WO1990008478A1

WO1990008478A1 - Food flavoring high-note enhancement by microbead delivery

Info

Publication number: WO1990008478A1
Application number: PCT/US1990/000461
Authority: WO
Inventors: Steven E. Zibell; Lindell C. Richey; Michael J. Greenberg; David Witkewitz
Original assignee: Wm. Wrigley Jr. Company
Priority date: 1989-02-06
Filing date: 1990-01-25
Publication date: 1990-08-09
Also published as: CN1044580A; AU5166290A; PH27116A; NZ232237A

Abstract

A food product that contains porous polymeric beads impregnated with flavoring components, and a method of making such a food product.

Description

FOOD FLAVORING HIGH-NOTE ENHANCEMENT BY MICROBEAD DELIVERY

BACKGROUND OF THE INVENTION

This invention relates in general to food flavoring, and in particular to foods prepared such that "high-note" flavors are enhanced.

Food flavorings are very complex chemically. Many food flavorings are oily substances that include complex mixtures of compounds that have varying degrees of volatility. Each mixture essentially has its own signature identified by the types, relative amounts, and volatility of its component compounds.

Unfortunately, food processing, transportation, and storage involves subjecting foods to sufficient heat that can drive off the most volatile fractions of flavoring. The most volatile fractions of a flavoring are typically the "high-notes" or "low boiler" fractions. Once the high notes are reduced or eliminated in a food flavoring, the flavoring or food containing the flavoring typically tastes noticeably different. In some cases, the flavoring is unrecognizable

An example will illustrate the point. Many flavorings are spray-dried, that is, they are dissolved in a gelatinous matrix (e.g. in gum arabic and starch) and the mixture is sprayed thorough an orifice to dry off the water. A dry particulate material containing the flavoring is the result. An unintended result is that at least some of the high notes in the flavoring are volatilized during spray-drying.

Still another problem with some food flavorings is shelf-life. Some flavorings oxidize over time so they no longer impart the desired flavor to the food even though the food is otherwise acceptable. Other flavorings can react with other food ingredients over time with the same loss of food flavor.

Efforts have been made to extract high notes from foods or flavorings prior to food processing and add the high notes back to the food after processing. However, such procedures do not solve problems of volatilization of high notes or oxidation or reactions of ^"food flavorings during storage.

SUMMARY OF THE INVENTION

According to the current invention, a food product has dispersed in it water-insoluble, porous polymeric beads that have microporous passages in them impregnated with one or more food flavorings containing volatile substances. In narrower aspects of this invention, the beads are coated with water-soluble coatings to entrap the flavorings in the beads until the beads are exposed to water. Alternatively, the beads can be coated with a coating that melts when heated so that the flavoring will not be released until the food is heated. Because the beads of this invention are polymeric, they exhibit an affinity toward food flavoring oils that retards the volatilization of the high notes. In addition, the entrapment of the food flavoring in the microporous passages reduces the exposure of the flavoring to oxidants and to other substances- in the food that may react with the flavoring during storage.

DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS OF THE INVENTION

In the present invention, a food product (or matrix) contains porous polymeric beads that have microporous passages impregnated with flavoring agents. The flavoring agents may comprise essential oils, synthetic flavors, or mixtures thereof, including but not limited to, oils dried from plants and fruits such as citrus oils, fruit essences, peppermint oil, spearmint oil, clove oil, oil of wintergreen, anise, and the like. Artificial flavoring components are often included. Those skilled in the art will recognize that natural and artificial flavoring agents may be combined in any sensorially acceptable blend. All such flavors and flavor blends are contemplated by the present invention.

By "food product" or "food matrix" is meant an edible substance that delivers nutrition or taste pleasure to humans or other animals. Food matrices include any foods that have typically had their taste enhanced by the addition of flavoring agents. Food matrices include but are not limited to meats, baked goods (i.e. breads, cakes, cookies, and pies and the like), puddings, syrups, gums, and the like. Food matrices also include dry or condensed mixes that upon addition of water or other ingredients form an edible substance that can be eaten immediately or eaten after cooking or further processing. Mixes include baked good mixes, soup mixes, pudding mixes, and the like.

Food matrices also include liquid beverages and concentrates for liquid beverages. With liquid beverages or concentrates, the porous polymeric beads containing flavorings can be added to the liquid im-- mediately before the product is packaged so the "high notes" will not be lost. The flavoring is released to the drink from the beads during storage and shipment of the product. This release can be delayed by using a water-soluble coating that dissolves over time. Food matrices also include powdered or granular mixes for liquid beverages that are mixed with water to produce liquid beverages. A powdered or granular beverage mix usually includes a beverage base that ordinarily has flavoring (e.g. coffee or citrus flavor) and often a sweetener and the like. Beverage bases are known in the art and include instant coffee, milk shakes, fruit drinks, and the like. The flavor- impregnated microbeads of this invention can be coated with a water-soluble coating that dissolves to release flavoring upon addition of water to the mix (.e.g. a cocoa, chocolate .or fruit flavor delivered to the water by beads) . Alternatively, the beads can be coated with a coating (e.g. fat) that melts when hot water is added, a feature desirable in hot drink mixes such as cocoa or coffee.

In making syrups, the process involves boiling a juice (e.g. a fruit juice or a maple tree sap) to drive off water. In the process "high notes" are lost. These "high notes" can be distilled from the vapors generated during boiling, absorbed into microbeads that are then coated, and the microbeads can be added back to the syrup.

The present invention contemplates the addi¬ tion to a food matrix described above of water-insoluble porous polymeric beads preferably of size not discernible to the consumer where the beads have microporous passages impregnated with one or more flavorings described above. The preferred size range is between 10 and 100 microns, and the most preferred is between 20 and 50 microns. Preferably, the porous polymeric beads' are coated with a coating that influences the release of the flavoring oils within the microporous passages in the porous polymeric beads. Such coatings include zein, wax, gum arabic, fatty acids, fats, a food-grade shellac, carbohydrates, silica, water-insoluble polymers (e.g. , polyvinyl acetate), proteins such as casein, starches, dextrins, or modified or unmodified cellulosics such as ethyl, methyl, hydroxy- propyl or hydroxyethyl cellulose. The use of such coated beads controls the release of the flavoring oil high notes in the porous polymeric beads, typically such that the ingredients within the beads are released at a time when the food product is used by the consumer.

The present invention also contemplates the addition of other food additives together with flavorings to microbeads. For example, anti-oxidant compounds such as BHT and BHA can be mixed with a flavoring oil, and the mixture impregnated into microbeads. The anti-oxidant and the location of the flavoring oil in the microbeads will retard oxidation of the flavoring oil. Oxidation is a particular problem with some flavoring oils such as peppermint oil because oxidation can cause the flavor to change. The location of the flavoring oil in the microporous passages reduces exposure to oxygen. The addition of an anti-oxidant enhances the preservation of the flavoring. One advantage is that anti-oxidant can be targeted to the flavoring oil, and need not be in high concentration throughout the food.

The polymeric beads of this invention are polymerized in such a fashion that the microporous passages are formed during polymerization. Such a procedure is described below. Residual monomer is then extracted as described below so that the particles can be impregnated with flavoring oils or components thereof. The beads are then optionally coated with one or more coatings and added to the food matrix. The details of microparticle polymerization, monomer extraction and microparticle impregnation and coating are described below, followed by Examples I through XIV that illustrate various specific foods and polymeric beads of the current invention. I. POLYMERIC BEAD POLYMERIZATION

In one embodiment of the present invention, the polymeric beads can be polymerized as taught in U.S. Patent 4,690,825 to Won dated September 1, 1987, the entire disclosure of which is incorporated herein by reference. Specifically, the beads used in the food matrix of the present invention can be prepared by polymerizing one or more polymers by a free radical suspension polymerization process. A monomer or pair of comonomers is dissolved in an inert porogen to form^" a solution that is suspended in a phase or solvent incompatible with that solution. Such a phase or solvent can be water with stabilizing additives. After the solution is suspended in the phase, the solution and phase are agitated to form droplets of solution suspended in the phase. After the formation of the droplets, the monomer or monomers in the droplets are activated to initiate a polymerization reaction in which the monomer is cross-linked or where two or more monomers are polymerized to form porous beads having a network of pores with the porogen within the network of pores. The activation may be triggered by an initiator that is insoluble with the monomer solution. Alterna¬ tively, activation may be triggered by an energy source such as radiation. The inert porogen serves as an internal diluent during polymerization and introduces the desired sponge-like microporous structure or network of pores into the finished bead. The inert porogen does not react with the monomer present during polymerization or inhibit the polymerization. The bead may or may not swell in the inert porogen. After formulation of the porous beads, the beads are separated from the phase and subjected to one or more extraction steps such as washing to remove any unreacted monomer or impurity from the beads. After extraction, described below, the beads may be dried to obtain a powder-like substance that includes the beads but without either porogen or solvent.

An example of a polymer that can be used to form porous polymeric beads for the food product of this invention is a copolymer of divinylbenzene and styrene. Such beads can be polymerized in water as taught in the aforesaid Won patent or as described in Example I below. If such a copolymer is used, monomers (nonfood approved additions) are typically not com¬ pletely reacted, and excess monomer concentration should be reduced to levels less than 30ppm [as illustrated by the styrene monomer standards for food-grade styrene-butadiene rubber (Food Chemical Codex, 3rd Edition, pg. 42. )] if the beads are to be used in a food product. Typically, the amount of free cross linking agent (divinylbenzene) in the beads after poly¬ merization is quite low compared with styrene because divinylbenzene has two reaction sites, and thus is more reactive than styrene. Thus, the extraction is primarily to extract styrene monomer, the divinylbenzene monomer present in the polymer already being close to or lower than the 30ppm value. An extraction procedure is ex¬ plained in Section II below and in Example I.

To avoid or reduce the effort required in monomer extraction, one can copolymerize divinylbenzene with a food-grade monomer that can polymerize with divinylbenzene. By a food-grade monomer is meant any monomer that is a food additive permitted for direct addition to food for human consumption under 21 CFR, part 172 or substances generally recognized as safe under 21 CFR, part 182. Examples of such monomers are one or more of the following: estragole, limonene, carvone, eugenol and ocimene. Limonene is illustrative inasmuch as it is a naturally-occurring compound in many citrus fruits. Still other examples are provided in Example V, infra.

The food-grade monomer need not be extracted unless one wants to extract it for flavor reasons. But in many instances, the food-grade monomer may enhance the flavor of the food. Thus, any extraction of monomer after polymerization may only have to focus on divinylbenzene reduction, a comparatively simple proposition because it is already in comparatively low concentration.

II. MONOMER EXTRACTION

If monomer extraction is desired or required, it can be -accomplished by washing the beads first with water followed by several (preferably three) washings of isopropanol, four to five washings with acetone and four to five washings with hexane. The excess solvent is removed by evaporation under a nitrogen blanket to leave dry beads having a powder-like consistency.

III. POLYMERIC BEAD IMPREGNATION WITH FOOD FLAVORING COMPONENTS

The impregnation of the pores in the polymeric beads with food flavoring components can be accomplished by soaking the beads in an equal or greater weight of the flavoring component so that the beads are completely immersed. The impregnation proceeds over a period of at least six and preferably

48 hours. The impregnation may be carried out at reduced temperature if stability or volatility of the flavoring is a particular concern. Of the total dry weight of the loaded beads after impregnation, 60% or even more may be active ingredient. Such loadings are possible using this procedure, although some bead/active agent combinations will yield lower loadings. In some cases, pretreatment of the flavoring may be desirable. For example, if the flavoring is a solid, it must first be dissolved, suspended or slurried in a liquid carrier before impregnation. If a liquid flavoring is viscous, dilution may be desirable before impregnation.

Some flavors may have sufficiently low viscosities for easy impregnation, but the low viscosity may lead to loss of the flavoring from the porous microbead during subsequent handling and/or storage of the food product. In such cases it may be desirable to increase viscosity before or after impregnation. This may be accomplished by gellation, coagulation, precipitation, or through use of thickeners.

Yet another embodiment is the use of meltable active agents or carriers. In such cases, impregnation is carried out at a temperature above the melting point of the active agent or carrier/active agent blend. After impregnation, excess meltable ingredient is removed and the beads are cooled to incorporate the active agent into the beads.

IV. POLYMERIC BEAD COATING

As indicated above, the porous polymeric beads are preferably coated with a coating that retards the release of the flavoring from the pores of the beads or prevents premature release during storage. Illustrative coatings include water-soluble or permeable compositions such as hydroxypropyl methyl-^' cellulose, sugars, and the like. Depending on the thickness and porosity of the water-soluble or permeable coatings, such coatings retard the release of the flavoring in the pores of the polymeric beads by first requiring the coating to dissolve before the flavoring is released.

Water-insoluble coatings may also be em¬ ployed. Such coatings include food-grade shellac as disclosed in U.S. 4,673,577 to Patel dated June 16, 1987 that is incorporated herein by reference. Water- insoluble wax coatings also include waxes such as those disclosed in United States Patent Application Serial No. 07/137,114 entitled Method of Making Chewing Gum with Wax-Coated Delayed Release Ingredients by Steven E. Zibell which is incorporated herein by reference, and zein.

Fatty acids can also be employed as coatings for the beads. Fatty acids, depending upon chain length, have varying water solubilities. A mixture of fatty acids can be prepared that has tiie desired degree of water solubility that controls the dissolution of the coating until the desired time. Combinations or mixtures of various water-soluble and water-insoluble coating agents may be employed as coatings for the porous beads to control the release of the flavoring from the beads.

In some applications, it is advantageous to have coatings that melt when heated. For example in hot drink mixes such as coffee or cocoa mixes, beads containing chocolate flavoring, for example, can be coated with a fat that melts when hot water is added. In baking mixes, the flavoring is released from the beads when a coating is melted. Such coatings are those that melt at temperatures above 30°C, preferably above 100°C. The preferred coatings are fats.

It is also possible to have different popula¬ tions of beads within the food, each population coated with a different coating having a different water solu¬ bility or melting point than the other populations, or - 1 I - one or more populations being left uncoated while one or more populations are coated with various coatings having different solubilities or melting points. One after another, the various populations will release their active ingredients to extend the overall time of release greatly. The prolonged release of flavoring is useful, for example, in baked goods that release volatile flavor/aroma compounds during baking. A variety of methods to coat the beads can be used. Several are described generally below, and in detail in the Examples, infra.

A. Spray Drying

An emulsion/solution of flavoring-impregnated beads and encapsulant is atomized into an air stream that evaporates the solvent to leave coated beads. A Niro spray dryer may be used. This technique should be used only where it does not allow substantial amounts of the high notes in the flavoring to volatilize. It is believed to be a workable technique in some cases because certain flavors are entrapped in the passages in the beads. In addition, exposure of the microparticles to air is very brief, and not much flavor is lost.

B. Spray Chilling

A suspension of beads in molten encapsulant is atomized and chilled to produce beads coated with encapsulant.

C. Fluid Bed Coating

Beads are suspended in an air stream (fluidized bed) . The beads are sprayed with a solution of the encapsulant in a volatile solvent. The solvent is evaporated or dried by the air stream to produce beads coated by the encapsulant. D. Granulation/Agglomeration

A damp mix of beads and granulant is prepared, then dried and ground to desired particle size.

E. Gel Encapsulation

Beads are suspended in a gelatin solution that is cooled to gel, then ground to desired particle size.

F. Melt Blending

Beads are mixed into a molten agglomerant which is cooled to harden and ground to the desired particle size.

The following examples- of the invention are provided by way of explanation and illustration. They are not intended to limit the invention.

Example I Peppermint Non-Tack Gum A) Preparation of Microbeads

Gelatin (250 mg) is added to a three-necked flask purged with nitrogen. Water (150 ml) is heated to 50°C and added to the flask to dissolve the gelatin. While the contents of the flask are stirred, a freshly prepared solution of benzoyl peroxide (1.25 grams; 1.03 mmole) and styrene (22.9 grams; 0.22 mole) monomer is added, followed by divinylbenzene (12.0 grams; 42- m oles) . The mixture is heated to 90°C while maintaining a constant stirring rate, and passing nitrogen through the flask.

The mixture is stirred for two hours, and cooled to room temperature, and the supernatant liquid is decanted. The polymer beads are washed with hexane several times, and stirred in hexane (200 ml) for two hours to remove any excess divinylbenzene or styrene, and dried overnight at 50°C in a vacuum to yield dry microbeads. B) Impregnation of Microbeads with Peppermint Oil

A solution of 50% peppermint oil and 50% of a 2% aqueous solution of egg albumin is mixed vigorously to disperse the peppermint oil in the water. Micro- beads from part A are mixed with an equal weight of this solution for six hours. Excess solution is removed by filtration or centrifugation. The mixture is warmed to about 50-75°C to coagulate the solution. The resulting beads will contain approximately 25% peppermint oil by weight.

C) Preparation of Gum Base

A gum base set forth in Table I below is prepared as described in U.S. Patent No. 3,984,574.

Table I

Ingredient

Polyvinyl Acetate

Hydrogenated Soybean Oil

Partially Hydrogenated Vegetable Oil

Calcium Carbonate

Polyisobutylene (Molecular

Weight 6-12 M) Isobutylene-isoprene Copolymer Mono and Diglycerides of Fatty Acids Hydrogenated Cotton Seed Oil

Specifically, the polyvinyl acetate, polyiso¬ butylene, and the isobutylene-isoprene copolymer are melted, and added to a mixer. Then the fatty acids, oils, and remaining ingredients are added and mixed until the mixture is well mixed.

C) Preparation of Peppermint Gum

To the base of part B, sugar, 45° Be' corn syrup, glycerin, peppermint oil, and microbeads from part B are added in the proportion by weight set forth in Table II .

Table II

Percent Ingredient by Weight

Base 20.0

Sugar 58.9

45° Be' Corn Syrup 17.4 Glycerin 0.7

Peppermint Oil 0.6

Microbeads 2.4

Example II Spearmint Sugarless Gum

A) Preparation of Microbeads

Gelatin (250 mg) is added to a three-necked flask purged with nitrogen. Water (150 ml) is heated to 50°C and added to the flask to dissolve the gelatin. While the contents of the flask are stirred, a freshly prepared solution of benzoyl peroxide (1.25 grams; 1.03 mmole) and ocimene (29.92 grams; 0.22 mole) monomer is added, followed by divinylbenzene (12.0 grams; 42 mmoles) . The mixture is heated to 90°C while-main¬ taining a constant stirring rate, and passing nitrogen through the flask.

The mixture is stirred for two hours, and cooled to room temperature, and the supernatant liquid is decanted. The polymer beads are washed with hexane several times, and stirred in hexane (200 ml) for two hours to remove any excess divinylbenzene, and dried overnight at 50°C in a vacuum to yield dry microbeads.

B) Impregnation of Microbeads with Spearmint Oil

Spearmint oil and a 2% aqueous solution of guar gum are mixed vigorously at a 50:50 ratio by volume so that the oil is dispersed throughout the guar gum solution. The microbeads from part A are mixed in the spearmint oil/guar gum mixture for 24 hours. The mixture is cooled so that it gels.

C) Preparation of Spearmint Gum

LADCO Astro Base (A) 2031, a commercially available gum base from the L.A. Dreyfus Company of Edison, New Jersey, is mixed with an aqueous solution of 70% sorbitol, crystalline εorbitol, glycerin, spearmint oil, and microbeads from part B of this example according to the proportions in Table III to produce a spearmint gum that is rolled into sheets and cut into pieces.

Table III

Ingredient

LADCO Astro Base (A) 2031

70% Sorbitol Solution

Sorbitol

Glycerin

Spearmint Oil

Microbeads 2.4

Example III Sugared Cherry Gum A) Preparation of Microbeads

Gelatin (250 mg) is added to a three-necked flask purged with nitrogen. Water (150 ml) is heated to 50°C and added to the flask to dissolve the gelatin. While the contents of the flask are stirred, a freshly prepared solution of benzoyl peroxide (1.25 grams; 1.03 mmole) and limonene (30 grams; 0.22 mole) monomer is added, followed by divinylbenzene (12.0 grams; 42 mmoles) . The mixture is heated to 90°C while maintaining a constant stirring rate, and passing nitrogen through the flask. The mixture is stirred for two hours, and cooled to room temperature, and the supernatant liquid is decanted. The polymer beads are washed with hexane several times, and stirred in hexane (200 ml) for two hours to remove any excess divinylbenzene and dried overnight at 50°C in a vacuum to yield dry microbeads.

B) Impregnation of Microbeads With Cherry Flavoring

A wax (melting point 115°F) is melted and mixed with a cherry flavoring in a ratio of 25% wax and 75% flavoring by weight. Microbeads from part A are added in equal weight to the molten wax, allowed to set for six hours, and excess wax is removed. The mixture is cooled to leave finely divided microbeads impregnated with cherry flavor and coated with wax.

C) Preparation of Cherry Gum

LADCO Bubble Base T 2198, a commercially available gum base available from L.A. Dreyfus Company, is mixed with 43° Be* corn syrup, sugar, glycerin, cherry flavor, and microbeads from part B above according to the proportions in Table IV to produce a cherry-flavored gum that is rolled into sheets and cut into pieces.

Table IV

Percent Ingredient by Weight

LADCO Bubble Base T 2198 20.0

43° Be' Corn Syrup 25.0

Sugar 52.7

Glycerin 0.5

Cherry Flavor 0.6

Microbeads 1.2 Example IV Peppermint Sugar Stick Gum A) Preparation of Microbeads

Gelatin (250 mg) is added to a three-necked flask purged with nitrogen. Water (150 ml) is heated to 50°C and added to the flask to dissolve the gelatin. While the contents of the flask are stirred, a freshly prepared solution of benzoyl peroxide (1.25 grams; 1.03 mmole) and eugenol (36.1 grams; 0.22 mole) monomer is added, followed by divinylbenzene (12.0 grams; 42 mmoles). The mixture is heated to 90°C while maintaining a constant stirring rate, and passing nitrogen through the flask.

B) Impregnation of Microbeads with Peppermint Flavor

The procedure of Example I, part B is repeated using the microbeads of part A of this example to obtain microbeads impregnated with peppermint flavor.

C) Preparation of Peppermint Sugar Stick Gum

LADCO Paloja® Base, a commercially available gum base from The L.A. Dreyfus Co., is mixed with 45° Be' corn syrup, sugar, glycerin, peppermint oil and microbeads from part B in the proportions set forth in Table V below, to produce a peppermint sugar stick gum.

Various microbead polymers are possible con¬ sistent with the teachings of this invention. A number of types of microbeads can be prepared following the procedure set forth in Example III part A, altering the amount of monomer to be polymerized with divinylbenzene, or changing the monomer to be polymerized with divinylbenzene. Alternatively, the amount of divinylbenzene can be varied. A summary of such microbead formulations is set forth in Table VI below.

Table VI

Table VI Cont'd

Monomer Monomer Amount g) Ocimene 29.92 g; 0.22 mole h) Ocimene 29.92 g; 0.22 mole i) Divinyl- sulfide 18.96 g; 0.22 mole j) Vinyl ethylketone 15.42 g; 0.22 mole k) 4-methyl-5-vinyl thiazole 27.5 g; 0.22 mole

1) 2-methyl-5-vinyl pyfazine 26.1 g; 0.22 mole m) Vinyl pyrazine 23.32 g; 0.22 mole n) l-penten-3-ol 18.92 g; 0.22 mole o) l-octen-3-ol 28.16 g; 0.22 mole

P) carvone 33.00 g; 0.22 mole q) limonene 29.92 g; 0.22 mole r) diallyl- disulfide 32.18 g; 0.22 mole s) allylsulfide 25.13 g; 0.22 mole t) allyl al¬ pha ionone 51.12 g; 0.22 mole

The monomers identified above to be polymer¬ ized with divinylbenzene can also be combined with styrene to yield the desired beads. In addition, divinylbenzene can be replaced with allylacrylate as the crosslinker or with other suitable divinyl com¬ pounds.

Microbeads produced from the polymers de¬ scribed above are made from food-grade monomers that can polymerize with divinylbenzene. The residual food-grade monomer in the microbeads can contribute flavor to the food. Accordingly, to achieve a proper blend of food-grade monomer with the flavoring of the food to achieve good taste, certain combinations of food-grade monomer and food flavorings are preferred, as indicated in Table VII below.

Table VII

Gum Flavoring Monomer(s) Mint Estragole, ocimene, vinyl- methyl ketone, l-octen-3-ol, l-penten-3-ol, carvone, limonene, allyl alpha ionone

Onion Divinylsulfide, diallyldisulfide, allylεulfide

Citrus Ocimene, carvone, limonene Peanut 4-methyl-5-vinylthiazole, 2-methyl-5-vinylpyrazine, vinylpyrazine

Meat 4-methyl-5-vinylthiazole, 2-methyl-5-vinylpyrazine, vinylpyrazine, diallyldisulfide, allylεulfide

Fruit Eugenol, allylcyclohexyl propinate, limonene

Cinnamon Estragole, eugenol, limonene

The polymerized food-grade monomer also forms a polymer with regions that have an affinity toward certain flavorings that can be absorbed into the microbeads. This can improve the impregnation of the microbeads into the pores of the polymeric beads. These regions are essentially polymeric chains of food-grade monomer. If the flavoring agent can dissolve into or has an affinity toward the food-grade monomer, the flavoring agent will likely have an affinity toward the polymeric chains in these regions. Example VI

Menthol Chewing Gum Containing Microbeads Made from Block Copolymers of Styrene and Butadiene

A) Preparation of Microbeads

The flexibility or sponginess of the microbeads can be controlled by forming the microbeads from block copolymers of styrene and butadiene. Copolymers of styrene and butadiene can be polymerized as di-block copolymers, tri-block copolymers, and tetra-block copolymers by varying the proportions of styrene and butadiene in the reaction mixture, as is known in the block copolymer art. The advantage of block copolymers of styrene and butadiene is that gum active ingredients in the microbeads will diffuse into the rubbery domains in the microbeads, resulting in slower release of gum active ingredients. The beads can also be made more crack resistant than styrene- divinylbenzene beads.

Beads of styrene and butadiene block copolymers are made by dissolving such a block copolymer (5 g Kraton D1101 from Shell Chemical Company) in toluene (150 g). In a separate beaker, polyvinylalcohol (1.5 g) is dissolved in water (450 g) at about 40°C. The block copolymer solution is mixed with styrene monomer (90 g), and divinylbenzene monomer (45 g) and benzoyl peroxide (1.5 g) are added to the mixture, and the mixture is agitated at room tem¬ perature. The mixture with block copolymer is added to the polyvinylalcohol solution, and the combined mixture is agitated with a motor-driven propeller.

The mixture is heated to 80-90°C for at least four hours during which time it is agitated. The mixture is cooled, and filtered to remove the beads. B) Impregnation of Beads with Menthol

Menthol is dissolved in molten wax (melting point 95°F) in a 75% menthol - 25% wax ratio. The molten mixture is mixed well, and an equal weight of microbeads from part A are added. The excess wax is removed, and the beads are cooled.

C) Preparation of Menthol Gum

A menthol gum is prepared using the gum base of Example IV, part C, the microbeads of part B are used instead of the microbeads of Example IV, part B.

Example VII Red Cherry/Grape Chewing Gum

A) Preparation of Microbeads

Microbeads are prepared as taught in Example I, part A.

B) Impregnation of Microbeads

Half of the beads in part A is impregnated with grape flavor using the method of Example III, part B using grape flavoring instead of the cherry flavor of Example III, part B. The latter half of the microbeads is added to an equal weight of a solution containing 5% blue dye FD & C #1 in water, and allowed to remain in the solution for six hours. Excess solution is removed by filtration, and the beads are dried.

C) Coating of Microbeads

All the beads are then fluicized-bed coated with shellac/ethanol solution (70% beads/30% shellac dry basis) .

D) Gum Preparation

Bubble gum is prepared as in Example III, part C except microbeads of part C are used at 2.0% and sugar at 51.9%, and lOOppm FD & C red #40 lake is added. The gum includes cherry flavor as in Example III, part C. The gum will initially be cherry flavored and change to purple grape upon chewing when the cherry flavor is extracted from the gum base and the microbeads yield the grape flavor and blue color.

Example VIII Peppermint Non-Tack Gum with Coated Microbeads The procedure of Example I is repeated, except that the microbeads of part B are coated with a gelatin coat as follows. A mixture (by weight) of 10% of the microbeads, 30% 300 Bloom gelatin, and 60% water is prepared where the water is heated to 63°C prior to the addition of the gelatin and microbeads. The mixture is then cooled so that it gels, and the gel is ground to produce coated microbeads. The coated microbeads, are then formulated into a gum as described in Example I, part C.

Example IX Tabletted Peppermint Mints Microbeads prepared as described in Example I, parts A and B impregnated with peppermint oil are formulated into a mixture in the proportions set forth in Table VIII.

Sorbitol ICI 834 Microbeads Magnesium Stearate Talc

The sorbitol (ICI 834 available from ICI Incorporated of Delaware) and microbeads are mixed for 15 minutes. The magnesium stearate and talc are added, and the composition is mixed for five more minutes. The mix can then be tabletted into a mint in a conventional fashion.

The tabletted mint can also be prepared as taught above by replacing the sorbitol with sugar.

Example X Acidified Smoked Meats

A) Preparation of Microbeads Impregnated With Citrus Flavor

Microbeads are prepared as described in Example 1, part A. The beads are impregnated with an equal weight of an acidic solution of citric acid and ascorbic acid as taught in Section III above. The microbeads are spray-chilled coated with a fat having a solid fat index such that the fat will melt over a range of temperatures normally encountered during smoking of meats.

B) Preparation of Meat Emulsion

The microbeads of part A are dispersed in the fat phase of a meat emulsion of frankfurter, salami, bologna, liver sausage, head cheese or the like. The emulsion is stuffed and linked into a natural or . cellulosic casing. The links are cooked by either immersion in boiling water or cooking in a smoke house. The microbeads allow the gradual release of the acids for controlled acidification of the meat, avoiding premature coagulation of the meat proteins.

Example XI Butter Flavored Refrigerator Bread Dough A) Preparation of Butter-Impregnated Microbeads Microbeads prepared as described in Example I part A are impregnated with concentrated butter extract (having 0.1% ginger oil added to it) by immersing the beads in the extract for six hours. The

- 24 - microbeads are filtered from the excess extract, and coated with a high melting point (50 C) fat by spray chilling.

B) Preparation of Refrigerator Bread Dough The ingredients in Table IX below are combined in a conventional manner and allowed to rise. When the loaf doubles, one part of the microbeads from part A is blended into the mixture to form a. refrig¬ erator bread dough that can be frozen until baking. The microbeads prevent volatilization and oxidation of the butter flavor during storage.

Table IX

Ingredient Amount (Parts)

Bread Flour 54

Shortening 5

Sugar 6

Salt 1

Whole Milk Powder 2

Eggs 4

Water 32

Yeast 3

C) Baking of Refrigerator Bread Dough

The dough is thawed and allowed to rise to double its previous size. The bread is baked at 180°C. The flavor is released upon baking whαn the fat coating on the microbeads melts.

Example XII

Chocolate Pudding Mix

A) Preparation of Chocolate- Impregnated Microbeads

Microbeads prepared as described in Example I part A are immersed in chocolate flavor and allowed to absorb the flavoring for 24 hours. The microbeads are coated as described in Example VIII with gelatin. B) Preparation of Pudding Mix

A pudding mix is prepared by adding the microbeads of part A to the ingredients in Table X below.

Table X Ingredient % by Weight

Sugar 65.2%

Creaming agent CW-2 10.0%

(Beatrice Co., Chicago, IL)

Modified Tapioca Starch (T8-1801) 5.5% from National Starch Co, (New Jersey)

Pectin 6.0%

Cocoa Powder 8.0%

Microbeads 1-0%

Salt 0.3%

Caramel Color 4.0%

The pudding mix can be made into a pudding by adding hot water (100°C) to the mix, stirring -the mix for three minutes, and allow to cool, preferably in a refrigerator for at least a half hour.

-'^•Example XIII Citrus Beverage Mix A beverage base is prepared according to the proportions listed in Table XI by mixing the dry ingredients together.

Table XI Ingredient Percent by Weight

Sugar 67.5

Dextrose 23.6

Citric Acid 7.5 Table XI Cont'd

Ingredient Percent by Weight

Sodium Citrate 1.0

Ascorbic Acid 0.2

Microbeads 0.2

The microbeads are prepared as described in Example I, part A, and impregnated with lemon and lime oils according to the procedure in Example I, part B, substituting a mixture of lemon and lime oils for peppermint oil. The microbeads are then coated with gelatin as described in Example VIII, and blended into the beverage base above. The beverage mix is reconstituted by mixing the mix (100 g) with watεr (24 oz. ) .

Example XIV Microwaveable Rum Cake

A) Preparation of Rum Extract Impregnated Microbeads

Microbeads prepared as described in Example I, part A are mixed with an equal weight of rum extract The excess extract is removed by filtration. The microbeads are coated with a fat that melts above 50 C.

B) Preparation of- Microwaveable Rum Cake Syrup

The microwaveable rum cake syrup is prepared by adding the microbeads of part A to the ingredients listed in Table XII below.

Table XII Ingredient Percent By Weight

Microbeads 0.07

Sugar 59.93

Water 30.00

Glucose 10.00 C) Baking of Cake

A rum cake is prepared in a conventional manner. The syrup of part A is poured over the cake.

The cake is placed in a microwave dish, and exposed to microwave radiation for three minutes. During exposure, the water in the rum extract in the microbeads will heat, and force rum flavor from the pores of the microbeads, and through the fat coating if the fat is not already melted.

Example XV Dry Dog Food

A) Preparation of Meat Flavor

A roasted meat flavor is prepared by dissolving 2-me hyl-3-furanthiol (200 rag.) and 2,5- dimethyl-3-furanthiol (200 mg) into ethanol. To this solution is added 2-methyl-3-ethyl pyrazine (50 mg) and 4,5-dimethyl thiazole.

B) Preparation of Microbeads Impregnated With Meat Flavor

Microbeads prepared as described in Example I, part A are immersed in an equal weight of the flavoring solution of part A for 24 hours. The excess solution is removed by filtration. The microbeads are then coated by dry blending with an equal quantity of HPMC and adding water to produce a damp mix. The water is dried off and the mixture is ground.

C) Preparation of Dry Dog Food

The microbeads of part B are coated onto a dry dog food prepared in a conventional manner such as taught in U.S. Patent 3,380,832. The coating is done by dusting the microbeads onto the dry dog food immediately after the microbeads are suspended in warm fat, and the warm fat is sprayed onto the dry dog food. Example XVI Peppermint Mints Microbeads prepared as described in Example I, parts A and B impregnated with peppermint oil are added to a sugar syrup (70% sucrose, 30% water by- weight) . The mixture is freeze dried and then ground. Magnesium stearate (0.9% by weight) and talc (0.8% by weight) are added to the ground material, and the mixture is tabletted in a conventional manner to produce a tabletted mint candy.

Example XVII Polymeric Beads Including Styrene-Butadiene Rubber

Styrene-butadiene rubber (10.0 g) is dissolved in toluene (9Q.0 g) . In a separate beaker, polyvinylalcohol (1.5 g) is dissolved in water (450.0 g) at about 40°C. The copolymer solution is mixed with styrene monomer (150.0 g) and divinylbenzene monomer (30.0 g) . Benzoyl peroxide (1.5 g) is added to the mixture, and the mixture is agitated at room temperature. The mixture with copolymer is added to the polyvinyl alcohol solution, and the combined mixture is agitated with a motor-driven propeller.

The mixture is heated to 80 - 90°C for at least four hours during which time it is agitated. The mixture is cooled, and filtered to remove the beads. The beads can be used in any of the foods in the previous examples.

While several embodiments of the invention have been described, other embodiments will be apparent to those of ordinary skill in the art. Such embodi¬ ments are included within the scope of the present invention unless the following claims expressly state otherwise.

Claims

I CLAIM:

1. A food product, comprising: a food matrix containing porous polymeric beads impregnated with a food flavoring containing volatile substances.

2. The food product of claim 1 wherein said porous polymeric beads are coated with a water-soluble coating.

3. The food product of claim 1 wherein said porous polymeric beads are coated with a coating that melts when heated.

4. The food product of claim 3 wherein said coating melts at a temperature greater than 30°C.

5. The food product of claim 4 wherein said coating melts at a temperature greater than 100°C.

6. The food product of claim 3 wherein said food matrix comprises a pudding mix.

7. The food product of claim 3 wherein said food matrix comprises a baked good.

8. The food product of claim 5 wherein said food matrix comprises plural populations of said porous polymeric beads, each population adapted to release its flavoring at a different time.

9. The food product of claim 1 wherein said porous polymeric beads are impregnated with an anti-oxidant.

10. The food product of claim 3 wherein said coating comprises a fat.

11. The food product of claim 1 wherein said food flavoring is an oil that has been emulsified in water.

12. A food product, comprising: a liquid that has been concentrated by evaporative means; and a plurality of porous polymeric beads, said beads containing a food flavoring having volatile flavor components, said beads being dispersed throughout said liquid.

13. The food product of claim 12 wherein said liquid comprises a syrup.

14. The food product of claim 13 wherein said syrup is maple syrup and said flavoring is a maple syrup flavoring component.

15. The food product of claim 14 wherein said syrup is a fruit syrup and said flavoring is a fruit flavoring component.

16. The food product of claim 12 wherein said liquid is a citrus juice, and said flavoring is a citrus flavoring.

17. The food product of claim 12 wherein said liquid is a fruit juice, and said flavoring is a fruit flavoring.

18. The food product of claim 12 wherein said beads are coated with a water-soluble coating.

19. A granular food product that dissolves in water to produce a beverage, comprising: a substantially soluble beverage base and a plurality of porous polymeric beads containing a beverage flavoring having volatile substances.

20. The granular food product of claim 19 wherein said beverage base comprises a sweetener and a fruit flavoring, and said beads contain a fruit flavoring.

21. The granular food product of claim 19 wherein said beverage base comprises a coffee bean extract.

22. ,The granular food product of claim 19 wherein said beads contain a coffee flavor.

23. The granular food product of claim 21 wherein said beads contain a cocoa flavor.

24. The granular food product of claim 21 wherein said beads contain a chocolate flavor.

25. The granular food product of claim 19 wherein said beverage base comprises a milk shake base.

26. The granular food product of claim 25 wherein said beads contain a chocolate flavoring.

27. The granular food product of claim 26 wherein said beads contain a fruit flavoring.

28. The granular food product of claim 19 wherein said beads are coated with a water-soluble coating, component.