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WO1999002046A1 - Procede de renforcement du parfum - Google Patents

Procede de renforcement du parfum Download PDF

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Publication number
WO1999002046A1
WO1999002046A1 PCT/US1998/014116 US9814116W WO9902046A1 WO 1999002046 A1 WO1999002046 A1 WO 1999002046A1 US 9814116 W US9814116 W US 9814116W WO 9902046 A1 WO9902046 A1 WO 9902046A1
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WO
WIPO (PCT)
Prior art keywords
flavorant
mer
reaction
reaction product
flavors
Prior art date
Application number
PCT/US1998/014116
Other languages
English (en)
Inventor
Henry B. Schur
Original Assignee
Schur Henry B
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schur Henry B filed Critical Schur Henry B
Priority to AU86577/98A priority Critical patent/AU8657798A/en
Publication of WO1999002046A1 publication Critical patent/WO1999002046A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/70—Fixation, conservation, or encapsulation of flavouring agents
    • A23L27/72—Encapsulation
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/70—Fixation, conservation, or encapsulation of flavouring agents
    • A23L27/74—Fixation, conservation, or encapsulation of flavouring agents with a synthetic polymer matrix or excipient, e.g. vinylic, acrylic polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/141—Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers
    • A61K9/146—Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers with organic macromolecular compounds

Definitions

  • the present invention relates to the modification of flavorants by reaction of mers, i.e., a monomer, prepolymer and/or polymer (including mixtures of the foregoing) , in the presence of flavorants to form products of significantly increased molecular weight.
  • the invention relates to reactions of mers in the presence of flavorants in liquid systems to form products of substantially increased molecular weight, in which products the flavorants are distributed for performing their characteristic functions in a host medium outside the reaction product.
  • Flavorants are any of a wide variety of materials which perform useful functions by distributing themselves via physical and/or chemical transport mechanisms, such as diffusion, evaporation of the like, throughout a host medium, such as a gas, liquid, solid or combination thereof.
  • Some examples of flavorant materials which find wide use in industrial, commercial, domestic and medical applications are disinfectants, foods, pharmaceuticals, flavors, insecticides, insect repellents, cleansing and cleaning materials, preservatives, emollients, exipients, stabilizers, dyes, diluents, lotions, inhalants, fungicides, air fresheners, anti-static agents, corrosion inhibitors, fertilizer, enzymes, poisons and lures.
  • the present invention is a method of modifying a flavorant comprising forming a liquid system including a solution of a mer with a flavorant, reacting the mer in the presence of the flavorant in a portion of the liquid system which contains substantial amounts of both mer and flavorant for significantly increasing the molecular weight of the mer under conditions which substantially preserve at least one useful flavorant function of the flavorant, continuing the reaction under such conditions to a sufficient extent for substantially reducing the diffusion rate, volatility flammability, toxicity or susceptibility to oxidation or other form of environmental attack upon the flavorant, and recovering a product of reaction of said mer substantially without rearrangement the liquid system into separate phases and substantially without encapsulation of the flavorant and having a consistency ranging from a liquid to a non-self-supporting soft gel, from which product the flavorant may escape for performing its flavorant function in or on a host medium outside the reaction product.
  • Products produced according to the foregoing method are also part of the invention.
  • the invention includes certain further improvements, all of which can be used singly or in any operative combination in or with the above-described methods and products of the present invention. These further improvements are discussed below under the heading "Detailed Description of Preferred Embodiments". Among them are a number of particularly preferred embodiments of the invention, including recovery of the product of reaction as a liquid.
  • the flavorant may include a flavor, pesticide, repellant, cleansing or cleaning material, preservative, emollient, excipient, stabilizer, dye diluent, lotion, anti-static agent, corrosion inhibitor fertilizer, enzyme or lure.
  • polyvinylpyrrolidone a cyclodextrin, algin, chitin or a monomer or derivative of any of them.
  • Polyvinylpyrrolidone is the preferred mer, especially with a molecular weight in the range of about 5,000 to about 200,000 and more preferably about 7,000 to about 160,000.
  • a preferred cyclodextrin is betacyclodextrin having a molecular weight of at least about 1,000.
  • the mer includes algin
  • the preferred reaction product includes an alginate.
  • Chitosan is a preferred chitin derivative.
  • Valuable products can be produced by applying the reaction product of the method to a substrate, and the invention therefore includes the corresponding products.
  • the invention provides the opportunity for obtaining one or more of the following advantages with respect to the performance of the flavorant in its end-use application(s) , including, for example, reduction of diffusion rate, volatility, flammability, toxicity, and oxidation or other environmental attack.
  • the invention provides opportunities for providing or enhancing one or more of the following properties in the resultant product, including longevity of the action of the flavorant, gloss, moldability, resiliency and miscibility with certain liquids. Because certain flavorants are not readily convertible to gel-form by other means, the invention opens up new applications for certain of these flavorants.
  • a reaction is conducted in a liquid system which comprises, or consists essentially of, or consists of, a mer and a flavorant and other liquid or non-liquid ingredients useful in forming certain reaction products.
  • a liquid system which comprises, or consists essentially of, or consists of, a mer and a flavorant and other liquid or non-liquid ingredients useful in forming certain reaction products.
  • flavorants are materials which perform useful functions by distributing themselves via physical and/or chemical transport mechanisms, such as diffusion, evaporation or the like, throughout a host medium, such as a gas, liquid, solid or combination thereof .
  • the desired materials have utility in performing a flavorant function in a host medium outside the reaction product.
  • the flavorant is transported into and treats or otherwise acts upon something in an adjoining or surrounding host medium, including the host medium itself.
  • flavorants include flavors, medicaments and pesticides.
  • Useful flavors include for example those based on aldehydes, ketones or alcohols.
  • aldehyde flavors include: acetaldehyde (apple) ; benzaldehyde (cherry, almond) ; anisic aldehyde (licorice, anise) ; cinnamic aldehyde (cinnamon) ; citral, i.e., alpha citral (lemon, lime); neral, i.e., beta citral (lemon, lime) ; decanal (orange, lemon) ; ethyl vanillin (vanilla, cream); heliotropine, i.e., piperonal (vanilla, cream); vanillin (vanilla, cream) ; a-amyl cinnamaldehyde (spicy fruity flavors) ; butyraldehyde (butter, cheese); valeraldehyde (butter, cheese); citronellal
  • ketone flavors include: d-carvone (caraway) ; 1-carvone (spearmint) ; diacetyl (butter, cheese, "cream") ; benzophenone (fruity and spicy flavors, vanilla); methyl ethyl ketone (berry fruits); maltol (berry fruits) menthone (mints) , methyl amyl ketone, ethyl butyl ketone, dipropyl ketone, methyl hexyl ketone, ethyl amyl ketone (berry fruits, stone fruits) ; pyruvic acid (smokey, nutty flavors) ; acetanisole (hawthorn heliotrope) ; dihydrocarvone (spearmint) ; 2 , 4-dimethylacetophenone (peppermint) ; 1, 3-diphenyl- 2-propanone (almond); acetocumene (orris and basil, spicy); isoja
  • Example of alcohol flavor include anisic alcohol or p- methoxybenzyl alcohol (fruit, peach) ; benzyl alcohol (fruity) ; carvacrol or 2-p-cymenol (pungent warm odor) ; carveol; cinnamyl alcohol (floral odor) ; citronellol (rose like) ; decanol; dihydrocarveol (spicy, peppery); tetrahydrogeraniol or 3,7- dimethyl-l-octanol (rose odor) ; eugenol (clove) ; and, p-mentha- l,8dien-7-0 or perillyl alcohol (floral-pine).
  • any of the flavorants when they are incorporated into the liquid system, may be in the form of a precursor or derivative of the flavorant which can be converted or activated to perform its flavorant function at a later time, and the term flavorant should therefore be understood to include such precursors or derivatives.
  • the flavorant may be converted or activated prior to or during the reaction herein, during use of a composition containing the reaction product or over a period of time that such a composition is in use.
  • the useful flavors include flavor acetals and flavor ketals which are converted by hydrolysis during use to corresponding alcoholic, aldehydic or ketonic flavor compounds as illustrated in United States Patents No.
  • the flavorant in its pure state may for example be a solid or a liquid under standard conditions of temperature (20°C) and pressure (1 standard atmosphere) .
  • Solid materials should be convertible to liquid form, such as by melting or dissolving in a solvent.
  • Liquid flavorants are particularly preferred for use in the invention.
  • the reaction employed herein is one which includes reaction of molecules of mer with other mer molecules and/or with other material present in the liquid system.
  • the flavorant may or may not participate chemically in the reaction, but it does participate in the reaction at least in the physical sense of becoming intimately distributed among or in the mer and/or mer molecules as the reaction proceeds.
  • a synthetic or natural mer that is a monomer, prepolymer and/or polymer (including mixtures of the foregoing)
  • a liquid system comprising a flavorant (including mixtures thereof)
  • the suitable mers are those which are capable of undergoing (with the aid of catalysts, promoters and/or other additives as required) significant increases in molecular weight in a liquid system comprising a selected flavorant.
  • the liquid system may, for example, be a flavorant which is itself a liquid, or the flavorant may be distributed in a liquid, such as by solution.
  • the mer is reacted while dissolved in the liquid system, for example in the flavorant itself.
  • the mer can be a single material, such as a polyhydroxy polymer that complexes with the flavorant or a monomer which forms a homopolymer.
  • the singular term "mer" also refers to combinations of materials which perform the mer function.
  • a mer may be composed of a blend of two materials that are each individually reactive, i.e., they will each react in the desired manner without the other, but the blend is useful for one or more reasons, such as contributing a particularly desired combination of physical and/or chemical properties to the resultant product.
  • the mer may involve a combination of two or more dependent reactants, such as a monomer and co-monomer which react by copolymerization.
  • Other applicable combinations include a polymer and an accompanying organic or inorganic cross -linker, coupler or coagulant.
  • mers which may be selected for use in the invention may be either natural or synthetic substances and include, without limitation, polyhydroxy compounds, acrylic resins, amides, and alkenyl aromatic monomers.
  • polyhydroxy compounds which are preferred mers, include, without limitation, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, algin, agar, chitin derivatives, dextrose, cyclodextrin, cellulose and its derivatives and starch and its derivatives.
  • Typical of the cellulose derivatives are methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellose, and carbomethyl cellose.
  • Typical starch derivatives are amylose, amylopectin, glycogen, methyl starch and hydroxyethyl starch.
  • Examples of monomers of the acrylic resin type include, without limitation, the hydroxy lower alkyl acrylates and hydroxy lower alkyl methacrylates such as 2-hydroxyethyl acrylate, 2- hydroxy-propyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethylene methacrylate, diethylene glycol onomethacrylate, 2-hydroxypropyl methacrylate, 3-hydroxy-propyl methacrylate and dipropylene glycol monomethacrylate.
  • the hydroxy lower alkyl acrylates and hydroxy lower alkyl methacrylates such as 2-hydroxyethyl acrylate, 2- hydroxy-propyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethylene methacrylate, diethylene glycol onomethacrylate, 2-hydroxypropyl methacrylate, 3-hydroxy-propyl methacrylate and dipropylene glycol monomethacrylate.
  • Cross-linking agents which may be used with the hydroxy lower alkyl acrylates and hydroxy lower alkyl methacrylates include without limitation ethylene glycol diacrylate, propyleneglycol diacrylate, ethylene glycol dimethacrylate, 1,2- butylene dimethacrylate, 1-3-butylene dimethacrylate, 1,4- butylene dimethacrylate, and propylene glycol dimethacrylate.
  • Example of amides which may be used include acrylamide, n- methylacrylamide, n-isopropyl ethacrylamide, n-methyl methacrylamide, n-12-hydroxyethyl acrylamide and n-(2- hydroxyethyl methacrylamide) .
  • Various cross-linkers may be used with the polyamides, such as N,N methylene-bis-acrylamide, various persulfates and others.
  • the acrylamides may also be cross-linked by irradiation with UV light.
  • alkenyl aromatic monomers examples include styrene, o-, m- and p-methylstyrene , ethyl sytrene, o-chlorostyrene, vinylbenxyl chloride and p-tert-butyl styrene.
  • Examples of additional useful mers include 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, vinylidene chloride acrylonitrile, vinyl acetate, divinyl benzene, butadiene, chloroprene, isoprene, itaconic acid, acrylonitrile, and acrylamides.
  • Example of useful copolymers include, without limitation aromatic diisocyanates together with mono- or dialkanolamines .
  • Typical diisocyanates include 2 , 6-toluenediisocyanate, 4,4- diphenyldiisocyanate, and diphenylmethane diisocyanate.
  • useful alkanolamines for copolymerization with the diisocyanates include monoethanolamine, monoisopropanolamine, and cyclohexylethanolamine.
  • Particularly preferred mers include the polymers described as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, vinyl a ine copolymer, algin, agar, chitin, dextrans, cyclodextrins (cyclodextrin compounds, especially ⁇ - cyclodextrin) , and cellulose, including the monomers and the derivatives of all of the foregoing.
  • Other suitable mers may also be employed.
  • the most preferred mers at present are polyvinylpyrrolidone, alginates and chitosan, but j3-cyclodextrin is also believed to be of substantial interest.
  • Polyvinylpyrrolidone, its chemical and physical propertied and its methods of manufacture and uses are described in Chapter 21 of the "Handbook of Water-Soluble Gums and Resins" by Robert L. Davidson, copyright 1980 by McGraw-Hall, Inc. , which is incorporated herein by reference.
  • the mer currently considered best is polyvinylpyrrolidine. While the use of polyvinylpyrrolidone and its derivatives with average molecular weights in the range of about 5,000 to about 1,000,000 is contemplated, including quaternized polyvinylpyrrolidone with average molecular weights in the range of about 50,000 to about 1,000,000, best results have been obtained to date with an unmodified polyvinylpyrrolidone having an average molecular weight in the range of about 5,000 to about 200,000, and more preferably in the range of about 7,000 to about 160,000 with an average molecular weight of about 10,000 having produced the best results.
  • liquid system constitutes a substantially homogeneous liquid mixture of liquid, and in certain circumstances non-liquid, components.
  • the mer and flavorant which are liquid components of this mixture, are present in forms which are substantially compatible and preferably substantially miscible with one another, most preferably constituting substantially a single phase as distinguished from an emulsion or mere mechanical dispersion. More particularly, it is preferable that the mer and flavorant constitute a solution, which in the present invention includes sols and true solutions.
  • a portion including preferably the bulk or major weight portion of the mer may be dissolved to the point of disappearance into the liquid system while a minor portion thereof may be in microscopically observable colloidal "solution" or suspension.
  • liquid flavorants e.g. , essential oils are preferred, and it is most preferred that the mer be dissolved in the flavorant in the liquid system.
  • a liquid system which is usually but not necessarily a solvent solution of the flavorant.
  • the flavorant may be introduced into a solvent solution of the mer.
  • solvent-based liquid systems are preferably based in solvent (including solvent mixtures) that is a co-solvent for mer and flavorant and which may be polar or non- polar, aqueous or hydrophobic, organic or inorganic, using stirring and solubility aids as necessary.
  • the present invention makes possible the production of controlled release flavorant concentrated which exhibit a high degree of uniformity from batch to batch and are, therefore, usable as intermediates, dependable blending components, for production of end products having lower overall concentrations of flavorant.
  • the flavorant is present at a high weight concentration as compared to normal average concentrations in the end products, For example, in many food and beverage products, flavor essential oils are present on concentrations typically below about 1% or even below 0.1% by weight.
  • olfactant and polymer have been used to impart a final olfactant/litter substrate ratio (solvent free basis) of about
  • the weight percentage of flavorant in the liquid system is generally substantially above 5% typically about 10% or more and most preferably about 20% or more, with about 50% or more where possible and the use of uncut essential oils being considered best. Also, it is preferred that the weight of flavorant
  • solvent free basis exceed the weight of mer (solvent free basis) included in the liquid system; for example flavorant to mer weight ratios (solvent free basis) of about 1.05 or more, typically about 1.3 or more and frequently about 1.5 or about 2 or more are contemplated.
  • flavorant to mer weight ratios solvent free basis
  • flavorant and mer are essential ingredients of the liquid system, it may contain other ingredients, including components which are and are not chemically active in the reaction or final product. Included are additives which catalyze or promote polymerization and/or plasticize the resultant product, such as glycerol, carboxymethylcellulose, diethyl phthalate, sorbitol, tannic acid, persulfates, multivalent (preferably divalent) metal salts such as calcium, barium, aluminum, iron and the like, polyphosphates and other materials with similar utilities, as well as solvents, agents for adjusting or otherwise controlling the particle size of the reaction product, surfactants, bentonite, PEG, carbopols and other modifiers and additives.
  • additives which catalyze or promote polymerization and/or plasticize the resultant product, such as glycerol, carboxymethylcellulose, diethyl phthalate, sorbitol, tannic acid, persulfates, multivalent (preferably divalent) metal salts such
  • the final product is intended for pharmaceutical use, or for ingestion as a foodstuff, or for use in a product constituting an indirect food additive, it may be necessary or desirable to use only ingredients which are USP listed or have GRAS status, and it is an advantage of the invention that it can be readily performed with such ingredients, whereby the products will be useful in the pharmaceutical, cosmetic and food industries.
  • the liquid system should be pourable at specified temperatures and pressures.
  • the herein described reaction can be conducted at temperatures of about 60°C or less, and the liquid system should therefore constitute a pourable liquid at temperatures of about 60°C or below, more preferably about 50°C or below, and still more preferably at about 40°C or below.
  • those liquid systems which are pourable at about room temperature e.g. , 20°C are particularly preferred.
  • the foregoing temperatures are assumed to correspond with standard atmospheric pressure or with the vapor pressure of the liquid system, whichever is greater.
  • the liquid system should be formulated for stability. More specifically, the liquid system should be stable, in the face of the reaction, the foregoing temperatures and such agitation as may be necessary, against coagulation, stratification and such other forms of undesired deterioration as may seriously interfere with performance of the process.
  • the identities of the materials and the relative proportions can both be selected in the foregoing manner and will be governed in par by the intended end-use of the product, with due regard as to whether it must be soluble or insoluble in a given solvent, whether it must be biologically safe, whether it will be a final product or an intermediate of another process or product, whether product life is a consideration, whether the volatility of the final product is important and to what degree, and whether the flavorant includes a fragrance whose scent must be faithfully reproduced in the final product.
  • the mer and other non-fragrance materials are preferably selected to be substantially odor-free when reacted, and preferably also when in their unreacted state.
  • solid material In the preparation of the liquid system, where one or more of its components is (are) solid material(s), it may be of assistance to grind either or both of them to a fine particle size before attempting to form the above described homogeneous mixture.
  • solid mer may be ground before being dissolved in liquid flavorant.
  • Solid flavorant may be ground before being mixed with liquid mer.
  • Solid mer and flavorant may both be ground to fine particle size and either premised dry for simultaneous solution in a co-solvent or may be dissolved sequentially. Sequential solution with the mer being added to liquid flavorant or flavorant solution is preferred and where possible it is preferred that the mer be dissolved directly in substantially undiluted flavorant.
  • the reaction contemplated by the present invention is a reaction of mer in the presence of flavorant with participation of the flavorant either chemically or at least in the sense of becoming intimately distributed among or in the mer and/or resultant polymer molecules as the reaction proceeds, including a significant increase in the molecular weight of the mer.
  • the reaction may be any chemical change which results in a significant increase in the molecular weight of the mer accompanied by a substantial reduction in the diffusion rate, volatility, flammability, toxicity or susceptibility to oxidation or other form of environmental attack, on the part of the flavorant.
  • the contemplated reactions are:
  • Polymerization - forming chain-like (including branched) macro-molecules which are the result of combining many small molecules (i.e., monomers), including homo- and co-polymerization.
  • Crosslinking - forming inter-connected macro-molecular chains which are the result of: opening bonds (which may include opening rings) along and intermediate the ends of adjacent chains of 2 (or more) similar or dissimilar macro-molecules and connecting those bonds with one another- to connect the chains together. Opening bonds (which may include opening rings) along and intermediate the ends of adjacent chains of 2 (or more) similar or dissimilar macro-molecules and connecting those bonds through the residue of a different molecule of low, medium or high molecular weight acting as a cross-linking agent, forming ionic bonds along and intermediate the ends of adjacent chains of two or more similar or dissimilar macro-molecules; see C.F.
  • the significant molecular weight increase employed in the present invention is in general an increase which sufficiently provides or enhances at least one beneficial characteristic of the flavorant and/or its performance in its end-use (s) to have practical application(s) .
  • beneficial characteristics are set forth herein in the discussions of advantages and uses of the invention under the headings Summary of the Invention and Industrial Applicability. It appears that increases in the molecular weight of the mer which are very small in numerical terms can be useful for particular flavorant applications, such as about one, two, three or five percent of more, ranging upwards to about fifty percent or more, based on the molecular weight of the mer prior to the reaction.
  • the molecular weight increase may appear significant or insignificant in purely mathematical terms, but should be significant in terms of its effect (s) on one or more characteristics of the flavorant and/or its performance.
  • the course of the reaction and the nature of the reaction product can be controlled by making appropriate selections of proportions of mer and flavorant in the liquid system.
  • the concentration of mer in the liquid system can be up to about the maximum amount of mer that is soluble in the liquid system or in the flavorant, but lesser amounts are preferred.
  • relatively low mer concentrations may be preferred for certain applications, especially in the manufacture of long lasting medicaments, perfumes and similar personal care products in which an excessive amount of reacted mer might introduce excessive tackiness into the resultant reaction product, leading to an unpleasant "feel" when the reaction product is used as perfume. It has been found for instance that a concentration of about 0.1 to about 2 percent by weight of mer based on the weight of mer plus flavorant is quite adequate and effective for such applications.
  • One convenient measure of relative proportions of reacted mer and fragrance in the reaction product in liquid, gel-type and paste-like compositions is the ratio of the weight of polymer, in grams, to the volume of the essential oil (uncut basis) in milliliters, expressed as a percentage.
  • Useful products may for example be prepared in the range of about two or three to about eighty percent, and more preferably about eight to about thirty percent, with about fifteen percent being best for producing gels for encapsulation.
  • the polymer to fragrance ratio may thus be varied to select the desired physical form and longevity of the fragrance.
  • a convenient measure of relative proportions of reacted mer and medicament in the reaction product in liquid, gel-type and paste-like compositions is the ratio of the weight of the medicament to the weight of polymer (solvent-free basis) expressed as a percentage.
  • Useful products may for example be prepared in the range of about two or three to about eighty percent, and more preferably about eight to about thirty percent, with about fifteen percent being best for producing gels for encapsulation.
  • the polymer to medicament ratio may thus be varied to select the desired physical form and longevity of the medicament.
  • One convenient measure of relative proportions of mer and flavor in the reaction product in liquid, gel-type and paste-like compositions is the ratio of the volume of the essential oil(s) (uncut basis) , in milliliters, to the weight of polymer, in grams, expressed as a percentage.
  • Useful products may for example be prepared in the range of about 0.05 or 0.5 to about 80%, and more preferably about 0.1 to about 5%, with about 0.5% being best for producing gels for edible strips.
  • the polymer to flavor ratio may thus be varied to select the desired physical form and longevity of the fragrance.
  • reaction may be commenced merely by combining and mixing the ingredients.
  • initiators, catalysts, promoters and other reaction aids can be useful in practicing the invention. It has been found that the order of addition of such reaction aids can be varied.
  • modifiers, reaction aids and other additives are added to a mixture formed by mixing the mer thoroughly and very uniformly with the flavorant, preferably for a few or even many hours. See the examples set out below.
  • the afore-mentioned mixture can also be added to the catalyst, such as to a liquid system containing the catalyst in solution.
  • plasticizers are used, they can be added slowly with constant stirring to the afore-mentioned mixture. In certain instances, addition of plasticizer will initiate or at least promote polymerization. Generally, agitation is continued during the reaction until the desired final product is obtained. However, agitation sufficiently vigorous to emulsify the contents of the liquid system should be avoided.
  • the reaction will proceed readily with extended stirring at room temperature.
  • the process clearly is not limited to room temperature operations, it is a particular advantage of the invention that it can be performed at room temperature and at temperatures of about 60°C or less, preferably about 50°C or less and still more preferably about 40°C or less, thereby permitting the use of temperature sensitive materials, including fragrances and other flavorants which are temperature sensitive, in the product.
  • the flavorant may be desirable to provide it with partial or complete protection from atmospheric, air, such as by using a sealed reactor or mixing under vacuum or an inert atmosphere.
  • Superatmospheric pressure or vacuum may also be employed to control particle size in those circumstances where the reaction is conducted to produce a particulate product.
  • the process is not limited to substantially neutral conditions, e.g., a pH of about 6 to about 8 or about 6.5 to about 7.5, it is an advantage of the invention that at least certain of its embodiments can be carried out within one or both of these ranges, thus making it possible to readily entrap pH sensitive materials in the resultant reaction product.
  • the process can be conducted in such a manner that it is compatible with biologically sensitive materials, and such materials can be incorporated into various forms of reaction product.
  • biological materials it may be necessary to take precautions to protect such materials from contamination and degradation.
  • the progress of the reaction may be monitored in any suitable manner.
  • viscosity and/or preferably specific gravity measurements can be used.
  • increasing viscosity and/or specific gravity signifies increasing molecular weight of the mer in the liquid system.
  • the minimum acceptable proportion of mer to flavorant and the minimum acceptable extent of reaction for any mer/flavorant combination will be that proportion and that extent of reaction which are sufficient to cause the reaction to proceed and to cause a substantial reduction in the diffusion rate, or volatility, or flammability, or toxicity or susceptibility to oxidation or other form of environmental attack, upon the flavorant.
  • Persons skilled in the art can ascertain appropriate proportions and minimum extent of reaction for the potentially useful mer/flavorant combinations with the aid of simple experiments guided by the discussion which follows.
  • the quantity of mer and extent of reaction should be sufficient to provide in the resultant reaction product an average molecular wight of about 1,000 or more.
  • some of the lower molecular weight cyclodextrins have an average molecular weight of about 1,000. More commonly, the reaction product will have an average molecular weight of about 2,000 or more.
  • "high" polymers meaning macro-molecules having an average molecular weight of about 5,000 or about 6,000, such as for instance cellulosic polymers. Algin has been described as a natural high polymer.
  • reaction products having an average molecular weight of about 7,000 or more for example those based on polyvinylpyrrolidone, the polyvinylpyrrolidone/flavorant reaction product that is presently most preferred having an average molecular weight above about 10,000.
  • the reaction may be terminated while the liquid system is still substantially liquid or when it has progressed to a non-shape retaining soft gel, i.e., a gel which when formed into a 2 inch unreinforced and unsupported homogenous cube, does not spread more than 20% linearly in any dimension upon standing for 8 hours at about standard atmospheric pressure at 20°C.
  • a relative humidity of 50% is assumed.
  • reaction products thus formed are useful as ingredients in controlled release compositions in which the flavorant is used for performing a flavorant function in a host medium outside the reaction product.
  • the flavorant may constitute either the main active ingredient or an auxiliary component of the composition.
  • utilization of the reaction product in such compositions will tend to stabilize the flavorant and/or enhance its effect in one or more of the ways described below and/or change the properties of the flavorant in a way that makes it more useful.
  • reaction product will be found to reduce the differential diffusion of component parts of flavorants containing multiple components. This can be useful in lengthening the shelf life of the composition by preserving the entire composition for a longer period of time.
  • compositions containing flavorants which do not have components which exhibit differential diffusion tendencies incorporation of the reaction product in the composition will be found to reduce the overall diffusion rate of the flavorant as compared to otherwise similar compositions containing the unreacted flavorant.
  • shelf life can be increased and absorption of the product into packaging can also be reduced.
  • a reduction in overall diffusion rate can also impart more longevity to the composition while it is in use.
  • An additional potential benefit is reducing wastage of the flavorant, enabling its diffusion rate to be matched to the need for the flavorant in the host medium into which it is released.
  • compositions are a bread or cookie dough and the flavorant is a flavor to be incorporated in such dough prior to baking, substituting a er/flavor reaction product can retard chemical change in the flavor during baking.
  • the composition is a packaging material and the flavorant is a olfactant
  • formation of a mer/olfactant reaction product and incorporation of that product into the packaging material can reduce the tendency for chemical change in the olfactant during hot processing of the packaging material.
  • formation of the reaction product can slow or stop environmental attack upon the flavorant by oxygen, water vapor, carbon dioxide, carbon monoxide, nitrogen and other environmental factors.
  • the advantage of enhancement of flavorant effect follows from the manner in which formation of the reaction product affects diffusion of the flavorant. Because of this stabilization, the same amount of flavorant can be made more potent (available in a higher concentration) at a given time interval after initial application of the composition. This can in turn lead to the further benefit that fewer applications of the composition may be required.
  • formation of the reaction product can make the flavorant more useful in controlled release compositions, such as by making the flavorant available in altered forms.
  • Potential physical improvements include increased viscosity, changing normally liquid materials into solids, increasing the iscibility of flavorants with other ingredients of controlled release compositions, increasing the gloss and moldability of the flavorant or increasing its resilience.
  • Potential chemical changes which can be affected by converting the flavorant to a mer/flavorant reaction product include reducing the reactivity or toxicity of the flavorant. In other cases side effects can be controlled.
  • the product recovered from the above-described reaction may be ready for use, i.e., may be used in exactly the same form in which it is recovered from the reaction.
  • many of the uses of the reaction product will involve its further modification prior to use, including changes in physical form, combining the reaction product with other materials, encapsulation and application to various substrates.
  • the viscosity of liquid reaction products may be adjusted to higher or lower levels and they may be converted into gels or incorporated, such as by absorption, into solid products.
  • liquid or gel type products may be dispersed or emulsified in compatible and incompatible liquids. Gels may be converted to solids or liquids and solids may be converted to gels or liquids by heating and/or solvent action.
  • the reaction products may be treated, as necessary or desirable, with appropriate coupling or cross-linking agents, which may be applied for example during or subsequent to the reaction of the present invention.
  • appropriate coupling or cross-linking agents for example, certain types of irradiation will cause polyvinylpyrrolidone to cross-link with itself.
  • suitable reagents include multivalent (preferably divalent) metal salts such as calcium, barium, aluminum, iron and the like.
  • Exemplary reagents for chitosan are polyphosphates and others described by Varlop et al, supra.
  • a biopolymer such as alginate or chitosan
  • the resultant reaction product can then be formed into droplets in a suitable solution containing the coupling or cross-linking reagent. This may be accomplished by means as simple as dropping the flavorant/mer solution dropwise into the reagent solution or by mechanically projecting droplets beneath the surface of the reagent solution.
  • the final product can, for example, be resilient, hydrated gel-beads whose particle size may be varied by controlling the size of the droplets of flavorant/mer solution initially formed in the ionic solution.
  • reaction product With regard to combining the reaction product with other materials, they may be incorporated into carriers which may comprise active materials or may consist or consist essentially of physiologically inert materials. Gaseous, liquid and solid diluents, as well as propellants and/or preservatives may also be mixed with the reaction products. Prior to or during their incorporation into controlled release compositions, the reaction products of the present invention may be further reacted with other materials.
  • reaction products are their application to substrates prior to or during release of the flavorant into the host medium in which it is intended to perform.
  • the mode of application may comprise coating, including coating on the surface or absorption into the interior of the substrate.
  • porous and non-porous as well as permeable and non-permeable substrates are contemplated.
  • living substrates are animate (animal, insect, reptile, marine or human) and plant life substrates.
  • the reaction product or compositions containing the same may for example be applied to hair, skin, nails and internal parts.
  • the reaction products and compositions thereof may be applied to leaves, stems, fruits, vegetables, roots, seeds and the like.
  • inanimate substrates There are so many potential inanimate substrates that a complete listing herein would be impractical.
  • a number of applicable categories of inanimate substrates include large surfaces, such as the floors and walls of buildings and the surfaces of machinery and equipment, the surfaces of particular solids, both organic and inorganic, and the surfaces and interstices of fibrous webs.
  • gel-beads are only one of a wide variety of physical forms in which useful reaction product may be manufactured.
  • Liquid and paste-like reaction products which may or may not be in bead form can be useful for spreading on (including into) paper, cloth and other substrates and can, for example, be employed in the manufacture of the above- mentioned scented papers, scented clothing and other products.
  • Other examples of applicable categories of substrates are non- fibrous webs, including polymeric films and metal sheeting.
  • a particularly useful form of substrate is the edible web which can be used to make valuable articles when coated with reaction products (encapsulated or non-encapsulated) of a mer which includes flavor, food or medicament. Since these coated webs are intended for oral ingestion or for preparing other materials for oral ingestion, they should be composed of hygienic materials and kept sanitary. Applicable edible webs include those of paper, cardboard, polymeric films and other forms.
  • Some examples of the applicable chemical species for making these webs include for example, natural and chemically modified starches as, for example, dextrin, dextran, amylose, and amylose cross-linked with a polyol or polypeptide; cellulose derivaties such as sodium carboxymethylcellulose , hydroxypropylmethylcellulose, hydroxyethylcellulose and the like; animal proteins such as collagen and gelatin; vegetable proteins such as corn, wheat, peanut and bean proteins; and other polysaccharides such as pectin, acacia, xanthan gum, guar gum, algin and the like; and synthetics such as polyvinylpyrrolidone, polyvinyl alcohol and the like.
  • natural and chemically modified starches as, for example, dextrin, dextran, amylose, and amylose cross-linked with a polyol or polypeptide
  • cellulose derivaties such as sodium carboxymethylcellulose , hydroxypropylmethylcellulose, hydroxyethylcellulose and the like
  • a basic characteristic of these edible webs is that they will readily disintegrate and preferably also dissolve in aqueous fluids, for example water, beverages, saliva and gastrointestinal fluids, including those of the stomach or intestines.
  • Certain of these edible web products may also contain a binder which should preferably also readily disintegrate or preferably also dissolve in the above-described fluids.
  • Such binder may for example be used in forming multiple layers of the edible web material, adhering protective material to the webs, and where applicable, securing to the web microcapsules containing reaction product of mer with food, flavor and/or medicament.
  • the binder should be physiologically acceptable, meaning that it is physiologically inert or therapeutic or at least free of effects which would bar any necessary government approval for its use.
  • the coatings applied to these edible webs are preferably stable and distributed substantially uniformly over the surface of the web.
  • reaction product of the invention includes complexes of olfactants in personal care products, other primarily odor emitting products, flavor substances, packaging materials, other shaped objects of polymeric material, candy and chewing gum, cleansing agents, pesticides, repeHants, medicaments and advertising samplers containing any of the foregoing.
  • Mer/flavor reaction products may for example be used in beverages, foods, cigarette/cigar, papers/wrappers, tobacco and medicaments.
  • Illustrative beverages include soft drinks, coffee or tea and alcoholic beverages.
  • In candy and related products mer/flavor reaction products may for example provide the flavoring for chewing gum, cough drops and breath mints.
  • the invention can be used to make separate mer/flavor reaction products of two different flavors which can then be separately polymer inclusioned and then mingled in a coating on an edible strip.
  • One example would be peanut butter and jelly flavor.
  • Reaction products of mer and flavor are also useful in rendering medicaments more palatable, either by incorporation mer/flavor reaction product directly in a medicament composition, such as in a menthol inhaler or by incorporating the reaction product in an edible surrounding member for the medicament.
  • a medicament composition such as in a menthol inhaler
  • An example would be a flavored aspirin pill having an aspirin core surrounded by an edible strip impregnated with the reaction product of mer and chocolate flavor.
  • Another example would be a flavored capsule prepared from an otherwise conventional capsule formulation into which a reaction product of mer and flavor had been introduced prior to actual formation of the capsule wall.
  • mer/flavorant reaction products in packaging materials, including such flavorants as olfactants, bacteriostats and the like.
  • a mer/olfactant reaction product may be applied to a product container or its label either on surface or within a web forming the label or within a wall defining the container.
  • the controlled release properties of the reaction product may for example perform one or more of the stabilizing functions described above.
  • Reaction products of mers and flavorants in accordance with the invention also have application to other shaped objects of polymeric material, including both resinous and elastomeric materials.
  • mer/flavor reaction products may be applied to or incorporated within the surfaces of toys, edible book pages, baby pacifiers, baby bottle nipples, dental bridgework supports and athletic mouthpieces.
  • Mer/olfactant reaction products can be applied to or molded into hair brushes, combs and other products.
  • Reaction products of mer and flavorant may be formed with the main and/or auxiliary ingredients of the various cleaning agents, including detergents, sanitizing agents, solvents, waxes and the like.
  • compositions of cleansing agents may contain reaction products of mers with olfactants or sanitizing agents.
  • the invention meets several requirements, including suitable mechanical properties and biodegradation kinetics, tissue compatibility, drug compatibility, drug permeability and ease of processing.
  • the invention can be used with or without a water soluble strip which holds the reaction products of mer and biologically active substances.
  • the reaction products are, depending on the needs, fully soluble in the liquids of the body, but without swelling therein, and dissolve slowly, to provide an extended period of action for a given drug in some special dosage form.
  • Reaction products in liquid or gel form including those which have and have not been substrate that is edible and that is intended to be eaten or at least partly ingested orally by a prospective customer.
  • the edible substrate could carry or include a reaction product of mer and food, flavor, beverage, medicament or the like which was connected with advertising material and intended to be eaten or chewed by the prospective customer.
  • the reaction product could be coated as a dissolvable layer upon an edible or non-edible substrate, including insoluble substrates, and could be swished about in a liquid to form a drink containing flavor or medicament which the prospective customer could swallow.
  • Associated advertising material could be printed upon the substrate itself or upon a flyer or brochure packed in a container with the substrate, or upon a protective outer member for the substrate.
  • reaction products of the present invention are but one example of many types of controlled-release means which can be utilized for controlling release of the flavor.
  • any presently existing or future controlled release means may be applied to these strips and samplers.
  • the sampling layers containing the reaction product are applied to a "continuous" travelling web by printing or draw down techniques using a draw down bar, doctor blade or the like or any other suitable technique. Webs printed in this manner can then be cut to the appropriate size for the sampler and, if desired, combined with a suitable protective covering.
  • a protective covering can be any device which has sufficient structural integrity to withstand normal handling of the advertising sampler during production, shipment and distribution to the prospective customer and will at least partially enclose or fully surround the portion of the sampler containing the reaction product.
  • Partial enclosures assist in preventing premature mechanical rubbing of sample layers and particularly microcapsules while also excluding dirt. Examples of such partial enclosure include self-folds formed in substrates and a cellophane or polymeric film flap covering one or both major surfaces of a sampler substrate.
  • a fully surrounding protective covering provides and opportunity to exclude bacteria and further reduce the opportunity for oxygen, moisture and other environmental factors to attack the reaction product. Examples of fully surrounding protective coverings include substrates confined between impermeable protective layers having full edge seals, sealed envelopes and the like.
  • the substrate bearing the sample is typically connected with graphic material, including print, art work and pictures, advertising the sampled product.
  • the appropriate connection may be direct, i.e., a connection of the graphic material and sample through the substrate which bears the sample. Examples include samplers where the sample and graphic material are on the same web or on webs which are attached to each other.
  • the connection may be provided by having the graphic material and sample within one or more envelopes, such as by placing both within a common envelope.
  • two-envelope systems are also applicable in which a first envelope encloses the sample while a second envelope encloses the first envelope and the graphic material.

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Abstract

L'invention concerne la modification d'aromatisants par réaction de mères en présence d'aromatisants en vue de la formation de produits ayant un poids moléculaire considérablement élevé.
PCT/US1998/014116 1997-07-08 1998-07-08 Procede de renforcement du parfum WO1999002046A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU86577/98A AU8657798A (en) 1997-07-08 1998-07-08 Flavor enhancement process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US88972397A 1997-07-08 1997-07-08
US08/889,723 1997-07-08

Publications (1)

Publication Number Publication Date
WO1999002046A1 true WO1999002046A1 (fr) 1999-01-21

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CN109925983B (zh) * 2019-03-08 2021-12-28 紫罗兰家纺科技股份有限公司 基于乳木果油的双层微胶囊及其整理到纺织面料中的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998974A (en) * 1972-10-25 1976-12-21 Dynapol Corporation Comestibles containing non-nutritive flavoring
US4285983A (en) * 1979-05-02 1981-08-25 Norda, Incorporated Fixing volatile flavoring agent in starch hydrolysate
US4423030A (en) * 1981-05-13 1983-12-27 Colgate-Palmolive Company Flavored aqueous oral composition
US4448789A (en) * 1982-08-27 1984-05-15 Warner-Lambert Company Enhanced flavor-releasing agent
US4906488A (en) * 1987-05-01 1990-03-06 Arcade, Inc. Modification of permeant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998974A (en) * 1972-10-25 1976-12-21 Dynapol Corporation Comestibles containing non-nutritive flavoring
US4285983A (en) * 1979-05-02 1981-08-25 Norda, Incorporated Fixing volatile flavoring agent in starch hydrolysate
US4423030A (en) * 1981-05-13 1983-12-27 Colgate-Palmolive Company Flavored aqueous oral composition
US4448789A (en) * 1982-08-27 1984-05-15 Warner-Lambert Company Enhanced flavor-releasing agent
US4906488A (en) * 1987-05-01 1990-03-06 Arcade, Inc. Modification of permeant

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