MXPA99001559A - Process for the formation of plasticized proteinaceous materials, and compositions containing the same - Google Patents

Abstract

Process for the formation of a plasticized proteinaceous material in which a plasticizer component is selectively matched with a protein component to form a blend. The blend is heated under controlled shear conditions to produce the plasticized proteinaceous material having the plasticizer component uniformly distributed within the protein component. The plasticized proteinaceous material is used for a variety of purposes including the production of gums and confectionery compositions.

Description

P OCESO FOR THE FORMATION OF PROTEINASE MATERIALS PLASTICIZED, AND COMPOSITIONS THAT CONTAIN THE SAME BACKGROUND OF THE INVENTION Field of the Invention The invention relates to the formation of plasticized proteinaceous materials and compositions containing them especially for the preparation of chewing gums and confectionery compositions. The plasticized proteinaceous materials have properties that allow them to replace one or more conventional ingredients in chewing gums and confectionery compositions to provide products that are edible and / or biodegradable.

The plasticized proteinaceous material is made by first combining at least one protein and at least one plasticizer that has been coupled according to the criteria: - desirable. The solid state combination is then treated under controlled heat and cut conditions to produce a plasticized proteinase material having unique properties, which is especially suitable for gums and confectionery compositions.

Description of the Prior Art Proteins are polypeptide chains of amino acids that have molecular weights of from about 5,000 up to and even several million. All proteins are constructed from the same set of twenty amino acids. The side chains of these amino acids vary in size, shape, charge, capacity of bond with hydrogen and chemical reactivity. Thus, different proteins can exhibit different chemical and physical properties.

Although many proteins can have similar amino acid compositions, the amino acid sequence is unique to each protein. The protein polypeptide chains can be doubled in specific forms, depending on their amino acid sequences. The structure of the proteins themselves is determined and maintained by the interactions between the different amino acids that make up the polypeptide. The specific linear sequence of amino acid residues that determines the native biologically active structure is influenced by environmental conditions. Diversity in protein structures and functions means that the relative importance of the intrinsic properties in polypeptides and proteins depends on each of the individual proteins.

The chemical and physical, covalent and non-covalent forces that generally determine the structure and the specific conformations adopted by the proteins include covalent bonds, hydrogen bonds, electrostatic interactions, hydrophobic interactions and weak, attractive and non-specific repulsive forces.

The proteins are maintained in their respective conformations through a number of different interactions, such as hydrophobic interactions, hydrogen bonds, interactions of ion pairs, coordination of metal ions and van der Waals interactions. The cross-links of several protein portions by the formation of disulfide bonds between pairs of amino acid residues can also impact protein conformations.

The three-dimensional structure adopted by the proteins in solution is a result of all the aforementioned interactions. The structure can also be changed by altering the temperature or the conditions of the solution. Heat, pH and changes in solvent conditions can lead to changes in the conformation which causes the proteins to denaturate and lose their native structures. The denaturation of proteins is typically irreversible. Naturally, these changes lead to changes in the properties of the proteins, which may be either beneficial or detrimental to the formation of a product.

Denaturation is the most unique property of proteins since no other natural polymer can be denatured. Denaturing is defined herein as "any modification of the secondary structure, tertiary or quaternary of a protein molecule, that does not break the covalent bonds. "A change in the structure of the protein is usually related to some changes in at least one of the physical, chemical or functional properties of the protein. protein denaturation is often considered as a two-state process, so that proteins are either in a state of native conformation or in the state of denaturation.Now it is clear, however, that this is an oversimplification , since it is believed that there are several additional intermediary states that proteins assume.

The degree of change in the structure of proteins and thus in their properties depends on the nature of the individual protein itself, as well as on the type and extent of denaturation. Very little is known about the intermediate states of the structure of the protein. It is possible that intermediary states may have degradation in solubility; (2) loss of biological activity; (3) increase in reactivity of the constituent groups; and (4) changes in molecular shape and size.

Denaturation can be achieved through the application of physical, chemical and biological methods. Physical methods include heating, freezing, application of surface forces, sound waves, grinding, pressure and radiation that includes ultraviolet radiation and ionization. Chemical methods include the use of chemical agents such as solvents, pH adjusters and salts. Biological methods include the use of proteolytic enzymes.

Protein denaturation obtained by heating, usually at 55 ° has: at 75 ° C, requires conventionally the use of a solvent to, inter alia, avoid concomitant decomposition of the polypeptide chain, and preferably to provide a diluted solution to avoid intermolecular interactions of denatured proteins. The non-aqueous and aqueous solutions - alcohol have all been used.

A general discussion of proteins that includes protein classification can be found in John M. deMan, "Principles of Food Chemistry" 2nd edition, Van Nostranl Reinhold, New York, New York (1990) on pages 89 and ff, and the Dictionary of Chemistry of Grant & Hackh, 5th edition, McGraw-Hill, Inc., New York, New York (1987) pages 477-478, each of which is incorporated herein by reference.

The chewing gums are traditionally composed of a portion of water-insoluble base and a water-soluble portion containing flavors and sweeteners. The portion 1 of the base includes a rubber base portion that includes a chewing substance that imparts the chewable characteristics to the final product. The typical gum base defines the release profile of flavors and sweeteners and plays a significant role in the gum product. The flavors and sweeteners provide the sensible liking aspects of chewing gum.

The bases of chewing gums conventionally contain materials called elastomers that provide the character of bounce or gum to the gum. The elastomers are insoluble polymers in water, both natural, such as natural gums and chewing gum, and synthetic polymers, such as polymers of styrene butadiene, polyisobutylene, polyethylene and the like. Elastomers are usually combined with polyvinyl acetates (PVAc) of variable molecular weight to provide flexibility or elasticity to the gum base. The conventional gums will also contain materials such as resins that are used as elastomer solvents to soften the elastomer; waxes; fats and / or oils that can act as plasticizers; Fillers and, optionally, antioxidants and emulsifiers.

The ingredients and conventional techniques for the manufacture of chewing gums are known as those described in Sugar Confectionery Manufacturing, 2nd edition, E.B. Jackson, publisher, Blackie Academic & Proffesional, Glasgow, NZ (1995), at pages 259-262, incorporated herein by way of reference.

The ingredients and conventional techniques for the manufacture of confectionery compositions such as, for example, tablets are presented in "Apparel of choice", Walter Eichmond, Chapter 14, page 250, Manufacturing It would be a major advance in the art to provide proteinase materials having the properties of one or more ingredients of conventional gums and confectionery products such as elastomers., PVAc, waxes and the like, and which can be used in chewing gums and confectionery products as substitutes for one or more conventional ingredients. It would also be desirable to provide chewing gums and confectionery products based on proteinase materials that provide the feel of a conventional confectionery gum or confectionery, that can be eaten as food and can be digested, and / or that are biodegradable.

SUMMARY OF THE INVENTION., To present invention is in part directed to plasticized proteinaseos materials derived from the combination or blend of at least one protein (i.e. a protein component) and at least one plasticizer (i.e. a plasticizer component ) that have been coupled so that the final product (plasticized protein material) can be used for a variety of purposes and is especially suitable for use in gums and confectionery compositions.

The present invention is also directed to the formation of p? Astific proteinase materials from a mixture. The mixture preferably is heated under conditions rupture controlled to produce a plasticized proteinaseo material which can replace one or more conventional ingredients of chewing gums and confectionery compositions such as elastomers, waxes, resins and polyvinyl acetate (PVAc) while imparting the desired properties of the product as well as making the product edible and / or biodegradable.

More specifically, the present invention is directed, in part, to a plasticized proteinase material composed of at least one protein (protein component) and at least one plasticizer (plasticizer component) wherein a solid state mixture of the protein and the plasticizer component it is heated under controlled breaking conditions at a temperature of about 20 ° C to about 140 ° C. n another aspect of the invention a method is provided for producing a mixture of a (omponent protein and appropriate to form a plasticized proteinaseo material comprising plasticizing component: $ choose a protein or mixture of proteins (protein component) having a ppr? er solubility parameter defined by the formula (I) si = soi + spi + sm where n: cu is the value of the total solubility parameter of the protein or the mixture thereof (5DI is the value of the solubility parameter contributed by the dispersant forces of the protein or the mixture thereof, spi is the value of the solubility parameter contributed by the polar forces of the protein or the mixture thereof, cm is the value of the solubility parameter contributed by the bonds of hydrogen of the protein or the mixture thereof; t) choosing a plasticiser or mixture of plasticizers (plastifying component) having a second parameter d e solubility defined by formula (II) 2 2. 2, 2 0"2 = 0" D2 + 0 * P2 + 0"H2 where: - 2 is the value of the total solubility parameter of the plasticizer or the mixture thereof; JD2 is the value of the solubility parameter contributed by the dispersing forces of the plasticizer or the mixture thereof; -rp2 is the value of the solubility parameter contributed by the polar forces of the plasticizer or the mixture thereof; ra is the value of the solubility parameter contributed by the hydrogen bonds of the plasticizer or the mixture thereof; 3n where at least a couple of the values of the solubility parameter si-s2, spi -so2, spj-sp2 and sm-0? 2 are within 15% of each.

N another aspect of the invention, the selected blends of the protein component and the plasticizer provides composite that meet the above criteria may optionally be subjected to an additional selection in which the values of the free volume (FV) of mixtures selected are determined conformance to the following formula (III): FV = 0.025 + ad (T - Tgd) + ap (- Tgp) where: oca is the coefficient of the thermal expansion of the plasticizer or the mixture thereof. CIP is the coefficient of the thermal expansion of the protein or the mixture of the same gd is the glass transition temperature of the plasticizer or the mixture thereof 'gp is the glass transition temperature of the protein or the mixture of the same; 1 and Successful formation of a plasticized proteinase material according to the present invention depends first on the proper selection of one or more mixtures that comprise a protein or mixture thereof and a plasticizer or mixture thereof as determined by a variable referred to as solubility parameter and optionally the free volume of the mixture as described below.

The resulting mixture of the protein component and the plasticizer component is then processed, preferably with heating and under controlled breaking conditions to provide a plasticized protein material that can replace one or more conventional ingredients in chewing gums and confectionery products as well as making said edible and / or biodegradable products. In particular, the plasticized proteinaceous material possesses the characteristics of a polymer (including tensile strength, deformability, elasticity and hardness).

In accordance with the present invention, the preferred process denatures the protein component in a molten state, that is, a protein component in the form of a viscous liquid. More specifically the process comprises heating under controlled breaking conditions the mixing of the protein component and the plasticizer component preferably in the solid state before processing, so that after cooling, the plasticizer component becomes entrapped within a denatured matrix of the protein component.

Fusion is a term generally used to describe the transformation of materials from the solid phase to the liquid phase through the application of heat. The material that is melted has little flow and processability. How it meets many of the polymers Synthetics, proteins usually do not melt or flow after heating. They usually break down before the temperatures needed to melt a protein can be reached. Plasticizers are substances that are usually added to polymeric materials to provide a mixed material that will flow after heating and thus increase the fluidity or flexibility of the polymer. It has now been found that heating a mixture of a plasticizer component with a protein component in the solid state so that the molten state occurs with the concomitant decomposition of the protein component and with the denaturation of the protein component.

According to the present invention, the coupling of an appropriate protein or mixture thereof and plasticizer or mixture thereof to form a mixture for the formation of the plasticized protein material is important to achieve the desirable properties of any product employing the same. It is the coupling of the protein component and the plasticizer component and the manner of obtaining the desired mixture of these materials which provides a significant aspect of the present invention. It will be understood that a single protein or a mixture of proteins can be combined with a single plasticiser or mixture of plasticizers to form a mixture. For reasons of convenience only, reference can be made here to a mixture formed from a single protein and a single plasticizer.

The choice of an appropriate protein or mixture thereof will depend in part on the molecular weight of the protein and its processability within the range of temperatures desired for the final product (e.g., gums and confectionery compositions). Typical processing temperatures to form chewing gums and compositions of Confectionery are within the range of from around 20 to 120 ° C. An appropriate protein is also suitable for processing using conventional mixing equipment that includes extruders, blenders and the like. i The molecular weight of the protein must be high enough for the protein to be classified as a polymer. Molecular weights of at least about 5,000, preferably at least about 10,000, are appropriate.

The protein chosen for the formation of the plasticized proteinase material should be coupled with an appropriate plasticizer. Therefore, the combination of proteins and plastifics was random and only by trial and error, which often led to mixtures that did not impart the desirable properties to the final product. According to one aspect of the present invention, the combination of protein and plasticizer is achieved in part by coupling the solubility parameters of the protein component and the plasticizer component within a desired range and using only those combinations that are closely related.

The coupling of an appropriate protein component with a plasticizer component therefore depends first on the consideration of the solubility parameters of the protein component and the plasticizer component that are determined by their relative cohesive properties. The solubility parameter of various materials and methods for calculating same are known in the art as presented in, for example D.W. Van Krevelen Elsevier "Properties of Polymers" (1990), which is incorporated herein by reference.

The solubility parameter for a compound (eg, a protein) is the sum qe the solubility parameter values contributed by dispersing forces, hydrogen bond forces and polar forces. According to the present invention, a protein will be dissolved in a plasticizer or plasticized if either the total solubility parameter (s) or one or more of said dispersing forces (GD), polar forces (sp), and hydrogen bonding forces (sp) for each of the protein and the plasticizer are similar. In particular, applicants have determined that if any one or more of the solubility parameter values for a protein and plasticizer or respective mixtures of the organisms are within 15% of each, preferably 10%, the protein component and the Plasticizer component can present a potential appropriate mixture to make the material proteaseified or plasticized.

More specifically in accordance with the present invention, the solubility parameter of a protein or mixture thereof chosen is determined according to the following formula I. where: < t? is the value of the total solubility parameter of the protein or the mixture thereof soi is the value of the solubility parameter contributed by the dispersing forces of the protein or the mixture thereof; TP: is the value of the solubility parameter contributed by the polar forces of the protein or the mixture thereof; C? HI is the value of the solubility parameter contributed by the hydrogen bonds of the protein or the mixture thereof. if the solubility parameter of a plasticiser or mixture of plastiñcadores proposed to form a mixture of solid state is determined by the following Formula II n where: (72 is the value of the total solubility parameter of the plasticizer or the mixture thereof; sD2 is the value of the solubility parameter contributed by the dispersant forces of the plasticizer or the mixture thereof; sp2 is the value of the parameter of the solubility contributed by the polar forces of the plasticizer or the mixture thereof, sm is the value of the solubility parameter contributed by the hydrological bonds of the plasticizer or the mixture thereof.

In accordance with the present invention if at least one of the following pairs of solubility parameter values si -s2, spi-sD2, s? - sp2 and sm-sH2 are within 15% of each, preferably within 10% of each, then the protein and plasticizer components present in a mixture that is an appropriate candidate to form a plasticized proteinase material in accordance with the present invention.

In a preferred form of the invention at least one of the pairs of solubility parameter values is within 10% of each. It is also preferred that the mixture of the protein component and the plasticizer component have similar values and / or vanes, especially when the chosen protein includes zein and / or gliadin. The most preferred are protein-plasticizer mixtures that have values s and so within the %, m | preferably 10% of each. - values of total solubility parameters (s) and the constituent forces of The misíjnos (so, sp, GH) for exemplary proteins and plasticizers are shown in the Table 1.

TABLE 1 Protein s * (J / cm3) 05 sD (J / cm3) 0-5 sp (J / cm 3) ^. 5 sH (J / cm3) 05 (P) / plasticizer ZEINA ÍP) 22.5 16.402 5.06 14.483 GLIAD? NA (P) 22.6 16.302 5.398 14.66 Metanoi 29.2 - 29.7 15.2 12.3 22.3 Ethanol 26 - 26.5 15.8 8.8 19.5 1 - propanol 24.4 - 24.5 15.9 6.8 17.4 Isopropyl alcohol 23.6 15.8 6.1 16.4 (2 - propanol) Isobutyl alcohol 22.9 15.2 5.7 16 Phenol 24.1 18 5.9 14.9 Propyl glycol 30.3 16.9 9.4 23.3 (1.2 pijopanediol) butylene glycol 29 16.6 10 21.5 0.3 - bentanitol) Glycerol 33.8 - 43.2 173 12.1 29.3 (1 , 2,3 - propanetriol) Formic acid 25 14.3 - 15.3 11.9 16.6 Acetic acid 18.8 - 21.4 14.5 - 16.6 13.5 Butyric acid 18.8 - 23.1 14.9 - 16.3 4.1 10.6 Water 47.9 - 48.1 12.3 - 14.3 31.3 34.2 2, 2, 2 O " D + sp + CH As illustrated in Table 1, the zein and gliadin proteins have s values similar (22.5 and 22.6), respectively. In addition, the values so, sp, sH are also Similar. Plasticizers that exhibit similar solubility parameter values for zein and gliadin are isopropyl alcohol and isobutyl alcohol. Mixtures of zein and / or gliadin and isopropyl alcohol and / or isobutyl alcohol (ie, having values of solubility parameters within 15% of each, preferably within 10%) would therefore be expected from In accordance with the present invention provide protein-plasticizer mixtures which are almost suitable for the formation of plastific proteinase materials of the present invention. Other candidates for the formation of blends of the present invention can be determined in a similar manner.

In an optional but preferred practice of the present invention appropriate mixtures, after a list of candidate mixtures is selected by comparison of the values of respective solubility parameters, can be determined by considering the free volume of each candidate mixture.

Free volume is the space between molecules. Free volume increases with increased molecular movement. According to the above, an inappropriate amount of free volume is related are end groups of chains in a polymer system.

Increase the concentration of groups of final chains, that is, decrease the molecular weight, and therefore increase the free volume. The addition of flexible side chains within macromolecules therefore increases the free volume. All these effects can be used for the internal plasticization, and the free volume is spatially fixed with respect to the polymer molecule. However, the addition of a small, molecule affects the free volume of large molecules at any position by the amount of the added material, which is known as external plasticization. The size and shape of the molecule that is added and the nature of its atoms and groups of atoms (ie, not polar, polar, hydrogen bonds or not, and density and light) determine how it works as a plasticizer.

The normal effect of increasing the free volume of a polymer is that it is plasticized (ie, the glass transition temperature is lower, the modular and tensile forces decrease, and the elongation and impact forces increase). However, the freedom of movement produced by the plasticizer also allows the polymer molecules, if it is their nature, to associate closely with each other.

In general, the free volume is based on the principle that an appropriate plasticizer increases the free volume of the protein. An increase in the free volume of p Otein increases the mobility of the protein and therefore the extension of the plasticization. Thus, if more plasticization is desired, the amount of the plasticizer should be increased.

Thus, in addition to the selection of appropriate protein and plasticizer candidates by comparing the values of solubility parameters, another selection of said candidates is governed by the following formula III FV = 0.025 + ad (T - Tgd) + ap (- Tgp) where: FV is the free volume of the mixture; ctp is the coefficient of the thermal expansion of the protein or the mixture of them; tXd is the coefficient of thermal expansion of the plasticizer or the mixture thereof is the reference temperature, typically environmental or the end-use temperature. tgd is the glass transition temperature of the plasticizer or the mixture thereof; and ÍTgp is the glass transition temperature of the protein or the mixture thereof Thus, the coefficient of thermal expansion of the protein component and the plasticizer component and their respective glass transition temperatures determine the free volume and therefore the degree of plasticization of the mixture. For most of the cases in the technique of chewing gum and confectionery, for a given protein and mixture thereof, the greater the free volume of the mixture, the more suitable the plasticizer. Thus, for a given protein component the most appropriate plasticizer component will be that which provides the mixture with the highest free volume value.

The free volume of the mixtures comprising the zein protein and various plasticizers is illustrated in Table 2.

TABLE 2 Protein (P) / Coef. of Expansion Temperature of free Volume of Thermal Plastifier 103 [K 1] transition to glass mixture with Zein Tg (° C) (CC) Zein (P) 0.290 82 Glycerin 0.281 18 0.0105 Propylene glycol 0.277 60 0.0320 Polyethylene glycol 0.313 12 0.0201 Ethanol 0.275 116 0.0473 As illustrated in Table 2, the combination of ethanol and zein provides the highest free void value of the potential candidates illustrated therein. Generally, the higher the free volume, the better the degree of plasticization of the materials that make up the mixture. According to the foregoing, free volume can be used as a tool in the selection of a desirable plasticizer component for a pre-selected protein or mixture thereof.

Once a potential mixture of a protein component and a plasticizer component has been identified by comparing the values of respective solubility parameters of the protein component and the plasticizer component alone or optionally the free volume of the mixture as discussed above, the Glass transition temperature of the final product (plasticized protein material) should be considered. For example, for chewing gums and confectionery compositions an appropriate glass transition temperature for the plasticized protein material is in the range of, for example, from about 35 to 45 ° C.

The determination of a glass transition temperature for the protein material, plasticized (Tg ^ x) is made according to the following formula (IV) Tgpüx = (ad / ap) .Vd. (Tgd - Tgp) + Tgp where : < 4 ap, Tgd and Tgp are as defined above; and Yd is the volume fraction of the plasticizer.

The glass transition temperature of the plasticized proteinaceous material is therefore determined by the ratio of the respective coefficients of thermal expansion, the fraction of the volume of the plasticizer component and the difference between the respective glass transition temperatures of the plasticizer component and the component proteinaceous. In general, the glass transition temperature of the plasticized proteinaceous material can be increased by the selection of a plasticizer component having a relatively high coefficient of thermal expansion and / or a higher glass transition temperature. If a lower glass transition temperature of plasticized proteinase material is desired, it is appropriate to choose a protein having a relatively high coefficient of thermal expansion and / or a temperature of As it is shown in this way, and as the temperature increases as the volume of the protein decreases, the glass transition temperature of the mixture decreases. Thus, the glass transition temperature of the plasticized proteinaceous material can be modified by altering the relative amounts of the protein and the plasticizer according to Formula (IV).

Suitable proteins for use in the present invention can be any protein, synthetic or natural as is any plant or animal protein and can be water soluble or water insoluble. The protein can be modified enzymatically, chemically modified or the product of genetic engineering technology. The protein can be substantially pure or it can be a part of a mixture as it is in a grain fraction. It will be understood that when the grain fractions are used, the The glass transition temperature of one group may differ from another and this may affect the values of the solubility parameter and / or the glass transition temperature thereof.

The protein can be chosen from but is not limited to: grain oroteins such as corn, wheat, barley, rice, oats, soy and sorghum proteins and their fractions including glutene and prolamines such as zein, gluteniria and gliadin; and animal proteins such as collagen, egg and milk proteins that include gelatin, egg albumin (ovalbumin), lactalbumin, casein and sodium caseinate, whey and milk isolates such as caseinate and whey mixtures.

The selection of the protein or mixture thereof for use in the preparation of a plasticized proteinase material of the present invention is based on several factors including the properties sought for the plasticized protein product. For a chewable confection such as a candy or a medically chewable one in which it is desirable to provide water solubility, it is preferred to use a proteinaceous component that provides a water soluble product. For a conventional chewing gum, it is desirable to use a protein component that provides a water-insoluble product, other factors include the desired viscoelastic properties for the product. For example, a product having a more viscoelastic character is generally provided by the use of a protein component chosen from wheat and corn protein clusters which include wheat zein and wheat gliadin, or gelatin and mixtures thereof. In contrast, a product having less viscoelastic character is generally provided by the use of a protein component chosen from egg white, whey and sodium caseinate.

As previously indicated, the selection of a protein or mixture thereof is dependent in part on its glass transition temperature. For many applications the proteins or mixtures thereof, having a glass transition temperature of from about 40 to about 120 ° C to process at temperatures in the range of from about 20 to 120 ° C, are preferred . It will be understood that many commercially available proteins have a significant residual water content. Water has to Dajar the glass transition temperature of proteins. Thus, the presence of water in a protein must be taken into account when choosing a protein component to make a plasticized protein material according to the present invention.

A single protein or combination of proteins can be used as the protein component to form a mixture. Protein combinations include, but are not limited to, zein / egg white, zein sodium caseinate, zein / milk isolate, egg white / milk isolate, glutene (gelatin, gelatin / zein, gelatin / caseinate). Sodium, gelatin / gliadin, gelatin / milk isolates and the like Combinations that combine different characters are preferred for some uses as is a combination that combines a more rubber-like protein such as gelatin, with a protein more similar to plastic, such as It's the gliadin.

The plasticizer, as discussed previously herein, is a material that provides both the ability to work with the plasticized protein material and contributes to its viscoelastic character. The plasticizer or mixture thereof suitable for use in the present invention can be chosen from a variety of materials including organic plasticizers and those similar to water that do not contain compounds organic Organic plasticizers that are the preferred class of plasticizers include:, but are not limited to, phthalate derivatives such as dimethyl, diethyl, dibutyl, phthalate; polyethylene glycols with molecular weights preferably from about 200 to 6,000; glycerol; glycols such as polypropylene, propylene, polyethylene and ethylene glycol; citrus esters such as tributyl, triethyl, and triacetyl citrates; active taut agents such as sodium dodecyl sulfate, polyoxyethylene (20) sorbitan and polyoxyethylene (20) sorbitan monool; ato, mixed with water; alcohols such as ethanol and isopropyl alcohol; organic acids such as acetic and lactic acids and their lower alkyl esters; crude sweeteners such as sorbitol, mannitol, xylitol and licasine; fats / oils such as vegetable oil, seed oil and castor oil; acetylated monoglyceride; triacetin; sucrose esters; traditional flavor oils; or mixtures thereof. The preferred organic plasticizers are polyols such as glycerol and glycols, especially propylene glycol, polypropylene glycol, ethylene glycol and polyethylene glycol and organic acids, especially lactic and acetic acid, and their corresponding esters.

The amount of the protein component present in the protein / plasticizer mixture will vary as discussed above. Consideration should be given to the desired glass transition temperature of the plasticized protein material. Typically the amount of the protein component will be at least 40% by weight and more typically at least 50% by weight. Especially good plasticized proteinaceous materials are usually obtained when the amount of the protein component is from about 60 to 75% by weight.

Preferred amounts of typical plasticizers based on the total weight of the protein / plasticizer mixture include, for example, aqueous ethanol (20-40% by weight), propylene glycol (20-40% by weight), ethylene glycol (10-30% by weight), and acetic acid and lactic acid (10-20% by weight), it will be understood that for applications involving foodstuffs (for example, example, chewing gums and confectionery compositions) ethanol may be preferred due to the regulatory requirements that govern its use. ., preferred protein mixtures and plasticizers for chewing gums and confectionery products include zein / propylene glycol / glycerol; zein glycerol propylene glycol / acetic acid / water; zein / lactic acid / glycerol / propylene glycol / glycol; and zein / lactic acid /] jethylene glycol / ethyl lactate / butyl lactate / ethyl acetate / glycerol.

The protein component and the plasticizer component are each used in the dry state, ie, a premix of protein and plasticizer would have the physical properties of a powder with the plasticizer dispersed uniformly with the protein. The protein / plasticizer mixture will usually be composed of a mixture of proteins and / or a mixture of plasticizers to take advantage of the property of each of the components thus maximizing the compatibility of the components of the mixture.

The protein and the plasticizer are combined in a mixture and the mixture is treated to form a mixture with the dispersed plasticizer within a protein matrix. In a preferred form of the invention, the mixture of the protein and the plasticizer comprises a highly viscous material in the molten stage of the protein (i.e., a plasticized proteinase material). Both the melting temperature and the viscosity of the mixture in the melting temperature can be affected by the type and amount of plasticizer present. In general, the greater the amount of plasticizer used, the lower the melting temperature and less will be the viscosity of the mixture used to form the plasticized protein material.

Other materials can be mixed with the protein component before melt plasticization. For example, in the chewing gums, while varying amounts of the protein component and the plasticizer component can be used to provide materials that can replace conventional elastomers and PVAc in the gum also provide rubber and other characteristics, the incorporation of other materials within the Molten plasticizing process can also be used for these additional features. For example, one example of the present invention combines a polysaccharide with the protein component before melt plasticization. While the polysaccharide has minimal effect on the viscoelasticity properties of the plasticized proteinaceous material, it can provide properties usually provided by components with the wax found in conventional chewing gum.

The polysaccharides suitable for use in the present invention can be neutral or ionic. Ionic polysaccharides include pectin, carrageenan, propylene glycol, alginate and the like. Neutral polysaccharides include cellulose esters and ethers.

The process can optionally be carried out in the presence of an acid. The acid affects the isoelectric point of the protein component which is predominantly a dipolar ion at neutral pH. Changing the pH improves the interaction of the protein component as well as the protein / polysaccharide mixture. Both organic and inorganic acids can be used to provide an acidic pH.

The formation of a plasticized proteinase material from a mixture of a proteinaceous component and a plasticizer component is preferably carried out at temperatures of from about 20 to 120 ° C under controlled breaking conditions. "Controlled breaking conditions" according to the present invention will mean that the mixture is exposed to rupture to a point sufficient to uniformly disperse the plasticizer within the shade of the protein. to rupture and its determination and effect in various materials is presented in Ronald Darby, 'Viscoelastic Fluids' (Marcel Deker, Inc., 1976) pages 7 and 8, which are incorporated herein by way of reference.

For the purposes of the present invention, the mixture of the protein component and the present plasticizer is subjected to breaking conditions which are more severe than those usually employed for the preparation of chewing gums and confectionery compositions. More specifically, gums and confectionery compositions are typically prepared in an open container using sigma mixing blades (ie, blades having an S-shape). The break is maintained at modest levels a) because the container is open and therefore the mixture can be raised inside the container during the batic or to release tension and b) because the S-shaped sigma blades provide only modest rates of break to the mix.

According to the present invention, the break applied to the mixture of the protein and the plastifier are greater than those used in the custom in the preparation of gums and confectionery compositions. Said equipment may be, for example, a mixer or extruder-one that uses roller knives and similar devices.

The plasticization of the protein and plasticizer mixture can be carried out in a mixer or in an extruder. In any case, the apparatus should be one that provides a break from medium to preferably high. A high break is preferred to uniformly disperse the plasticizer component within the matrix of the protein component. Low-break mixers such as those that use sigma blades as previously indicated, which are traditionally used in the manufacture of gum bases and chewing gums to provide sanding and kneading without imposing a strong compressive force, generally do not provide sufficient ptura to denature the protein. Cam blades are known to provide medium rupture and are useful for studying the properties of rubber and elastomeric materials. Roller blade mixers, however, are most suitable for use in the preparation of plasticized protein material because they provide a greater break due to their angular curve design. Suitable mixers of this type for use in the present invention include, but are not limited to, the Brabender, Hobart, Sigm kettle, Hakke and Planetary mixers.

The formation of a plasticized protein material from a mixture of a protein component and a plasticizer component is carried out at elevated temperatures under high rupture conditions. In a mixer, such as a Brabenc er mixer, the mixture of the protein and the plasticizer is heated to a temperature of about 20 ° C (ambient) to about 140 ° C, preferably from about 20 to 120 ° C. and it is processed under high rupture until the moment becomes constant indicating that a substantial denaturation has been completed. The time will depend on factors such as the type and amounts of protein and plasticizer. The temperatures high, up to 140 ° C, can be used to shorten the process time but higher temperatures can in some cases adversely affect the protein. Generally less time is required if more plasticizer is present. The mixer can be stopped at this time, the material is removed while it is hot, and then cooled, analyzed and used.

A mixer is particularly suitable for processing a protein or a mixture of proteins in the presence of a plasticizer to develop higher process moment values. For economic reasons such as shorter processing times and the potential for continuous processing, the preference process is carried out in an extruder. The extruders should provide a break capable of uniformly dispersing the protein in the plasticizer matrix (ie, high break). Suitable extruders include, but are not limited to, BerstofF, Killion, Brabender and Werner-Pfleiderrer extruders.

The extruder is particularly suitable for processing proteins or protein mixes that do not add excessively and therefore maintain a lower constant process momentum value. Preferably, the protein component is first mixed vigorously with the plasticizer component then molten extrudates are extruded. The extrudates can be collected in standard or film form and analyzed.

With either a mixer or an extruder the process of preference is carried out through the denaturing stage of the protein just before any excessive aggregation of the protein. The aggregation, or formation of networks, of the denatured protein occurs through the formation of intermolecular bonds. When the Proteins are denatured functional groups that were coupled into intermolecular hydrogen bonds and hydrophobic interactions in the native state become available for intermolecular interactions. The above results in aggregation to progressively form a visoelastic work network. The material goes from being a powder to a paste.

Materials that have a long window of processing time during the denaturation stage before aggregation or that do not add to any extension are preferred for use in making plasticized protein materials. It has been found that materials that exhibit viscoelastic properties can be provided herein by materials that do not add to any extent after denaturation. The processing of these materials is more easily controlled. When it is desirable to use the material in a process that makes chewing gum or confectionery compositions in one step, the material is kind in its use. Zeina, gliadin, milk and gelatin isolates, per se, can be processed very easily, as is best illustrated herein, and are particularly suitable as precursors for gum ingredients. For those materials that add excessively it is preferable to stop the molten plasticizing process just before the excessive aggregation. Proteins such as egg white, whey and sodium caseinate are more likely to aggregate after denaturation and have higher process viscosities with more limited process times as illustrated hereinafter. These materials can be used as mixtures with proteins that are prone to less aggregation to provide a desirable plasticized proteinase material.

The amount of the plasticizer component present can also have an effect on the processing time window. In general, the greater the amount of plasticizer present in the mixture, the longer the window of time of the process, despite the benefit that the additional plasticizer will offer. With proteins such as zein and the related prolamines it is preferred to have a protein / plasticizer mixture from about 90 to 75% protein and from about 10 to 25% plasticizer by weight, for proteins such as the clear egg is preferred to have from about 75 to 50% protein and from about 25 to 50% plasticizer in the mixture.

The plasticized proteinaceous material can be isolated after the plastifi < Processing or processing can be continued to prepare a final product such as a chewing gum. When the material is isolated, it can be used in traditional manufacturing processes. These processes are well known to those with experience in the technical field. Chewing gum can also be prepared using an extruder.

A one-step process, that is, a process that prepares a chewing gum directly, is a favorite example. Either a mixer or an extruder can be used for this process, although the use of an extruder is preferred. The extruder allows the manufacture of the chewing gum in a continuous process, that is, the ingredients of the chewing gum are added constantly while the product is removed through a port of exit. The protein component and the plasticizer component can be added to the initial barrels of the extruder or the plasticizer can be added to a second or third barrel and the mixture is heated under controlled breaking conditions as previously described. The resin and other ingredients of the gum base can also be added at this time or at a later stage. The components of the rubber of Traditional chews such as sweetener and flavor can be added at a later stage. The higher temperatures can be used initially with lower temperatures used for the incorporation of flavor and sweetener. As an alternative, a plasticized proteinaceous material can be prepared in an extruder, and the resulting material can be added to the initial barrels.

The extruder can be used to prepare a chewing gum composed of fast aggregation and slow aggregation proteins. Process times can be controlled by choosing the order of addition, proteins that do not add quickly and have low moment values can be added to the extruder at the beginning of the process. The proteins that add quickly can be used as short process time additives.

The plasticized proteinaceous material of the present invention can be used as a substitute for one or more conventional materials in gums and confectionery compositions, including waxes, elastomers and resins. This substitution makes it possible to produce products that are edible and / or biodegradable. However, it will be understood that traditional ingredients can be included in said composition.

The conventional elastomers used in chewing gum bases can be qua. any water-insoluble polymer known in the art. They include styrene-butadiene copolymers (SBR) and non-SBR types. Examples of natural elastomers include, without limitation, gums such as latex rubber (natural rubber) and guayula, and gums such as chewing gum, jelutong, gutta percha, lechi capsi, sorva, crown gum, medlar, rosidin-L perillo, niger gutta, tunu, gutta kay, pendare, cow's milk, chiquibul, rubber Suitable elastomer solvents for use herein include tall oil ester, partially hydrogenated wood, and gum resin; glycerol esters made of wood and rubber resin; partially hydrogenated wood / rubber resin, partially dimerized wood and rubber resin; dimerized wood and rubber resin; and stem oil resin; the deodorized glycerol ester wood resin; the pentaerythritol esters of wood and rubber resin; partially hydrogenated wood and rubber resin; the methyl ester and partially hydrogenated wood resin; esters methyl, glycerol and pentaerythritol of modified resins and resins such as dimerized and polymerized hydrogenated resins; terpene resins such as alpha-pinene or beta-inene polymers, hydrocarbon terpene resins; politerpenes; and the like and mixtures thereof. The elastomer solvent can be employed in the gum base composition in an amount of from about 2% to about 75% by weight of the gum base composition. i Waxes can be of mineral, animal, vegetable or synthetic origin. Non-limiting examples of mineral waxes include petrolatum waxes such as paraffin and microcystalline waxes, animal waxes including beeswax, vegetable waxes include carnauba, candelilla, rice bran, esparto, flax and sugar cane and the synthetic waxes include those produced by the Fisher-Tropsch synthesis, and mixtures thereof. Suitable oils and fats in gum compositions include hydrogenated or partially hydrogenated vegetable or animal fats, such as cottonseed oil, soybean oil, coconut oil, wheat palm oil, beef tallow, hydrogenated tallow, butter, cocoa butter, lanolin and the like; fatty acids such as palmitic, oleic, stearic, linoleic, lauric, myristic, capric, caprylic, decanic or esters and salts such as sodium stearate and potassium stearate. These ingredients when you used by or general are present in amounts of up to 14% by weight of the gum composition.

Typical emulsifiers include acetylated monoglyceride, glyceryl monostearate. monoglycerides of fatty acids, diglycerides, propylene glycol monostearate, lecithin, triacetin, triacetate glyceryl and the like and mixtures thereof. The preferred emulsifiers are glyceryl monostearate and the acetylated monoglycerides. These also serve as plasticizing agents. The emulsifier can be used in a quantity from about 1% to about 15% by weight of the composition of the gum base.

The gum base may also contain a surfactant. Examples of suitable surfactants include polyoxymethylene (20) sorbitan monoleate, polyoxyethylene (20) sorbitan monolaurate, polyethylene (4) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene ( 20) sorbitan tristearate, polyoxyethylene (5) sorbitan monooleate, polyoxyethylene (20) sorbitan trioeato, sorbitan monola-irate and the like. The amount of the surfactant present should be effective to provide the finished chewing gum with the desired smoothness. Typically, the agent: ensoactive is used in the base in an amount of from about 0.5% to about 3.0% by weight based on the total weight of the gum base.

The composition of the gum base may also include effective amounts of fillers. Useful fillers include organic and inorganic compounds such as calcium carbonate, magnesium carbonate, ground limestone, magnesium silicate, calcium phosphate, cellulose polymers, clay, alumina, aluminum hydroxide, aluminum silicate, talc, tricalcium phosphate, dicalcium phosphate and the like and mixtures thereof. Typically, the filler is employed in the gum base composition in an amount from about 1% to about 40% by weight of the composition of the base soma.

The gum base may also comprise an antioxidant. Non-limiting examples of antioxidants are butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA) and gallate propyl. Mixtures thereof can also be used.

Other conventional chewing gum additives known to those of ordinary skill in the chewing gum art can also be used in composing the gum base of the present invention.

The amount of gum base used in a traditional chewing gum composition will vary. In general, the base can be included in the final chewing gum product in amounts of from about 10 to 75% by weight of the product.

A chewing gum composition will also contain raw sweeteners. Suitable sugars include monosaccharides, disaccharides and polysaccharides such as xylose, ribulose, glucose (dextrose), mannose, galactose, fructose (levulose), sucrose (sugar), maltose, invert sugar, partially hydrolyzed starch and corn syrup solids, and mixtures thereof. Non-sugar raw sweetening agents include crude sugar alcohol agents such as sorbitol, xylitol, mannitol, galactitol, maltitol and mixtures thereof, isomalt, maltodextrins, hydrogenated starch hydrolysates; hexosas hydrogenated; hydrogenated disaccharides; and the like and mixtures thereof. The agents: or crude sweeteners described above, can be used in an amount of from about 17% to about 90%, by weight based on the total weight of the gum base composition.

The chewing gum compositions may also include a high density sweetening agent (sweeteners). Examples of suitable intense sweeteners include (A) intense naturally occurring water-soluble sweeteners such as dihydrochalcones, moneliji, steviosides, clicirrizin, dihydroflavenol and L-aminodicarboxylic acid, aminoalkanoic acid ester amides, such as those presented in the US Pat. No. 4,619,834 and mixtures thereof; (B) water-soluble artificial sweeteners including soluble saccharin salts such as sodium or calcium salts of saccharin, salts of; cyclamate, the sodium, ammonium or calcium salts of 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,3-dioxide, the potassium salt of 3,4-dihydro- 6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide (Acesulfam-K), the free acid form of saccharin, and the like and mixtures thereof; (C) dipeptide-based sweeteners including the sweeteners derived from L-aspartic acid, such as methyl 1-aspartyl-L-phenylalanine (Aspartame) and the materials described in US Pat. No. 3,492,1 1, hydrate of L - alpha --partyl - N - (2,2,4,4 - tetramethyl - 3 - thietanyl) - D - alaninamide (Alitame), methyl esters of L - aspartyl - L - phenyl - glycerin and L - aspartyl - L - , 5-di-prophenyl-glycine, L-aspartyl-2,5-dihydro-L-phenylalanine, L-aspartyl-L- (1-cyclohexene) -alanine and the like, and mixtures thereof; (D) Intense water-soluble sweeteners derived from naturally occurring sweeteners, such as chlorinated derivatives of ordinary sugar (sucrose), for example, chlorodeoxysugar derivatives such as chlorodeoxysucrose or chlorodeoxygalactosucrose derivatives, known, for example, example, under the Sucralose® product designation; Examples of chlorodeoxysucrose and chlorodeoxygalactosucrose derivatives include but are not limited to: 1-chloro - 1 '- deoxysucrose; 4-chloro-4-deoxy-alpha-D-galactopyranosyl-alpha-D-fructofuranoside; or 4-chloro-4-deoxygalactosucrose; 4-chloro-4-deoxy-alda-D -galactopyranosyl-1-chloro-deoxy-beta-D-fructo-furanoside or 4,1'-dichloro-4,1'-dideoxygalactosucrose; 1'-6'-dichloro-1'-6'-dideoxysucrose; 4 - chloro - 4 - deoxy - alpha - D-galactopyranosyl-1,6-dichloro-1,6-dideoxy-beta-D-fructofuranoside or 4,1 ', 6'-trichloro-4,1', 6'-trideoxygalactosucrose; 4,6-dichloro-4,6-dideoxy-alpha-D-galactoxyranosyl-6-chloro-6-deoxy-beta-D-fructafuranoside; or 4,6,6'-trichloro-4,6,6'-trideoxygalactosucrose; 6,1 ', 6'-trichloro-6,1', 6'-trideoxysucrose; 4,6-dichloro-4,6-dideoxy-alpha-D-galacto-pyranosyl-1,6-dichloro-1,6-dideoxy-beta-D-fructoft-ranoside or 4,6,1 ', 6'-tetrachlor - 4,6,1 ', 6'-tetradeoxygalacto-sucrose; and mixtures of riismos; and (E) intense sweeteners based on proteins such as thaumaoccous danielli (Thaumatin I and II). Intense sweeteners are usually used in an amount of up to about 1% by weight based on the total weight of the chewing gum composition.

The macar gum composition may also contain a flavoring agent chosen from those flavors known to those skilled in the art, and include natural and artificial flavors. Representative flavoring agents plus no limitantss include (A) flavoring oil such as mint, cinnamon, wintergreen oil (methyl salicylate), spearmint (menthol), clover, bay leaf, anise, eucalyptus, thyme, cedar leaf, oil nutmeg, jamaica pepper, sage oil, mace, sour almond oil and cassia oil; (B) artificial, natural and synthetic fruit flavors such as vanilla and citrus oils that include lemon, orange, lime, grapefruit and essences fruit trees that include apple, pear, peach, grape, strawberry, raspberry, cherry, peach, pineapple, and others; (C) aldehydes and esters such as acetaldehyde, benzaldehyde, anisic aldehyde, symnamic aldehyde, citral, neral, decanal, ethyl vanillin, hyliotrope, piperonal, van liillllín, alpha-amyl cinnamaldehyde, butyraldehyde, valeraldehyde, citronellal, decanal, dihydrobarbyl acetate , eugenil format, aldehyde C-8, aldehyde C-9, aldehyde C-12, 2-ethyl butyraldehyde, hexanal, tolyl aldehyde, veratraldehyde, 2,6-dimethyl-5-heptenal, 2,6 dimethylpctanal, 2-dodecenal, p-methylanisole and others. Generally any flavoring or food additive such as those described in the Chemicals Used in the Food Process, publication 1274, pages 63-258, of the National Academy of Sciences, which is incorporated herein by reference, may be used. Other ingredients that can be used in the flavoring component include acids such as citrus, tartaric, malic and similar acidulants. In gum compositions, the flavoring agent is generally present in amounts of from about 0.02% to about 5% by weight of the chewing gum composition. , the composition of the chewing gum may also contain a coloring agent chosen from but not limited to pigments such as titanium oxide, which may be incorporated in amounts of up to about 6% by weight of the gum composition, colors and natural food dyes suitable for edible, drug and cosmetic applications, known as FD dyes & C. - A list of all dyes F.D. & C. and their corresponding chemical structures can be found in the Kirk Encyclopedia -Othmer of Chemical Technology, 3rd edition, in volume 5 on pages 857-884, incorporated herein by way of reference.

Other conventional additives can be used in the chewing gum compositions Examples of other conventional additives that may be used include thickening agents such as methyl cellulose, alginates, carrageenan, xanthan gum, gelatin, carob, tragacanth and carob bean, acidulants such as it is malic acid, adipic acid, citric acid, tartaric acid, fumaric acid and mixtures thereof and fillers, such as those discussed above under the category of mineral adjuvants.

The present invention can be used to produce confectionery products such as candies. The candies are a combination of sweet smoothie and soft candy. Proteins such as egg whites or egg albumin are used in which most of the moisture is removed while the egg whites are mixed with the other ingredients that include honey, sugar, nuts such as pistachio and / or almonds and flavorings . The plasticized proteinaceous material of the present invention can be used as a substitute for the protein and / or the conventional ingredients contained therein or as an additive thereto.

There are two types of candies: chewy candy and short candy. Any type can be made by using egg albumen, egg frappe or other protein-based materials.

The short or chewy candy set is controlled by. the percentage of non-crystalline sugars, such as corn syrup, invert sugar or honey that contains the whole, and the method of mixing used in manufacturing. The highly cooked portion of the short caramel usually contains a higher percentage of sugar than the whipped portion of the whole. The highly cooked portion of the set should be add it slowly to the beaten egg shake, so that the heat of the highly cooked set does not cook the egg whites. The set with low cooking, to which the egg whites must be added, should be cooled enough so that the heat of the set does not cook the egg whites and thus destroy their quality of milkshake.Chewable candy contains more corn syrup than mild candy. The highly cooked set should contain less sugar than the short caramel. A candy set containing equal parts of sugar and honey corn syrup can become either a chewy candy or a short candy by varying the amount of sugar and corn syrup or honey used in the highly cooked and low-cooking sets.

The preparation of candies is presented in "Confectionery Options," Waller-Richmond (Chapter 14), pages 251-267, Manufacturin Confectionery Publishing Company (1954), incorporated herein by reference.

In accordance with the present invention the plasticized proteinase material can be employed in caramel products to provide desired characteristics. While chewing gums employ proteins that are insoluble, candies and other chewable confections are typically made in accordance with the present invention with soluble proteins.

The production of gums using the plasticized proteinase materials of the present invention requires that the initial protein or mixture thereof be insoluble in water.

The term "water-insoluble" should be used in its broad customary sense and will mean that the vast majority of the material in question does not dissolve in low water typical processing conditions. Examples of the water-insoluble proteins are zein, gluten and lactalbumin.

Proteins that are typically soluble in water and therefore can not be used in chewing gums can become insoluble in water. Such proteins can be treated with a binding agent to create a bound protein that is incompatible with water. Such binding agents should be of the food grade variety and include tannic acid, polyphenols, glutamic acid, L-lysine monohydrochloride, glutaric dialdehyde, D-glucose and gluteraldehyde.

- While the present invention has been described with respect to what is currently considered to be the preferred specimens, it should be understood that other specimens are within the scope of the invention and are included in the claims that form part of the application.

EXAMPLE 1 COUPLING OF PROTEIN AND PLASTIFIER The following shows an exemplary procedure for identifying an appropriate plasticizer to form a mixture with a preselected protein (ie, zein).

The solubility parameter for zein is determined by identifying or calculating its solubility parameter value s and the components of the same OD, sp, and sn. The respective solubility parameter values are illustrated in Table 5 below.

Ethanol Propylene glycol (1,2-propanediol) difference in solubility parameter value > 15% + difference in solubility parameter value < fifteen% ++ difference in the value of the solubility parameter > 10% From Table 6 it is observed that both ethanol and propylene glycol are potential candidates for forming a mixture with zein because each of them has at least one solubility parameter value (ie, so) within 15. % and preferably within 10% of the protein To determine the best of the plasticizers to form a mixture with zein, the free volume of each protein-plasticizer mixture is calculated according to Formula III as previously described. The results are illustrated in Table 7.

TABLE 7 Pr? Tein Coef. of expansion Temp. Transition Free Volume of Thermal Plastifyer 103 [K "1] to glass Tg (° C) Mixtures with zeina cc * Zeine 0.290 82 Propylene glycol 0 277 60 0.0320 Ethanol 0.275 - 116 0.0473 at a reference temperature T of 25 ° C.

As illustrated in Table 7, the mixture of zein and ethanol has a higher free volume than the mixture of zein and propylene glycol. As for these two specific mixtures, the mixture of zein and ethanol would be expected to be the preferred one for processing in comparison to the mixture of zein and propylene glycol for the formation of a plasticized proteinaceous material due to its greater free volume.

Once the mixture or potential mixtures have been determined as described above, the glass transition temperature of the expected final product (plasticized protein material) is determined in a chosen volume fraction of the plasticizer according to Formula (IV) described previously. The transition temperatures of zein and ethanoi. they are illustrated in Table 8.

TABLE 8 Protein / Plastifyer Transition temperature to glass Tg (° C) Zeina 82 Ethanol 116 From this information and the knowledge of a desirable range for the glass transition temperature of the final product, an appropriate amount of zein and ethanol can be used to form the mixture which can then be processed under heating and controlled breaking conditions for obtaining a plasticized proteinaceous material according to the present invention.

EXAMPLE 2 FORMATION OF PLASTIFIED PROTEINASE MATERIAL Batch Mixing This example illustrates that a selection of proteins and plasticizers or plasticizer mixtures can be successfully treated under the conditions of the present invention for provide a plasticized proteinaceous material. This example further illustrates the use of a batch-type batch apparatus with high breaking.

Zeina, isolated from milk and gelatin are shown as a mixture easily processed with fusion. Egg white, whey and sodium caseinate are also shown as easily processed with fusion. The latter displayed increased moment values and limited processability beyond a certain time and temperature in the trainer. All the plasticized proteinaceous materials formed in accordance with the present invention exhibit properties that can be used to replace the synthetic ingredients in chewable confections.

Protein denaturation is indicated by a maximum in the processing moment values (melt moment values) due to the phase transition from the powder to the viscous leg. The measurements of the moment values (a measure of viscosity), the glass transition temperatures and the mechanical properties of the materials are plasticized proteinaceous materials are provided.

Zein, egg white, milk (whey concentrate, sodium caseinate, milk isolates (mixture of 80% caseinate and 20% whey)) and gelatin (GP-8, 250 bloom) were obtained from Freeman Industries , Clofine Dairy and Food Products, Mew Zeland Milk Products and Hormel Foods Corporation, respectively. These natural proteins were used as they were received.

Propylene glycol and glycerol are from Sigma and triethyl citrate, polyethylene glycol and sorbitol are from Morflex, Aldrich and SPI Polyols, respectively.

The butyl rubber was poly (isobutylene-isoprene) copolymer (Butyl 077, molecular weight = 40,000) of Exxon; the poly (vinyl acetate) was AYAC, molecular weight = 12,800, from Union carbide; wax 175 was from Petrolite.

In these examples the proteins were plasticized using a Brabender C.W rheometer at the moment. (PL 2,000) with a mixer equipped with roller blades The Reammet or Brabender is a hot chamber that fits on two irregularly shaped rollers. A quantity of material is added to the chamber at 70% capacity by using the following expression: Sample load = 70% x volume of the mixer x specific gravity of the sample. The sample is melted, and the total moment required to make the rolls in the melt at a given rotational speed, which can be constantly varied, is measured with a dynamometer that includes a mobile gearbox coupled to a load cell by middle of a moment arm. The unit is pre-calibrated but can be recalibrated. The temperature of the polymer is determined using a thermocouple protruding inside the sample chamber. The data consist of measured values of moment (y axis) and temperature at constant rotational velocity against time (x axis) and represents the processability of the sample. The total amount of material used in the mixer was 250 g. The moment values were measured and recorded by a microprocessor as a function of time in half minute intervals at different temperatures. The tables represent the values considered significant at point q?e is illustrated.

The moment is expressed as "meter-gms" or as newton-meters. "These can easily be converted to other units such as poise or pascal-sec.

The zein powder was mixed with different amounts of glycerol, propylene glycol and water for comparison, and the mixtures were heated in the pre-mixer of the Brabenier mixer from room temperature to 120 ° C at 30 RPM. The plasticization of the zein with water was carried out from 30 ° C to 80 ° C to avoid the evaporation of water at elevated temperatures.

M Table 9 provides the moment values for the plasticization of zein with 20% plasticizer.

TABLE 9. Moment values of zein with 20% plasticizer Time (minutes) Glycerol Propylene glycol Water 0.5 756 897 829 1.0 756 897 829 2.0 665 897 829 3.0 711 2600 829 4.0 688 6144 829 5.0 3140 5511 1198 6.0 5042 3981 1244 7.0 6257 2313 2000 8.0 7185 1565 3386 9.0 4928 1197 2810 10.0 3690 989 2027 11.0 3140 805 1705 12.0 2842 713 1682 The maximums in the moment values, that is, the melting maxima, which include the process of denaturation in the protein structure under heat and rupture, are observed for all three plastifiers. Melting maxima occur at different temperatures when different plasticizers were used, ie 60 ° C, 80 ° C and 100 ° C for water, propylene glycol and glycerol, respectively. The foregoing indicates that the Denaturing of zein varies with different plasticizers and is related to its structure and solubility parameter values.

Tables 10a-10c provide the melting temperature, melting point values, and glass transition temperature values for the zema pl product as a melt of the plasticizer content.

TABLE 10a Fusion Temperature (° C) of Zeina 51 42 30 44 Table 10b shows that the moment values decrease in all cases and become constant after the fusion of the proteins since no further aggregation occurs. The fusion processing of the zein should be carried out at temperatures when the moment values remain constant. The above confirms the results obtained from the moment values. Although the zein fusion is best achieved by water followed by propylene glycol and glycerol, poor stability makes the water undesirable as a plasticizer. Cottonseed oil was also used as a plasticizer for the zein in the previous test but under the experimental conditions the fusion did not occur.

Table 11 provides the zein moment values as a fusion of the amount of plasticizer, and the drop is maximum for propylene glycol. The values of Momer to the water were obtained at a lower temperature (ie, 80 ° C). Propylene glycol is the most efficient plastiñcador among those exemplified.

Table 12 shows that a mixture of plasticizers (75% d glycerol and 25% propylene glycol) can be used to form a proteinaseous material with zein.

TABLE 12 l) Glycerol + Propylene glycol = 25% ha Table 12 shows the glass transition temperature values of the plasticized proteinaceous materials. Tg values of zein as a function of propylene glycol in the mixture of glycerol and propylene glycol are given. The Tg value of zein reduces to 35 ° C in the presence of (15% glycerol 20% propylene glycol) as the plasticizers.

B. EGG CLEAR: The egg white powder was mixed with 30% glycerol and the mixture was heated in the Brabender mixing container from 30 ° C to 120 ° C.

Table 13 provides the moment values for the plasticization of the egg white.

TABLE 13 Moment Values for Egg White Time 20% glycerol + 25% glycerol + 30% glycerol + 30% glycerol + (minutes) 20% water 20% water 20% »water 0% water Temp Temp - = 30 - Temp - = 30 - Temp - = 30 - - = 30 - 120 ° C 80 ° C 80 ° C 80 ° C 1.0 4708 2191 1218 92 2.0 7137 3229 1505 138 3.0 9451 5120 1896 138 4.0 7391 4151 1253 173 5.0 6251 2791 896 277 6.0 6147 2306 827 1083 JO 6009 2237 942 1821 8.0 4967 8.5 11479 As illustrated in Table 13, the moment value of the mixture was increased to 12,000 mg after denaturation at about 80 ° C. Table 13 also provides the egg white moment values from 30 ° C to 80 ° C with varying amounts of glycerol (20% to 30%) and fixed amount of water (20%). The mixture: iodinated from egg white with glycerol was only very fragile when examined after recovering it from the mixing container. The processes of denaturation and aggregation in the egg white protein are rapid. The water / glycerol mixtures allow the fusion processing of the egg white without excessive aggregation of the protein but as previously indicated, the water is undesirable as a plasticizer. The maximum denaturation (melting) is observed at around 50 ° C followed by the drop in time to a constant value at higher temperature (75 ° C). The moment of fusion reduces when the amount of glycerol is increased in the plasticizer mixture. No more aggregation of the egg white occurs due to the presence of water.

Table 14 shows the effect that the rate of rupture can have on the denaturing process.

TABLE 14 Momentum Values of Egg White in 25% glycerol and 50 ° C Egg white with 25% glycerol at 50 ° C was processed at rupture rates of 75 sec "and 225 sec". Higher rupture rates provide additional energy to accelerate the aggregation process.

Tables 15 and 16 provide additional examples of the use of plasticizer mixtures with egg whites such as protein. Variant quantities of glycerol and sorbitol were mixed in different proportions with the total amount of the plasticized content maintained at 30%. Before mixing with the egg white, the plasticizers mixed were heated to melt the sorbitol and form a homogeneous liquid with glycerol. The hot liquid was then mixed with the egg white and processed in the mixing container at 50 ° C.

Table 15 provides the moment values of the denaturation.

TABLE 15 Egg White Moment Values at 50 ° C Time (minutes) 30% glycerol / 0% 25% glycerol / 5% 15% gIiceroI / 15% sorbitol sorbitol sorbitol 1.0 392 564 1106 2.0 1452 2246 2707 3.0 1521 1993 2787 4.0 1176 2235 2833 5.0 1014 2776 2626 6.0 1360 3732 1843 JO 2063 6818 1843 8.0 4126 1682 8.5 6200 1739 9.0 1785 10.0 1981 12.0 2557 13.0 4227 13.5 6242 Denaturation occurred as previously observed with pure glycerol. However, excessive aggregation was significantly delayed in the presence of 15% sorbitol. The greater amount of sorbitol in the mixture was found to accelerate the aggregation process.

The Tg values of the egg white material as a function of the sorbitol content in the glycerol / sorbitol mixture are given in Table 16.

TABLE 17b Sodium Caseinate Moment Values at 50 ° C Time (minutes) 20% glycerol 30% glycerol 40% glycerol .0 622 230 450 .0 784 738 1039 .0 1210 830 1362 .0 1729 1279 1501 .0 4091 1567 1755 .5 7952 2636 2205 .0 3285 2286 0.0 5693 3394 1.0 7261 5460 1.5 9035 6246 2.0 6765 3.0 8035 4.0 9824 TABLE 17c TMP Moment Values at 50 ° C The data illustrated in Tables 17a-17c indicate that 20% and 30% glycerol can not improve processing of the whey protein as the aggregation process is followed almost immediately after the denaturation step. However, 40% glycerol delays aggregation and improves the plasticization of the protein considerably. The process window for sodium caseinate increases with increased amounts of plasticizers. Poly (ethylene glycol) was also used as u :? plasticizer for whey protein but under the experimental conditions the fiysis did not occur.

Tables 18a and 18b provide the melt plasticization of sodium caseinate and TMP with propylene glycol at 50 ° C.

The processing window of sodium caseinate increases with the increasing amount of plasticizers as observed with glycerol. Excessive aggregation was not observed with 50% propylene glycol that was produced at 80 ° C. The data show that this protein can be processed for extended periods of time and can be used in continuous processes such as those that use extruders. For milk isolates (TMP) 40% and 50% propylene glycol eliminates excessive aggregation as observed for sodium caseinate. The final moment values are very low.

Table 19 provides a comparison of the processing windows for the egg white, whey, sodium caseinate, and TMP proteins with glycerol as the plasticizer at 50 ° C.

TABLE 19 Processing Window Time (Minutes) for proteins at 50 ° C and Moment = 50,000 mg In general, the processing of these proteins must be carried out at 50 40.6 As illustrated in Tables 20a and 20b the Tg values fall with the decreasing amount of the plasticizer content. Both plasticizers are efficient in reducing the Tg values. .-- a Table 21 provide the moment value as a function of the plasticized gelatin processing time with different amounts of glycerol at 80 ° C.

TABLE 21 longer indicating that excessive aggregation does not occur. Glycerol proves to be an effective plasticizer for gelatin as the moment value decreases with Increased amount of plasticizer content. The moment values are lower when the gelatin is processed at high temperatures. Plasticized gelatin can be reprocessed after cooling similar to a thermoplastic material. The above indicates that the plasticized material can be very useful common continuous process.

The parameters evaluated in the denaturation process, mainly the moment values of the process and the temperatures of the process, and the Tg values, found in several of the preferred plasticized proteinase materials are summarized in Table 22.

TABLE 22 Summary of Protein Properties Material Plasticizer Moment, mg Temp. ° C Tg, ° C Zein 25% PG 350 120 42 30% glycerol 500 120 44 Egg white 40% glycerol 5000 50 34 15% glycerol + 5000 50 35 15% sorbitol Caseinate 50% PG 3250 80 40 50% glycerol 5000 50 41 TMP 50% PG 2500 80 35 50% glycerol 5000 50 35 Tables 23 to 20 provide mechanical properties found for the plasticized proteinaceous materials prepared by the process of the present invention. The decrease in modulus and strength, and the increase in elongation in the breaking values of the plasticized proteinaceous materials illustrates the efficiency of the plasticizing process to provide a useful final product. around 80 ° C to 8,000 psi. The mechanical properties were determined using the same specimen dimensions and test conditions as described in Example 2. Tables 34-41 summarize the properties of the various plasticized proteinaceous materials.

TABLE 34 Mechanical Properties of Gelatin / Sodium Caseinate / 30% Glycerol Maximum Stress Rate Modules (Kgf / miO Chain in mixtures (Kgf / mm2) break (%) 90 gelatin: 10 cas 0.62 1.6 184.2 70 gelasin: 30 cas 0.48 6.3 52.0 50 gelatin: 50 cas 0.47 5.5 83.3 TABLE 35 Mechanical Properties of Gelatin / TMP / 30% Glycerol Maximum Stress Rate Modules (Kgf / miO Chain in mixtures (Kgf / mm2) break (%) 90 gelatin: 10 TMP 0.46 0.84 214.6 70 Gelatin: 30 TMP 0J 3.9 125.6 50 Gelatin: 50 TMP 0.4 4.4 97.6 TABLE 36 Mechanical Properties of Gelatin / GIiadin / 30% Glycerol Mixture Ratio Maximum Voltage Modules (Kgf / mm) Chain in (Kgf / mm2) Break (%) 90 gelatin: 10 gliadin 0.34 0.63 233.6 70 gelatin: 30 gliadin 0.29 0.75 215.0 50 gelatine: 50 gliadin 0.20 0.52 256.0 TABLE 37 Mechanical Properties of Gelatine / Zeine / 30% Glycerol Maximum Stress Rate Modules (Kgf / mpT) Chain in mixtures (Kgf / mm2) break (%) 90 gelatin: 10 zein 0.41 1.1 164.2 70 gelatin: 30 zein 0.28 5.4 34.7 50 gelatin: 50 zein 0.48 20.9 9.1 TABLE 38 Mechanical Properties of Zein / Sodium Caseinate / 30% PG Maximum Stress Rate Modules (Kgf / mnr) Chain in ices (Kgf / mm2) break (%) 90 zeiná: 10 cas 0.09 1.6 166.8 70 zeiná: 30 cas 0.11 1.9 159.4 50 zeiná: 50 cas 0.07 0.8 152.9 TABLE 39 Mechanical Properties of Zein / TMP / 30% »PG Maximum Voltage Ratio Modules (Kgf / mnT) Chain in mixtures (Kgf / mm2) break (%) 90 zeine .: 10 TMP 0.03 0.43 409.6 70 zeiná: 30 TMP 0.04 0.65 330.4 50 zeiná: 50 TMP 0.04 0.43 232.4 TABLE 40 Mechanical Properties of Zein / Egg White / 30% Glycerol Maximum Stress Rate Modules (Kgf / mpr) Chain in mixtures (Kgf / mm2) break (%) 80 zeina: 20 CH 1.1 59.3 2.7 50 zeina 50 CH 1.0 41.2 5.6 TABLE 41 Mechanical Properties of Gelatine / Sodium Caseinate / 30% Glycerol Maximum Stress Rate Modules (Kgf / mm) Chain in ezclas (Kgf / mm2) break (%) 31 gei: 19 cas: 19 0.5 11.3 45.1 zeina A pre-extruded plasticized proteinase material made from gelatin with 30% glycerol was added to a Brabender mixing vessel at 100 ° C and processed for 4 minutes (moment = 4,000 mg). The rest of the ingredients of the gum base were added to the container in the order in which they are listed.

Increase) emplo A2 Gelatin with Egg White This example illustrates a gum base prepared without Ingredient Parts (grams) Gelatin / 40% glycerol 30.00 Filling 43.50 Resin 82.47 Egg white / 40% glycerol 50.00 Wax 22.50 Fat 12.50 Emulsifier 2.50 Antioxidant 6.45 Total 249.92 A pre-extruded plasticized proteinaceous material made from gelatin, egg white and glycerol was added to a Brabender mixer at 100 ° C to prepare gum base as before.

A3 Zeina sub-assembly This example illustrates the replacement of the traditional elastomer, PVAc and wax.

Ingredient Parts (grams) Zein 30.00 Glycerol 14.46 Filling 18.41 Mixture of Gliadin - gelatine 16.40 Resin of wood RS - 5 159.28 Oil 9.03 Grease 9.03 Total 248.73 The gum base was prepared using a Bestoff extruder configured to have eight barrels with an L / D of 40. The rpm was 200 and the temperature varied from 50 ° C to 85 ° C. The protein was added to the initial barrel heated to 50 ° C with plasticizer added to the second barrel. The protein-plasticizer mixture was exposed to high rupture at a temperature of from 75 ° C to 80 ° C. Resin and fat were added to the third barrel. The filling was added with the zein.

B. Preparation of Chewing Gum This example illustrates the preparation of chewing gums. Sub-examples Bl, B7, B8, B9 and B10 illustrate the preparation of a chewing gum in one step, ie without isolation of the plasticized protein material. Sub-examples B2-B4 illustrate the use of the plasticized proteinaceous material as prepared in previous examples. Sub-examples B5 and B6 illustrate the use of a proteinaseous material plasticized with additional protein.

Subejemplo Bl Zeina-based gum formulation In this example the plasticized proteinaceous materials are replaced by the elastomer, PVAc and were used in traditional ways. Ingredient Frozen parts Zein 22.12 Glycerol 14.46 Filling 18.41 Mixtures Gliadin - Gelatine 16.40 Wood resin RS - - 5 159.28 Oil 9.03 Grease 9.03 Crude sweetener 96.80 Flavor 6.23 Intense sweetener 1.25 Lecithin 1.75 Total 354.76 The chewing gum was prepared in a Brabender mixing vessel at 30 rpm from an initial temperature of 105 ° C to 50 ° C until homogeneous. The ingredients were added in the order listed - The crude sweetener was pre-dissolved in 20 ml of water.

The above gum formulation was compared by a test panel with a commercial gum product for initial hardness, bending capacity, acidity, taste, sweetness, wax, hardness, humidity, cohesiveness, adhesiveness and chewiness over time. The panelists determined that the gum from SubExample Bl was similar in hardness of the initial gum and the capacity of doubles and also in the total hardness, moisture, chewiness, taste and sweetness to commercial product. The gum from SubExample Bl was found to have a high acid character and a much stronger waxy character.

Sub-Example B2 Gliadin-based Rubber Formulation This sub-example and Sub-examples B3-B6 illustrate the use of pre-made plasticized protein materials to replace the traditional use of elastomer, PVAc and wax.

Ingredient Parts (grams) Gliadin 26.58 Glycerol 26.58 Filling 18.41 Wood resin RS - 5 159.28 Oil 9.03 Grease 9.03 Crude sweetener 96.80 Flavor 4.73 Intense sweetener 1.26 Lecithin 1.75 Total 353.45 A plasticized proteinaceous material containing gliadin / gelatin and glycerol was added to the Brabender mixing vessel at 100 ° C and the remaining ingredients were added to the container in the order in which they are listed.

Sub-Example B3 Gliadin / Gelatin Mix Rubber Formulation Ingredient Parts (grams) Gliadin 22.11 Gelatin 22.11 Glycerol 18.95 Filler 18.41 Resin wood RS 159.28 Oil 9.03 Grease 9.03 Crude sweetener 96.80 Flavor 6.23 Intense sweetener 1.26 Lecithin 1.75 Total 364.96 The formula was processed in the manner of Sub-Example Bl.

Sub-example B4 Gelatin / Glycerol Gum Formulation (Without the Gliadin-Gelatin Blend) Ingredient Parts (grams) Gelatin 37.21 Glicerol 15.95 Filling 18.41 Wood resin RS - 5 159.28 Oil 9.03 Grease 9.03 Unwrought sweetener 55.35 Taste 6.23 Intense sweetener 1.26 Lecithin 1.75 Total 313.50 The formula was prepared in a manner similar to Sub-Example Bl. A panel evaluated the rubber to assess the sensitive characteristics. The gum was found to have a texture close to the traditional rubber with more chewiness. After a hard initial mastication softened. The characterize was found to be one of flavor over texture.

Sub-example B5 Gelatin / Zein / Glycerol Gum Formulation In this example a plasticized proteinaceous material made from gelatin, zein and glycerol was plasticized by pre-melting, followed by the addition of a gelatin-gliadin mixture and then plasticized. Ingredients Parts (grams) Gelatine 12.80 zein 12.80 Glycerol 10.97 Gelatin-gliadin mixture 16.50 Filling 18.41 Wood resin RS - - 5 159.28 Oil 9.03 Grease 9.03 Unwrought sweetener 55.35 Flavor 6.23 Intense sweetener 1.26 Lecithin 1.75 Total 313.41 This example was processed in a similar way to Sub-Example Bl. The gum was found with a hard, caramel-like chew that tended towards a rubbery character. The gum was evaluated for having waxy properties related to a chewing gum.

Sub-Example B6 Gelatin / Glycerol Gum Formulation In this example a plasticized proteinaceous material made from gelatin and glycerol was plasticized by pre-melting, followed by the addition of a gelatin-gliadin mixture and then plasticized.

Ingredient Parts (grams) Gelatine 26.60 Glycerol 10.97 Gelatin mixture - gliadin 16.50 Filling 18.41 Wood resin RS - 5 159.28 Oil 9.03 Grease 9.03 Unwrought sweetener 55.35 Flavor 6.23 Intense sweetener 1.26 Lecithin 1.75 Total 313.41 This example was processed in a way similar to Submenu Bl. A panel evaluated the rubber to assess the sensitive characteristics. The gum was found to be initially firm, and then it was found to soften quickly and has less cohesion than a traditional chewing gum.

Subejemplo B7 Zeina formulations: The following examples show the preparation of a gum having the resin, gum and PVAc replaced by a plasticized proteinase material of the present invention. The ingredients used to formulate the gum are shown below.

The zein, propylene glycol, emulsion and CaCO3 were mixed in a vessel. The mixture was heated in a Brabender at 80 ° C for 2 minutes. The wax component was added and the resulting mixture was cooled to 70 ° C. The oil, emulsifier and soybean oil were added under stirring and the resulting mixture was cooled to 50 ° C. The sweeteners and the flavor were then added and mixed for two minutes.

The resulting gum exhibited rapid hydration, an initial gummy chewing and a smooth texture in the mouth.

Sub-example B8 Glutene Formulation: The following examples show the preparation of a chewing gum that has all rubber base materials replaced with a plasticized protein material in accordance with the present invention. The ingredients used to formulate the gum are shown below: The ingredients were combined in a manner similar to that described in Sub-Example B7. The resulting gum exhibited excellent elasticity, rebound and chewiness.

Sub-Example B9 Zein Formulation: The following examples show the preparation of a chewing gum in which the gum is replaced with a plasticized proteinase material of the present invention. The ingredients used to formulate the gum are shown below: Ingredient% by Weight Zein 19.86 Glycerin 8.41 Emulsion Biphasic oil / water 5.72 Resin (wood resin ester) 33.33 Microcrystalline wax 4.04 Hydrolyzed cottonseed oil 5.05 Glycerol monostearate 1.34 CaC03 17.17 Taste 2.02 Aspartame 1.34 Soybean oil 1.68 The zein, glycerin, emulsion and CaCO3 were mixed in a vessel. The mixture was heated in a Brabender at 85 ° C for two minutes. The wax component was added in minutes at 85 ° C. The oil and emulsifier was added in 15 minutes with stirring and the resulting mixture was cooled to 70 ° C. The sweetener, flavor and soybean oil were added in 5 minutes and mixed at 40 ° C.

The rubber composition demonstrated an exceptional potential for a replacement of a synthetic rubber base. The composition shows elasticity, rebound, chewiness and gives attributes of chewiness immediately after chewing.

BIO sub-example Zeine formulation: The following examples show the preparation of a chewing gum in which the resin, gum and PVAc are replaced with a plasticized proteinase material of the present invention. The ingredients used to formulate the gum are shown below.

Ingredient% by Weight Zein 27.27 Propylene glycol 20.45 CaC03 11.36 Sugar 28.40 Corn syrup 4.54 Lecithin 3.40 Acetic acid 0.45 Flavor 1.13 Sweeteners 1.17 The zein and the propylene glycol were mixed in a vessel. The mixture was heated in a Brabender at 60 ° C for 5 minutes. CaCO3 and sugar were added and mixed for 10 minutes and the resulting mixture was cooled to 55 ° C. Corn syrup and the lecithin were added under stirring for 10 minutes and the resulting mixture was cooled to 50 ° C. The acetic acid, the sweetener and the flavor were then added and mixed for 10 minutes at 50 ° C.

The resulting gum exhibited rapid hydration, an initial gummy chewing and a smooth texture in the mouth.

EXAMPLE 4 Sub-Example Cl Candy Formulation: A soft candy confectionery product in accordance with the present invention was prepared from the ingredients shown below: Ingredient% by weight Gelatin 1.13 Gum arabic 0.34 Corn syrup 44Be 16.36 Water 1.75 Granulated sugar 38.87 Fat 1.83 Flavor 0.50 Demineralized whey protein 1.50 Glycerol 0.33 Powdered sugar 2.74 Cellulose powder 0.91 Scraping was formed by the addition of the gelatin to hot tap water (60 gm) and mixed until dissolved. The solution was allowed to stand for 30 minutes. The gum arabic was added to cold tap water (27.6 gm) and treated in the same way as the gelatin. The gelatin and gum arabic solutions were added to 818.0 gm syrup. hot 44Be corn in a Hobart mixer and mixed there at low and then moderate speeds for a total of 4 minutes.

A Bob syrup was prepared by mixing 1503.5 gm of 44 Be corn syrup, 943.5 gm of granulated sugar and 600 ml of water. The mixture was heated to 130 ° C.

The Bob syrup was added slowly to the shaving under stirring for about 5 minutes. The cellulose powder was added under stirring for 2 minutes after the successive addition of sugar and fat. Thereafter the demineralized whey protein / glycerol plasticized proteinase material was added under stirring followed by the addition of the sweeteners and flavorings.

The resulting candies exhibited all the properties including the chewiness and texture of a conventional candy.

Sub-examples C2 - C4 Caramel Formulations: The method of SubExample Cl was repeated except that glycerol (0.33% by weight) was replaced with the same amount of ethyl lactate (Subejemplo C2), lactic acid (Subejemplo C3) and butyl lactate (Subejemplo C4), respectively. The resulting candies produced according to Sub-examples C2-C4 exhibited all the properties of a conventional candy including chewiness and texture.

Claims (54)

1. EIV INDICATIONS: 1. A method for identifying compatible proteins and plasticizers for the formation of a plasticized proteinase material comprising: a) choosing a protein component; b) determine the solubility parameter of the protein component as defined by Formula I if 2 = soi 2 +, spi 2 +, s-Hi 2 where: if it is the value of the total solubility parameter of the protein component; sDi is the value of the solubility parameter contributed by the dispersing forces of the protein component; spi is the value of the solubility parameter contributed by the polar forces of the protein component; spi is the value of the solubility parameter contributed by the hydrogen bonds of the protein component; c) choosing a plasticizer component having a second solubility parameter defined by Formula (II): s2 2 2 2: 0"D2 + sP2 + OTH2 where: s2 is the value of the total solubility parameter of the plasticizer component; is the value of the solubility parameter contributed by the dispersing forces of the plasticizer component; sp2 is the value of the solubility parameter contributed by the polar forces of the plasticizer component; sH2 is the value of the solubility parameter contributed by the hydrogen bonds of the plasticizer component; and coupling a protein component with a plasticizer component wherein at least one of the following pairs of values of the solubility parameter si-s2, soi -s > 2, spt - sp2 and sHi - OH2 are within 15% of each.
2. 2. The method of Claim 1 wherein at least one of the pairs of the solubility parameter values are within 10% of each.
3. 3. The method of Claim 1 wherein if and s2 are within 15% of each.
4. 4. The method of Claim 1 wherein ODI and so2 are within 15% of each.
5. 5. The method of the Claim which further comprises calculating the free volume of the coupled protein and plasticizer components conforms to Formula (III): FV = 0.025 + ad (T-Tgd) + ap (- Tgp) where: FV is the free volume of the mixture; ap is the coefficient of thermal expansion of the protein component; aa is the coefficient of thermal expansion of the plasticizer component; Tgd is the glass transition temperature of the plasticizer component; Tgp is the glass transition temperature of the protein component; and T is a reference temperature.
6. 6. A method for producing a plasticized proteinase material comprising: a) choosing a protein component having a first solubility parameter defined by formula (I): si = sDi + spi + s where: if it is the value of the solubility parameter total protein component; soi is the value of the solubility parameter contributed by the dispersant forces of the protein component; spi is the value of the solubility parameter contributed by the polar forces of the protein component; spi is the value of the solubility parameter contributed by the hydrogen bonds of the protein component; b) choosing a plasticizer component having a second solubility parameter defined by Formula (II): wherein: s2 is the value of the total solubility parameter of the plasticizer component; sD2 is the value of the solubility parameter contributed by the dispersing forces of the plasticizer component; sp2 is the value of the solubility parameter contributed by the polar forces of the plasticizer component; sH2 is the value of the solubility parameter contributed by the hydrogen bonds of the plasticizer component; where at least one of the following pairs of solubility parameter values si -s2, soi-s? > 2, Opi - sp2 and sm - sm are within 15% of each. c) combining the protein and plasticizer components to form a mixture to form a plasticized proteinase material wherein the plasticizer component is uniformly dispersed within the protein component.
7. 7. The method of Claim 6 wherein at least one of the pairs of the solubility parameter values are within 10% of each.
8. 8. The method of Claim 6 wherein if and s2 are within 15% of each.
9. 9. The method of Claim 6 wherein s and so2 are within 15% of each.
10. 10. The method of Claim 6 further comprising calculating the free volume of the coupled protein and plasticizer components conforms to Formula (III): FV = 0.025 + ad (T - Tgd) + ap (- Tgp) where: FV is the free volume of the mixture; o-p is the coefficient of thermal expansion of the protein component; ote is the coefficient of thermal expansion of the plasticizer component; T is a reference temperature; Tgd is the glass transition temperature of the plasticizer component; and Tgp is the glass transition temperature of the protein component.
11. 11. The method of Claim 6 wherein the step of treating the mixture comprises heating the mixture to a temperature of from about 20 to 140 ° C under controlled breaking conditions.
12. 12. The method of Claim 11 comprising heating the mixture to a temperature of from about 20 to 120 ° C.
13. 13. The method of Claim 11 comprising treating the mixture in a closed mixer or extruder.
14. 14. The method of Claim 13 comprising contacting the mixture with roller blades.
15. 15. The method of Claim 6 further comprising selecting a desired glass transition temperature for the plasticized proteinase material and choosing the amount of the protein component and the plasticizer component according to Formula (IV): T = (ad / ap ) .Vd. (Tgd - Tgp) + Tgp wherein: gmix is the glass transition temperature of the plasticized or proteinaceous material; o-d is the coefficient of thermal expansion of the plasticizer component; ap is the coefficient of thermal expansion of the protein component; Vd is the volume fraction of the plasticizer. Tgd is the glass transition temperature of the plastiñcador component; and Tgp is the glass transition temperature of the protein component.
16. 15. The method of claim 6 wherein the amount of the protein component is at least 40% by weight based on the total weight of the mixture.
17. 17. The method of claim 16 wherein the amount of the protein component is at least 50% by weight based on the total weight of the mixture.
18. 18. The method of claim 17 wherein the amount of the protein component is from about 60 to 75% by weight based on the total weight of the mixture.
19. 19. The method of claim 6 wherein the protein component is soluble in water.
20. 20. The method of claim 6 wherein the protein component is insoluble in water.
21. 21. The method of claim 6 wherein the protein component is selected from the group consisting of grain proteins, animal proteins, egg proteins and milk proteins.
22. 22. The method of claim 21 wherein the protein component is a grain protein selected from the group consisting of zein, glutenin, gliadin and mixtures thereof.
23. 23. The method of claim 21 wherein the egg and milk protein components are selected from the group consisting of gelatin, egg albumin, lactalbumin, casein, sodium caseinate, whey and mixtures thereof.
24. 24. The method of claim 6 wherein the plasticizer component is at least one organic plasticizer.
25. 25. The method of claim 24 wherein the organic plasticizers are selected from the group consisting of propylene glycol, ethylene glycol, acetic acid, lactic acid, polypropylene glycol polyethylene glycol, glycerol and ethanol and mixtures thereof.
26. 26. The method of claim 19 further comprising reacting the water soluble protein with a binding agent to form a water insoluble protein.
27. 27. A plasticized proteinaceous material produced by the method of Claim 6.
28. 28. A plasticized proteinaceous material comprising a protein component and a plasticizer component wherein a solid state mixture of the protein component and the plasticizer component has been heated under controlled breaking conditions at a temperature of from about 20 ° C to about 140 ° C to form a plasticized proteinase material.
29. 29. The plasticized proteinaceous material of Claim 28 wherein the protein component includes zein, glutenin or gliadin.
30. 30. The plasticized proteinaceous material of Claim 28 wherein the plasticizer component is at least one organic plasticizer.
31. 31. A method for forming a gum or confectionery composition comprising: a) choosing a protein component; b) determine the solubility parameter of the protein component as defined by Formula I m 2 if +, spi 2 +, sm 2 where: if it is the value of the total solubility parameter of the protein component; ODÍ is the value of the solubility parameter contributed by the dispersant forces of the protein component; spi is the value of the solubility parameter contributed by the polar forces of the protein component; sHi is the value of the solubility parameter contributed by the hydrogen bonds of the protein component; c) choose a plasticizer component having a second solubility parameter defined by Formula (II): 2 2, 2, 2 s2 = so2 + s? + sH2 where: s2 is the value of the total solubility parameter of the plasticizer component; so2 is the value of the solubility parameter contributed by the dispersing forces of the plasticizer component; sp2 is the value of the solubility parameter contributed by the polar forces of the plasticizer component; s? 2 is the value of the solubility parameter contributed by the hydrogen bonds of the plasticizer component; where at least one of the following pairs of values of the solubility parameter if - s2, sDi - sD2, spi - sp2 and sm - s are within 15% of each. d) combining the corresponding protein and plasticizer components to form a mixture; e) treating the mixture to form a plasticized proteinase material wherein the plasticizer is dispersed evenly within the protein; Y f) combining the plasticized proteinaceous material with other ingredients sufficient to form said gum or confectionery composition.
32. 32. The method of claim 31 wherein the pairs of values of solubility parameters are within 10% of each.
33. 33. The method of claim 31 wherein if and s2 are within 15% of each.
34. 34. The method of Claim 31 wherein sDi and D2 are within 15% of each.
35. 35. The method of Claim 31 further comprising calculating the free volume of the coupled protein and plasticizer components conforms to Formula (m): FV = 0.025 + ad (T - Tgd) + ap (- Tgp) where: FV is the free volume of the mixture; ap is the coefficient of thermal expansion of the protein component; ad is the coefficient of thermal expansion of the plasticizer component; T is a reference temperature; Tgd is the glass transition temperature of the plasticizer component; and Tgp is the glass transition temperature of the protein component.
36. 36. The method of Claim 31 wherein the step of treating the mixture comprises heating the mixture to a temperature of from about 20 to 140 ° C under controlled breaking conditions.
37. 37. The method of Claim 26 comprising heating the mixture to a temperature of from about 20 to 120 ° C.
38. 38. The method of Claim 38 comprising treating the mixture in a closed mixer or extruder.
39. 39. The method of Claim 38 comprises contacting the mixture with roller blades.
40. 40. The method of Claim 31 further comprising selecting a desired glass transition temperature for the plasticized proteinase material and choosing the amount of the protein component and the plasticizer component according to Formula (IV): Tgnüx = (ad / ap ) .Vd. (Tgd - Tgp) + Tgp where: Tgmix is the glass transition temperature of the plasticized or proteinaceous material; o-d is the coefficient of thermal expansion of the plasticizer component; o-p is the coefficient of thermal expansion of the protein component; Va is the volume fraction of the plasticizer. Tgd is the glass transition temperature of the plasticizer component; and Tgp is the glass transition temperature of the protein component.
41. 41. The method of Claim 40 wherein the amount of the protein component is at least 40% by weight based on the total weight of the mixture.
42. 42. The method of Claim 41 wherein the amount of the q is at least 50% by weight based on the total weight of the mixture.
43. 43. The method of Claim 342 wherein the amount of the protein component is from about 60 to 75% by weight based on the total weight of the mixture.
44. 44. The method of Claim 31 wherein the protein component is soluble in water.
45. 45. The method of claim wherein the protein component is insoluble in water.
46. 46. The method of Claim 31 wherein the protein component is selected from the group consisting of grain proteins, animal proteins and egg and milk proteins.
47. 47. The method of Claim 46 wherein the grain proteins are selected from the group consisting of zein, glutenin, gliadin and mixtures thereof.
48. 48. The method of Claim 46 wherein the egg and milk proteins are selected from the group consisting of gelatin, egg albumin, lactalbumin, casein, sodium caseinate, whey and mixtures thereof.
49. 49. The method of Claim 31 wherein the plasticizer component is at least one organic plasticizer.
50. 50. The method of Claim 59 wherein the organic plasticizers are selected from the group consisting of propylene glycol, ethylene glycol, acetic acid, lactic acid, polypropylene glycol, polyethylene glycol, glycerol and ethanol.
51. 51. The method of Claim 44 which further comprises reacting the water-soluble protein with a binding agent to form an insoluble protein in
52. 52. A gum produced by the method of Claim 31.
53. 53. The gum of Claim 52 that is biodegradable, edible or at the same time biodegradable and edible.
54. 54. A confectionery composition produced by the method of Claim 31. EXTRACT OF THE INVENTION Process for the formation of a plasticized proteinase material in which a plasticizer component is selectively coupled with a protein component to form a mixture. The mixture is heated under controlled separation conditions to produce the plasticized protein material having the plasticizer component evenly distributed within the protein component. The plasticized proteinaceous material is used for a variety of purposes including the production of gums and confectionery compositions.