPONENT WEIGHT % OF COMPONENT BROAD RANGE PREFERRED RANGE % rV: gum base gum base modifier other than glycerine aspartame moisture* additional sweetener coloring agent flavoring agent CaCO* (when present) + other fillers glycerine hydrogenated starch hydrolysate to 35 0 to 5.0 0.05 to 1.5 2 to 6 0 to 90 0.1 to 0.5 0.5 to 2.5 2 to 35 0 to 35 0 to 30 >0 to 30** to 30 0.3 to 3.0 0.1 to 0.3 3.5 to 5.0 40 to 65 0.15 to 0.3 0.18 to 1.2 3 to 10 0 to 30 5 to 15** to 25 ** Total 100 100 X— * moisture content primarily from hydrogenated starch hydrolysate ** wet basis + usually added as part of the gum base & ■-S 1 * f.

J © '© -13- 2 14424 GUM BASE The composition of the gum base will vary depending on whether the gum base is to be used in a chewing gum product which is to be a regular, or non-bubble, gum product or a bubble gum product. For use in making a bubble gum or regular chewing gum product, the following gum base formulations may be used, in accordance with the present invention: 2 1442 WEIGHT % OF COMPONENT IN GUM BASE FOR BUBBLE GUM PRODUCT REGULAR GUM PRODUCT Broad Preferred Broad Preferred COMPONENT Range Range Range Range masticatory material 8-22 9-18 8-25 9-18 plasticizer for ^ masticatory 5-35 10-20 2-30 8-20 material hydrophillic 0-30 4-10 5-35 10-25 detackifier plasticizer for hydrophillic 0-14 0-8 1-15 3-12 detackifier oleaginous 3-15 5-10 4-20 8-15 material CaC03 2-35 3-10 2-35 3-10 (when present) mineral filler other than CaCO^ 0-20 0-10 0-20 0-10 total filler,i.e., CaCO_ and others 2-35 10-30 2-35 3-10 3 antioxidant 0-0.1 0.05-0.09 0-0.1 0.03-0.09 ^ Total 100 100 '-■r.-k ■ V 2 14424 |! The masticatory substances are elastomeric | |]_ I materials which may be synthetic or natural in origin. The a ? masticatory substances of synthetic origin would include styrene-butadiene copolymer, butyl rubber (which is isobutylene-isoprene copolymer) and polyisobutylene. The natural masticatory substances would include chicle, crown gum, nispero, balata, jelutong, pendare, perillo, niger gutta, tunu, leche caspi, sorva and gutta hank kang.

The plasticizer for the masticatory substance will preferably comprise a hydrogenated ester gum, that is a ^ glycerol ester of hydroganated resin and/or dimerized ester ' gum. However, other resins may be employed such as pentaerythritol ester gum, polymerized ester gum, polyterpene resin and ester gum. yi The hydrophilic-type detackifier is a material • ' l1! | J which will absorb saliva and would include vinyl polymers I having a molecular weight of at least 2000, and preferably f of about 2000 to 80,000 or more, such as polyvinyl acetate, ; polyvinyl butyl ether and copolymers of vinyl esters and/or vinyl ethers with ethylene.

The plasticizers for the hydrophilic type detackifiers would include triacetin, acetylated glycerides and other flavor adjuvants such as ethyl acetate and triethyl citrate, and others as listed in U.S. Patent 4,452,820 at Column 4, Lines 27 to 46, the disclosure of PR ^ which is incorporated herein by reference.

The mineral fillers would include titanium dioxide, talc, alumina, tricalcium phosphate and mixtures thereof.

The oleaginous material includes waxes which are used primarily as compatibilizers/plasticizers between the elastomer and resin phases, where such two phases are employed. Examples of the waxes are petroleum waxes such • •;r^.'*TSK*"-'V •© -"- 2 1442 4 * as paraffin wax and microcrystalline wax; the polyethylene waxes; and natural waxes derived from either plant or animal sources such as candelilla wax, carnuba wax and bees 1 wax. The oleginous material may also include hydrogenated \ vegetable or animal fats, cocoa butter or other 5 ■■ softening-emulsifying agents such as phosphatides such as i lecithin and di and tri-glycerides of fatty acids. I I In addition, the gum base may include antioxidants \ such as butylated hydroxy toluene, butylated hydroxy anisole \ (?j and propyl gallate. \ J The chewing gum compositions of the present ! j ^ invention can be sugar based or sugarless. The sugar or sugar substitute used in the compositions of this invention 1 3 include natural sugars or non-sugar sweeteners. The amount ? —f { * ^ of natural sugar which can be present in the final [ composition can range from about 0.5 to about 90 weight J percent. The amount of non-sugar sweetener which can be ] used can range from 0 to about 2 weight percent of the final composition.

The term "natural sugar" includes one or more sugar containing materials, for example, monosaccharides of 5 to 6 carbon atoms, such as arabinose, xylose, or sorbose or mixtures of two or more of the foregoing monosaccharides; disaccharides such as sucrose, for example, cane or beet sugar including sucrose and dextrose, lactose, maltose or cellobiose; and polysaccharides such as dextrin, or corn syrup solids.

In addition, the dried higher polyhydricalcohols may be employed together with an artificial sweetener such as poorly water-soluble, as well as water-soluble, sweeteners, such as the free acid form of saccharin, sodium, calcium or i - 2 144 4*. ammonium saccharin salts, dihydrochalcones, glycyrrhizin, dipotassium glycyrrhizin, glycyrrhizic acid/ammonium salt, talin, acesulfame K, as well as Stevia rebaudiana (Stevioside), Richardella dulcifica (Miracle Berry), Dioscoreophylum cumminisi (Serendipity Berry), free cyclamic acid and cyclamate salts and the like or mixtures of any two or more of the above. The artificial sweetener may also be employed without any other sweetening agent.

In addition to the above, the chewing gum made by this invention can also contain conventional F. D. & C. and natural coloring agents.

The flavoring which can be included in the chewing gum compositions made in this invention can comprise peppermint oil, spearmint oil and mixtures thereof.

GENERAL PREPARATION OF CHEWING GUM PRODUCT The chewing gum products of the present invention are prepared by first separately preparing the gum base. To then prepare either a sugar based or sugarless chewing gum formulation, the gum base for the product is melted, at a temperature about 190 to 250°F. , and the other components of the composition are added thereto. The resulting composition is uniformly admixed. This takes about 3 to 7 minutes for commercial sized batches of these formulations. Each of the components is usually separately added to the formulated composition and uniformly mixed in before the next component is added. All of the admixing operations are conducted at temperatures in the range of about 115 to 185°F., and preferably of about 125 to 180°F for a total mixing time, at such temperatures, of about 10 to 20 minutes. These operations do not have to be conducted under anhydrous conditions in preparing the compositions of 2 14424 the present invention, and any amounts of moisture that are normally present in the raw materials that are used in the compositions of the present invention do not usually have to be removed therefrom either prior to, or during, the formulating process. The one exception to this concept of not removing water occurs when using rubber latices as the source of the masticatory substance. As in prior art practice, the moisture content of the latex is, essentially, normally removed after coagulating the latex.

The chewing gum formulations disclosed herein may thus be prepared, and processed into chewing gum products, using conventional chewing gum formulation mixing, processing and packaging equipment and concepts.

The following examples are merely illustrative of the present invention and are not intended as a limitation upon the scope therof.

Preparation of Chewing Gum Compositions Various chewing gum compositions were prepared using various of the gum bases prepared as described above. In preparing the chewing gum compositions they were prepared either in pilot plant sized batches or in commercial production sized batches in paddle mixers. In preparing each batch, the previously prepared gum base is melted at a temperature of up to about 245° ± 5°F and is premixed with lecithin and color additive, and, optionally, the hydrogenated starch hydrolysate until the temperature drops to about 185 to 189°F. Then there is sequentially added powdered sorbitol , (at a temperature of 180°F), liquid flavor (i.e. peppermint), liquid sorbitol, if used, glycerine, if used, alone or with the hydrogenated starch 2 144 hydrolysate, if the latter is not premixed with the gum base, any additional flavorants, and finally the aspartame, and, optionally any other intense sweeteners. Each component is paddle mixed in before the next is added.

Each mixing step takes about 0.5 to 5.0 minutes and the total mixing time is about 10-13 minutes. The resulting product is recovered and further processed and packaged using conventional chewing gum making procedures.

The hydrogenated starch hydrolysate used in the chewing gum compositions evaluated in the examples had a solids content of 75 ± 1%, a monosaccharide content of about 6 to 8%, a disaccharide content of about 50 to 55%, and a higher saccharide content of about 38 to 48%. The higher saccharides were about 20 to 25% in the 3-7 DP (degree of polymerization) range, and about 18 to 23% in the >7DP range The liquid sorbitol employed had a solids content of about 70 ± 1. The solid sorbitol is a high (>80%) gamma form having a M.P. of 99 ± 2°C. The aspartame, when used at a 0.10 to 0.50 weight % formulation level, is usually admixed, proportionally, with about 10 to 50 pounds of the formulated amount of powdered sorbitol before being added to the mixing vessel. When being admixed in and further processed the aspartame in the compounded product is usually exposed to a heat history of up to about 120 to 140° F for up to about 20 to 30 minutes.

Unless otherwise indicated, the ^0 content* reported below for each of the chewing gum formulations of Examples 1 to 12 is a calculated amount based on the water content of the hydrogenated starch hydrolysate (HSH) and glycerine (where used) used in the respective formulations. 2 J4424 The actual water content of these formulations is about 0.2 to 0.5% higher than the reported calculated values, since such additional amounts of water enter the final formulated product from the other components of the formulation and from the ambient atmosphere. The total of the reported weight %'s for the respective formulations of these Examples will thus total about 100% plus the respectively reported calculated water contents.

The test formulations were formed into chewing gum products as described above and then subjected to accelerated aging tests conducted at 105°F and at 30° relative humidity. The recoverable aspartame contents of the test products were periodically determined analytically by high performance liquid chromatography (HPLC). Samples of each of the tested formulations were thus analyzed for recoverable aspartame (APM) contents first at zero time, i.e., within 48 hours after the product was first made, and prior to its being subjected to any accelerated aging, and then at various intervals, after 8 to 52 days or more of accelerated aging.

The test formulations were prepared using batch pilot plant or production plant procedures. The pilot plant procedures were used to make the products of Examples 1 to 12 and 23 to 28, and production plant procedures were used to make the products of Examples 15 to 22. These procedures are as follows: The step wise pilot plant procedure used for the products of Examples 1 to 12 was as follows: Prior to beginning the pilot plant batch making process, where glycerine is to be used in the formulation being employed, two separate glycerine/ HSH batches are '/••"»>: >' :• t: 2 14424 1 prepared, each of which contains one-half of each of the formulated amounts of the glycerine and the hydrogenated starch hydrolysate that are to be used in making the product of each example. One of such premixtures is then used in each of steps 4 and 7 as noted below.

If glycerine is not used the HSH is added in two equal increments, as noted below, in each of steps 4 and 7. Step-Wise Pilot Plant Procedure 1. Into a pre-warmed sigma bladed mixer add molten © ^ gum base. The gum base temperature is between 150-200°F, and preferably between 170-190°F. 2. With the blades of the mixer operating, and the temperature in the cited range, the lecithin is added and the mixing is continued for one minute. 3. Add 1/3 of the bulk sweetener (sorbitol powder) and mix for two minutes, or until homogeneous. \ 4. Add one of the glycerine/HSH premixtures or the {. | first 1/2 of the HSH and mix for two minutes, or until | homogeneous. f . Add 1/3 of the sorbitol powder and continue mixing for two minutes. 6. The liquid flavor is then added and mixing is continued for one minute. 7. Add the second glycerine/HSH premixture, or the second 1/2 of the HSH and mix for two minutes. 8. Add the remaining 1/3 of the sorbitol powder and the aspartame. Prior to production of the batch, the aspartame is premixed with approximately 1/3 of the sorbitol powder. Continue mixing for two minutes, or until the batch is homogeneous. The final gum temperature is approximately 112°F.

— » - . V. u u 214424 9. The gum is removed from the mixer and conditioned at 70°F/ambient R.H prior to forming.

. The gum is rolled and scored into a stick configuration. Mannitol is applied to the surface of the scored gum to prevent surface adhesion. The gum is then transferred into fin-seal foil pouches and sealed.

Further formulations Examples 13 and 14 in the pilot plant procedure, the same 10 step procedure as outlined above is used, with the followiong varriations: in © 10 the control, when no hydrogenating starch hydrolysate is used, 1/2 the sorbitol solution is added in each of steps 4 and 7, instead of the glycerine/HSH premixtures or 1/2 of the HSH; when hydrogenating starch hydrolysate is used, it is used in Step 7 in lieu of the sorbitol solution O otherwise employed in Steps 4 and 7 of the control sample.

Step - Wise Production Plant Procedure 1. Into a pre-warmed sigma bladed mixer with the agitators on(in the forward direction) meter in the required amount of molten gum base. After the addition of the gum base is complete, and the gum base temperature is 180°F or less, add the lecithin. Mixing is continued for 7 minutes. 2. The aspartame is premixed with 50 # of sorbitol powder and stored separately until needed. 3. The full amount of the sorbitol powder is added to the mixer. Mixing is continued for 2 minutes. 4. The flavor is added after 30 seconds of mixing. Mixing continues for 2 minutes.

. The full amount of HSH is added to the mixer. Mixing is continued for 3 minutes. 6. The aspartame/sorbitol powder mixture is added to the mixer. Mixing is continued for 2 minutes. © 23 2 1 442 7. The completed gum batch is then transferred into hods and transported to an extruder where the gum is kneaded into ribbons, rolled to the correct thickness and scored into individual strips. The strips may then be conditioned up to 3 days (70°F/55% R.H.) before being scored into pieces. The pieces are dusted during the rolling operation with mannitol to prevent surface adhesion. The sticks of gum are then individually wrapped and packaged in accordance with standard practice in the industry.

In making control products in the production plant procedure an aqueous solution of sorbitol (68 to 69% solids content) is used in lieu of the HSH.

Q 2144 EXAMPLES 1-4 A series of four sugarless regular (non-bubble gum) chewing gum products were prepared using the pilot plant procedure described above and utilizing a gum base based on styrene-butadiene rubber. These formulations for these examples were so follows; in % by weight of each component thereof: o ■ - - i 2 14424 TABLE 1 Example 12 3 4 Gum Base 28.00 Sorbitol Powder 46.73 HSH 21.07 14.12 10.53 7.17 Mannitol** 2.00 Glycerine 0 6.95 10.53 13.90 Lecithin 1.00 Flavor 1.00 Aspartame 0.20 Calculated* 5.26 3.53 2.63 1.79 Water Content dusting agent** 0 1 2 1442 When subjected to the accelerated aging tests the products made from the test formulations of Examples 1-4 provided the following recoverable levels of APM: TABLE 2 %APM Recovered, after indicated Examples days of accelerated aging days: 0 7 21 1 95 90 81 83 2 87 87 78 71 3 90 85 76 68 4 85 86 74 66 These test results indicate the high recoverable levels of APM that can be obtained over extended periods of time with the products of the present invention. On the other hand, when regular chewing gum products are made under comparable conditions with the gum base of Examples 1-4 and with 0.1 to 0.3 % APM and a water content of about 2 to 8%, but without hydrogenated starch hydrolysate, no more than about 55% of the formulated amount of the APM is still recoverable, under the accelerated aging test conditions, after about 3 3 days of such test conditions.

EXAMPLES 5-8 2 144 A series of four sugarless bubble gum chewing gum products were prepared using the pilot plant procedure described above and utilizing a gum base based on polyisobutylene rubber. These formulations for these products were as follows, in % by weight of each component thereof: o * "- 21442 4 ' TABLE 3 Example 5 6 7 8 Gum Base 25.00 Plasticizer 2.00 Sorbitol Powder 47.50 HSH 22.60 16.95 11.30 7.46 Glycerine 0 5.65 11.30 15.14 Lecithin 1.00 I Flavor 1.50- ,-j ^ Artificial color 0.20- Aspartame 0.20 S Calculated* 5.65 4.24 2.82 1.87 Water Content w 15 o i r e 2 1442 When subjected to the accelerated aging tests the products made from the test formulations of Examples 5-8 provided the following recoverable levels of APM: TABLE 4 % APM Recovered, after indicated Example days of accelerated aging days: 0 21 35 108* 92 84 6 101* 91 84 7 103* 94 89 8 103* 94 89 •k The HPLC analytical test results for APM have a tolerance of up to about +8% These test results indicate the high recoverable levels of APM that can be obtained over extended periods of time with the products of the present invention. On the other hand, when bubble gum chewing gum products are made under comparable conditions with the gum base of Examples 5-8 and with 0.1 to 0. 3% APM, and a water content of about 2 to 8%, but without hydrogenated starch hydrolysate, no more than about 80% of the formulated amount of the APM is still recoverable, under the accelerated aging test conditions, after about 21 days under such test conditions. Based on experience it has been found that APM is less susceptible to decomposition in bubble gum based (^) formulations flavored with artificial and natural mixed fruit flavors. o n ..... ■ ■ !1 ~ n 2 1442 EXAMPLES 9-12 I 20 i A series of four sugarless regular chewing gum products were prepared using the pilot plant procedure described above and utilizing a gum base based on styrene jj butadiene elastomer and containing about 22 to 30% ) polyvinylacetate. f These products of Examples 9-11 contained 0.48% Ti02t and the product of Example 12 contained 0.6% O 10 Tl°2 * These formulations for these products were as •yj follows; in % by weight of each component thereof.

N • 4 Ipte TABLE 5 2 1442 J H 1 e Example 9 11 12 Gum Base 24.00 24.00 24.00 28.00 Sorbitol Powder 59. 90 52.90 44.90 54.75 HSH 7.00 14.00 22.00 .00 Glycerine 7.00 7.00 7.00 0.00 Flavor 1.00 1.00 1.00 1.00 Aspartame 0. 10 0.10 0.10 0.25 Lecithin 1. 00 1.00 1.00 1.00 Calculated* 2.1 3.5 .2 3.75 Water Content pH+ .6 .6 .9 — © "32" 2 14414 i When subjected to the accelerated aging tests the products made from the test formulations of Examples 9-12 provided the following recoverable levels of APM: TABLE 6 % APM Recovered, after indicated Example days of accelerated aging days: 0 9±2 + 3 ± 1 34 ; ' 10 9 83.5 95 93 87 — f \ 95.5 89 — 87.8 80 81 1 • 11 95.1 89 — 89.8 86 82 | £ 12 94 95 — 90 93 | These test results indicate the high recoverable levels of APM that can be obtained over extended periods of time with the products of the present invention. On the other hand, when regular bubble gum products are made under comparable conditions with the gum bases of Examples 9-12 and with 0.1 to 0.3% APM, and a water content of about 2 to 8%, but without hydrogenated starch hydrolysate, no more than about 70 % of the formulated amount of the APM is still recoverable, under the accelerated aging test conditions, after only about 21 days under such test conditions. jt- " *" "*• © 2 1442 1 EXAMPLES 13 and 14 A series of two sugarless, regular (non-bubble gum) calcium carbonate-containing chewing gum products were prepared using the pilot plant procedure described above and utilizing a gum base based on styrene-butadiene rubber and containing about 22% polyvinylacetate. The product of Examples 13 and 14 contained 6.488% CaCO^ as part of the gum base. Example 13 is a control sample. Example 13 produced a product of the present invention. The two € products had the following compositions, in weight %,: vi O -34- 2 14424 TABLE 7 Example 13 14 gum base 28.00 28.00 i ! sorbitol powder 46.83 52.75 j sorbitol solution 21.07 0 I HSH 0 15 ; lecithin 1.00 1.00 O mannitol 2.0 0 2.00 I i, flavor 1.0 0 1.00 I aspartame 0.1 0. 25 Total 100.00 100.00 calculated*water content 6.63 3.75 0 o 2 1442 When subjected to the accelerated aging tests, the products made from the test formulations of Examples 13 and 14 provided the following recoverable levels of APM: TABLE 8 % APM recovered after indicated days of accelerated aging Example days: 0 11 12 17 19 33 38 0 1 103. 1 — 79.2 — 69. 7 55 2 98 94 — 90 — — 83 These test results indicate the high recoverable levels of APM that can be obtained over extended periods of time with the products of the present invention, as exemplified by the products of Example 14. On the other hand, when a regular chewing gum product is made under comparable conditions with the gum base of Example 14, but without the HSH stabilizer of the present invention, as exemplified by the product of Example 13, no more than about 55% of the formulated amount of the APM is still recoverable, under the accelerated aging test conditions, after only about 33 days of such test conditions.

The analytical results for HPLC analyses have normal tolerances of up to about 8%, plus or minus.

The 38 days of accelerated testing for the Example 13 product is equivalent to about 266 to 285 days, or between about 9 to 10 months, of ambient storage conditions. ■o> W 2 14424 EXAMPLES 15-22 A series of eight sugarless regular chewing gum products were prepared using the production plant procedure described above and utilizing a gum base based on styrene butadiene rubber.

The formulations for these products were as follows in % by weight of each component thereof: 1.1 c 0 u> ui U> o rv> vn ro o H Ul H O Ul TABLE 9 Examples 6 7 8 9 21 22 Gum Base 28, .00 28, .00 28, .00 28, .00 , .00 , .00 . .00 . .00 Sorbitol powder 46, .90 46. .80 46. .70 46. .80 58. .75 58. .85 58. ,75 53. ,75 Sorbitol solution 21, .00 21. .00 21, .00 21, .00 0, .00 0, .00 0. .00 0. ,00 HSH 0, .00 0. .00 0, .00 0, .00 16, .00 11. .00 . . 00 16. ,00 Glycerine 0, .00 0. .00 0, .00 0, .00 0, .00 . .00 11. , 00 . ,00 Mannitol** 2. .00 2. ,00 2, .00 2, .00 2, .00 2. ,00 2. .00 2. ,00 Lecithin 1. .00 1. .00 1, .00 1, .00 1, .00 1. .00 1. .00 1. .00 Flavor 1. ,00 1. ,00 1. .00 1. .00 1. .00 1. ,00 1. ,00 1. ,00 Aspartame 0. ,10 0. .10 0. .20 0. .20 0. ,15 0. ,15 0. , 15 0. , 15 Na. Saccharin 0. ,00 0. , 10 0, .10 0. ,00 0. .10 0. ,00 0. ,10 0. ,10 Calculated* 6. .63 6. .63 6. .63 6. .63 4. ,00 2. ,75 1. .25 4. ,00 water content dusting agent ** NJ •fc.

NJ v O M 0 ^ 10 ^ 15 2 14424 When subjected to the accelerated aging tests the products made from the test formulations of Examples 15-22 provided the following recoverable levels of APM: TABLE 10 Example % APM Recovered after Indicated days: 0 13 .0+2 28 97 69 56.1 44 16 86 54 47.8 17 87 63 52.6 — 18 84.6 — 51.2 38 19 90.3 — 72.1 63 96.6 — 74.4 62 21 89.3 — 68.1 56 22 94.6 — 71.8 61 n ,6 "IB '• " " " " '" " """* O ~39~ € 2 14< TABLE 11 Example % APM Recovered after Indicated Days of Ambient Storage at 22°C, 50%RH days: 0 76 90 97 105 142 142+ 97 74 — 64 64 — 165/56 16 86 64 — 54 53 — 165/48 17 87 68 — — 60 — 240/49 18 85 — 57 57 — — 217/43 19 90 — 80 — — 72 — 97 — 81 — — 75 — 21 89 — 72 — — 68 — 22 95 — 77 — — 72 The test results of Examples 15 to 22 as shown in Tables 10 and 11 indicate that the use of HSH substantially improves the storage stability of APM when HSH is used as a stabilizer therefor.

The 142+ days for Examples 15 to 22 indicates that the last test for recovered APM for these samples was conducted on the 165th, 165th, 240th and 217th day, respectively, of ambient storage, and provided recovered APM%'s of 56,48,49 and 43 respectively. 2 144 EXAMPLES 23-28 A series of six sugarless regular (non-bubble gum) chewing gum products were prepared using the pilot plant procedure described above and utilizing a gum base based on styrene-butadiene rubber. These formulations for these examples were as follows; in % by weight of each component thereof: 41 2 1442 TABLE 12 1 Example 21 22 23 24 25 26 Gum base 28.00 28.00 28.00 28.00 28.00 28.00 Sorbitol Powder 41.80 37.80 46.80 46.80 46.80 41.80 Sorbitol solution — — 18.00 16.00 13.00 21.00 © 10 xu HSH 15.00 25.00 glycerine 11.0 5.0 3.00 5.00 8.0 5.00 Mannitol 2.00 2.00 2.00 2.00 2.00 2.00 ^ 15 lecithin 1.00 1.00 1.00 1.00 1.00 1.00 Flavor 1.00 1.00 1.00 1.00 1.00 1.00 aspartame 0.20 0.20 0.20 0.20 0.20 0.20 calculated* 3.75 6.25 5.7 5.0 4.1 6.6 water content W O W 2 1442 ^ When subjected to the accelerated aging tests the products made from the text formulations of Examples 23 to 28 provided the following recoverable levels of APM: TABLE 13 % APM Recovered, After Indicated Days of Accelerated Aging Examples 0 10 days; 0 7 28 23 96 92 79 24 89.5 89 75 85.5 79 49.3 26 97 85 52 27 97 87 56.8 28 95 82.5 45.8

Claims

m The test results of Examples 23 and 24 indicate that high recoverable levels of APM can be obtained over extended periods of time with the products of the present invention, which contain HSH. On the other hand Examples 25 to 28 indicate that the use of liquid sorbitol, in lieu 5 .... of HSH, does not provide compositions in which the APM is very stable over long periods of time. 2 144Z 0 10 15 20 25 v7 30 35 -44- 2144^ What is Claimed is:- WHAT -hfWE CLAIM IS:

1. A comestible composition comprising at least 0.5% moisture and a formulated amount of L-aspartic acid sweetening agent derivative stabilized with such t> stabilizing effective amounts of, as a stabilizer for said L-aspartic acid sweetening agent derivative, hydrogenated starch hydrolysate, that, when said composition is stored at 30° relative humidity and 105°F for at least 24 days, at ^ least 70% of said formulated amount of said L-aspartic acid sweetening agent is recoverable as such, and said formulated amount of said L-aspartic sweetening agent derivative is naboufe 20 to 50% less than the amount of said y •3 L-aspartic acid sweetening agent that would have had to £ w have been formulated into said composition, in the absence ; 15 f of said stabilizer, to provide said recoverable amount of ? said L-aspartic acid sweetening agent under said storage conditions, said moisture, L-aspartic acid sweetening agent and said stabilizer each being freely admixed into said composition, and said percents being weight percents and based on the total weight percent of said comestible composition.

2. A comestible composition as in claim 1 which is a chewing gum composition.

3. , A comestible composition as in claims 1 or 2 in which said L-aspartic Acid sweetening agent derivative is aspartame.

4. A comestible composition as in any of claims 1-3 in which moisture is present in such an amount as to deleteriously effect the said L-aspartic acid derivative in the absence of a stabilizer for said derivative. 20 25 30 35 -45- 21442

5. A comestible composition as in any of claims 1-4 having a heat history of at least 115°F for at least 10 minutes.

6. A comestible composition as in any of claims 1-5 wherein the moisture content of -about- 2 to 8%, an aspartame content of about 0.1 to 0.3%, and a hydrogenated starch hydrolysate content of >0 to about. 30%.

7. A comestible composition as in any of claims 1-6 further comprising > 0 to 30% of glycerine.

8. A comestible composition as in any of claims 1-7 which further comprises calcium carbonate.

9. A comestible composition as in any of claims 1-8 further comprising the following additional components,

10. A comestible composition as in claims 8 or 9 which comprises at least 2% calcium carbonate.

11. In a process for preparing and storing a comestible composition that is sweetened at least partially t with at least one L-aspartic acid sweetening agent derivative freely dispersed, as such, therein, and wherein said composition has a moisture content and/or a heat history, which unless stabilized against, upon the normal commercial storage of said composition would cause or accelerate the decomposition of said L-aspartic acid 15 to 35% 0 to 5.0% 0 to 90% 0.1 to 0.5% 0.5 to 2.5% 0 to 35% gum base gum base modifier additional sweetening agent coloring agent flavoring agent filler other than calcium carbonate V •• "A'h-. -»1 .1 A ^ "* A ' r- -46- V a 10 15 derivative into decomposition products which are devoid of sweetening characteristics, the improvement which comprises formulating said composition with, as a stabilizer for said L-aspartic acid derivative and freely dispersed in said composition, hydrogenated starch hydrolysate and in such amounts as to stabilize said L-aspartic acid derivative to the extent of allowing for the recovery from said composition of at least 70% of the formulated amount of said L-aspartic acid derivative after the storage of said composition for at least six months.

12. A comestible composition as claimed in claim 1 substantially ao olaimod in claim 1- specifically as hereinbefore described in any one of Examples 1-12, 14-28.

13. A process for preparing and stirring a comestible composition of claim 1 as hereinbefore described. 20 BALDWIN, SON & CAREY 'AnoeNE'fS FOR THE APPLICANTS 25 30 35 S F. V- £> 21442 10 ABSTRACT OF THE DISCLOSURE Comestible compositions such as chewing gum containing freely dispersed L-aspartic acid sweetening agent derivative, moisture, and optionally, a manufacturing heat history of at least 115°F, are rendered storage stable relative to the retention of recoverable levels of the L-aspartic acid derivative by adding freely dispersed hydrogenated starch hydrolysate thereto, thereby allowing for the effective use of relatively low levels of such L-aspartic acid derivative therein.