RU2700697C1 - Hair fixers including poly-glucose polymers based on starch esters - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: group of inventions relates to hair care. Hair fixation composition includes at least one polyglycosic polymer based on carboxylated starch esters, which is soluble in an alcohol-based solvent system, obtained by reacting at least one starch ester with at least two cyclic anhydrides, with the following structure (I):(I),in which R=H, Ror R,or a combination thereof, wherein at least one R is Rand where Ris: -CO-R, where Ris C-C-alkyl group; and Ris: a) -CO-CH-CH (R) -COOH, where R=H or C-Can alkenyl group, or b) -CO-CH=CH-COOH; or c) -CO-CH-C (= CH) -COOH; or d) -CO-CH-COOH, or e) -CO-CH-COOH; and where n = 10–500; solvent system based on alcohols, including at least one C-C-linear alcohol, C-C-trimethyl alcohol or mixture thereof in amount of 15 wt. %; and at least one cosmetically acceptable additive. Also disclosed is a method of producing the composition and use of a polyglucose polymer based on carboxylated starch esters as a hair fixing polymer.EFFECT: group of inventions provides excellent fixation of wave in high humidity conditions.15 cl, 9 tbl, 5 ex

Description

FIELD OF THE INVENTION

The invention relates to personal care compositions comprising polyglucose polymers based on carboxylated starch esters. More specifically, the invention relates to compositions for fixing hair, including polyglucose polymers based on carboxylated starch esters, which are soluble in alcohol-based solvent systems.

BACKGROUND OF THE INVENTION

The polymers used for personal care applications, such as hair styling and hair fixation, have traditionally been made using synthetic materials. For polymers to be suitable for such personal care applications, they must be soluble in alcohol-based systems and, in the case of aerosol-based hair sprays, they must also be compatible with the propellant. Conventional synthetic polymers are usually inexpensive and provide acceptable quality; however, since they are not made from renewable sources, they cannot be provided on a long-term basis. In addition, it is not easy to reproduce the cost and quality of synthetic polymers.

Therefore, there is a need for self care polymers made from renewable sources that provide the same or better quality at comparable costs than their synthetic alternatives, and which are soluble in alcohol based systems such as ethanol based systems, and optionally, compatible with propellants such as dimethyl ether.

SUMMARY OF THE INVENTION

According to an aspect, the present invention relates to a composition for fixing hair, comprising at least one polyglucose polymer based on carboxylated starch esters; an alcohol-based solvent system and a cosmetically acceptable additive. A polyglucose polymer is prepared by reacting at least one starch ester with an anhydride such as cyclic anhydride or acyclic anhydride, or mixtures thereof, and the polyglucose polymer is soluble in an alcohol-based solvent system. Starch ester can be prepared by reacting starch with at least one acyclic anhydride, at least one cyclic anhydride, or mixtures thereof.

In another aspect, the present invention relates to a method for preparing a composition for fixing hair, comprising reacting at least one starch ester with an anhydride, such as cyclic anhydride or acyclic anhydride, or mixtures thereof, to form a polyglucose starch ester polymer. In a further step, the method comprises dissolving or suspending a polyglucose starch ester polymer in an alcohol based solvent system. Starch ester can be prepared by reacting starch with at least one acyclic anhydride, at least one cyclic anhydride, or mixtures thereof.

In yet another aspect, the present invention relates to a polymer based on carboxylated starch esters, as defined herein, as a hair fixing polymer in a hair fixing composition, and to a hair styling method comprising applying a polyglucose polymer based on carboxylated starch esters as defined above on the hair.

DETAILED DESCRIPTION OF THE INVENTION

As used here, expansions of numerical ranges by endpoints include all numbers within this range (e.g., 1-5 includes 1, 1,5, 2, 2,75, 3, 3,80, 4, 5, etc. .). In addition, it is understood that in embodiments encompassing ranges as indicated herein, corresponding lower extreme points and corresponding upper extreme points include combinations of different lower and upper extreme points. For example, for ranges 1-20 and 5-10, respectively, ranges also include, but are not limited to, 1-10 and 5-20.

The hair fixation compositions of the present invention include carboxylated starch ester polymers combining the characteristic features of having a polysaccharide backbone containing at least one attached ester group and at least one carboxyl functional group.

It has been found that polyglucose polymers based on carboxylated starch esters can provide hair-fixing polymers that are not only made from renewable sources, but can also provide equal or better hair styling quality characteristics, such as spray intensity, viscosity, stiffness and curl fixation at high humidity, in particular as polymers used in hair sprays, at comparable costs compared to their synthetic alternatives. The polymers of the invention are soluble in an alcohol-based system and, optionally, are also compatible with propellants used in hair styling products.

The present invention generally relates to compositions for fixing hair, comprising at least one polyglucose polymer based on carboxylated starch esters having the following structure (I):

I,

I

in which R = H, R _H or R _A, or combinations thereof, where at least one R is R _A and where R _H is: –CO – R ¹ , in which R ¹ is C ₁ - A C ₂₁ alkyl group, preferably a C ₁ -C ₁₀ alkyl group, and more preferably a C ₁ -C ₃ ; and R _A represents: (a) –CO – CH ₂ –CH (R ² ) –COOH, where R ² = H or C ₁ –C ₁₈ is an alkyl or alkenyl group, preferably a C ₆ –C ₁₈ alkenyl group and more preferably a C ₈ -, C ₁₂ - or C ₁₈ - alkenyl group; or b) –CO – CH = CH – COOH; or c) –CO – CH – C (= CH ₂ ) –COOH; or d) –CO — C ₆ H ₄ —COOH, or e) –CO — C ₆ H ₈ —COOH; and where n = 10-500, more preferably 30-400, and even more preferably 30-150. Hair fixation compositions further include an alcohol-based solvent system and a cosmetically acceptable additive, wherein the polyglucose polymer is soluble in an alcohol-based solvent system.

In the above formula (I), R _H represents hydrophobic groups and R _A represents groups containing acidic functionality and, optionally, hydrophobic functionality. In general, carboxylated starch ester polyglucose polymers are prepared by reacting a polysaccharide ester such as starch acetate, starch propionate, starch butyrate, starch acetate butyrate and starch acetate propionate with an anhydride such as cyclic anhydride or acyclic. In an embodiment, the anhydride may be substituted anhydride or unsubstituted anhydride. In a further embodiment, the anhydride is more preferably a substituted anhydride. Suitable for the preparation of a succinate derivative, a maleate derivative or an itaconate derivative, a phthalate derivative or a tetrahydrophthalate derivative or combinations thereof, anhydrides include, but are not limited to, such as succinic anhydride, alkenyl succinic anhydride, maleic anhydride, itaconic anhydride, anhydride, or

In an embodiment of the present invention, the polysaccharide ester can be modified with substituted anhydride in an amount of about 15 wt.% To 50 wt.% Based on the weight percent of the polysaccharide ester. In another embodiment, the polysaccharide ester can preferably be modified with substituted anhydride in an amount of from about 20 wt.% To 45 wt.% And in yet another embodiment, more preferably from about 25 wt.% To 35 wt.%.

Non-limiting examples of carboxylated starch ester polyglucose polymers of the invention include polymers of formula I, wherein R _H is: –CO – R ¹ , in which R ¹ is a C ₁ –C ₂₁ alkyl group, preferably a C ₁ -C ₁₀ an alkyl group and more preferably a C ₁ –C ₃ alkyl group; and R _A represents: (a) –CO – CH ₂ –CH (R ² ) –COOH, where R ² = H or C ₁ –C ₁₈ is an alkyl or alkenyl group, preferably a C ₆ –C ₁₈ alkenyl group and more preferably a C ₈ -, C ₁₂ - or C ₁₈ - alkenyl group; and where n = 10-500, more preferably 30-400, and even more preferably 30-150; wherein R _H represents: -CO-R ¹ wherein R ¹ represents a C ₁ -C ₂₂ -alkyl group, preferably C ₁ -C ₁₀ alkyl group and more preferably C ₁ -C ₃ alkyl group; and R _A is: b) –CO – CH = CH – COOH, where n = 10–500, more preferably 30–400, and even more preferably 30–150; R _H represents: –CO – R ¹ in which R ¹ represents a C ₁ –C ₂₂ alkyl group, preferably a C ₁ –C ₁₀ alkyl group and more preferably a C ₁ –C ₃ alkyl group; and R _A represents: c) –CO – CH – C (= CH ₂ ) –COOH, and where n = 10–500, more preferably 30–400, and even more preferably 30–150; where R _H represents: –CO – R ¹ in which R ¹ represents a C ₁ –C ₂₂ alkyl group, preferably a C ₁ –C ₁₀ alkyl group and more preferably a C ₁ –C ₃ alkyl group; and R _A is: d) –CO — C ₆ H ₄ —COOH, and where n = 10–500, more preferably 30–400, and even more preferably 30–150; where R _H represents: –CO – R ¹ in which R ¹ represents a C ₁ –C ₂₁ alkyl group, preferably a C ₁ -C ₁₀ alkyl group and more preferably a C ₁ –C ₃ alkyl group; and R _A is: e) –CO — C ₆ H ₈ —COOH, and where n = 10–500, more preferably 30–400, and even more preferably 30–150. Combinations of the above are also included in the embodiment. In an embodiment, polyglucose polymers suitable for use in the present invention include, but are not limited to, starch acetate succinate, stenyl succinate, starch acetate phthalate, and combinations thereof.

In an embodiment, the carboxylated starch ester polyglucose polymers of the present invention may be present in the hair fixation composition in an amount of about 1 weight percent to 10 weight percent based on the weight of the hair fixation composition. In another embodiment, polyglucose polymers are present in an amount of from about 2 weight percent to 8 weight percent. In yet another embodiment, polyglucose polymers are present in an amount of from about 3 weight percent to 6 weight percent.

In another aspect, the present invention relates to a polyglucose polymer obtained by reacting starch with an anhydride, which may be acyclic or cyclic, and then further reacting the reaction mixture with another anhydride, which may also be acyclic or cyclic, to form a polyglucose polymer. For example, in an embodiment, starch can be reacted with at least one acyclic anhydride to form a starch ester, which can be isolated or further reacted in situ , and subsequently the reaction mixture or isolated starch ester is further reacted with cyclic anhydride to form a polyglucose polymer.

In one embodiment of the present invention, the starch material, which is first reacted with an anhydride, where the anhydride may be acyclic or cyclic, is not a material containing starch ether and ester.

In one embodiment, the starch ester is preferably prepared by reacting starch with at least one acyclic anhydride, such as acetic, propionic or butyric anhydride, or mixtures thereof, to form starch acetate, starch propionate or starch butyrate and / or mixtures thereof . In another embodiment, the polyglucose polymer is prepared by reacting starch ester with a cyclic anhydride such as succinic anhydride, alkenyl succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride or tetrahydrophthalic anhydride and / or mixtures thereof.

The polyglucose polymers of the present invention are based on starch or starch derivatives. Starch polymers can be obtained from any source of starch, including but not limited to corn, banana, barley, amaranth, arrowroot, canna, sorghum, wheat, rice, tapioca, potato, sago, peas or sweet potato. In an embodiment, the starch is from a corn, potato, wheat, rice or tapioca source. In another embodiment, starch comes from a potato or corn source. Suitable starches and starch derivatives include, but are not limited to, saccharides or their derivatives. Suitable saccharides include, for example, oligosaccharides and polysaccharides (e.g. maltodextrins, corn syrups, pyrodextrins and starches) and their hydrogenated varieties, such as hydrogenated starch or hydrogenated hydrolyzed starch. In an embodiment of the invention, polyglucose polymers are prepared from maltodextrin, pyrodextrin, or low molecular weight starch or oxidized starch. It has been found that starch-based polyglucose polymers cannot be effective when the polyglucose polymer is insoluble in an alcohol-based solvent system. Thus, according to embodiments of the invention, the weight average molecular weight of the starch is preferably less than about 500,000. Starches having such typical molecular weights are soluble in water. In another embodiment, the weight average starch molecular weight (Mw) may be approximately less than 200,000. In yet another preferred embodiment, the weight average molecular weight of starch may be less than about 100,000. In yet another preferred embodiment, the weight average molecular weight of starch may be less than about 50,000. In one embodiment, the weight average molecular weight of starch is about 1,000 or more, in another embodiment, preferably about 5., preferably about 10,000 or more.

In yet another further embodiment, polyglucose polymers can be prepared from maltodextrins, pyrodextrins, and chemically modified variants of maltodextrins and pyrodextrins. In an embodiment, the polysaccharide is preferably maltodextrin with dextrose equivalence (DE) of less than about 25, in another embodiment, preferably about 20 or less, and in yet another embodiment, more preferably about 15 or less. In an embodiment, when the polysaccharide is maltodextrin, it may have an DE of about 1 or more, more preferably about 5 or more, and in yet another embodiment, about 10 or more. The term dextrose equivalence, as used herein, is a measure of the amount of reducing sugars present in a sugar product with respect to glucose, and is a well-known term in the art.

In an embodiment, the starches used as starting materials may also have a high amylose content. As used herein, the term “high amylose” is intended to include starch containing at least about 50%, in another embodiment, preferably at least about 70%, and in yet another embodiment, more preferably at least 80 mass% amylose. Amylose moieties of fractionated starches are also suitable.

In an embodiment, the starch ester polyglucose polymer has a total degree of substitution (D.S.) in the range of about 1.0 to 3.0. In another embodiment, the polyglucose polymer has a common D.S. in the range of from about 1.5 to 3.0, and in yet another embodiment, from about 2.0 to 2.9. The number of substituted hydroxyl groups on the anhydroglucose unit is expressed through the degree of substitution (D.S.).

Polyglucose polymers based on carboxylated starch esters can be used either as obtained from natural sources or chemically modified. Chemical modification involves hydrolysis by acids, enzymes, oxidizing agents or heating, hydrogenation, esterification or etherification.

In another aspect, compositions for fixing hair include at least one polyglucose polymer and an alcohol-based solvent system. As used herein, an alcohol-based solvent system includes at least one alcohol, and may further include optional components such as water, a propellant, or other non-alcoholic, non-aqueous solvents. The polyglucose polymer must be soluble in an alcohol-based solvent system. In an embodiment, the amount of alcohol present in the solvent system should be about 1 weight percent or more, in another embodiment, preferably about 15 weight percent or more, and in yet another embodiment, more preferably about 25 weight percent or more. In an embodiment, the amount of alcohol present in the solvent system should be about 99 weight percent or less, in another embodiment, preferably about 50 weight percent or less, and in yet another embodiment, more preferably about 40 weight percent or less, based on the total mass of solvent system. In another embodiment, the alcohol solvent system should be anhydrous.

According to an embodiment of the invention, the composition for fixing the hair should include approximately no more than 85% volatile organic compounds (VOC), such as alcohol and / or propellant, with the rest of the solvent being water. In another embodiment, compositions for fixing the hair should include approximately no more than 55% volatile organic compounds.

For the purposes of the present invention, the term “soluble” is that from about 1 to 10 weight percent, and in another embodiment, preferably from about 3 to 6 weight percent of the polyglucose polymer, is soluble, with or without neutralization, in an alcohol-based solvent system. In an embodiment, alcohol-based solvent systems suitable for use in the present invention include at least one C ₁ -C ₆ linear or branched alcohol or mixtures thereof and optionally water, optionally one or more propellants and optionally one or more other non-alcoholic, non-aqueous solvents. In an embodiment, the alcohol solvent in the alcohol-based solvent system comprises at least one C ₂ or C ₃ alcohol or mixtures thereof. In an embodiment, the solvent system is substantially free of non-alcoholic organic solvents. In one embodiment, the solvent system is substantially free of acetone. As used herein with respect to a solvent system, the term “substantially free” means that the solvent system contains less than 50%, alternatively less than 40%, alternatively less than 30%, alternatively less than 20%, alternatively less than 10%, alternatively less than 5% non-alcoholic organic solvent or acetone, respectively.

In an embodiment of the invention, the compositions for fixing hair additionally include at least one neutralizing agent. In an embodiment, the polyglucose polymer is typically at least about 50% neutralized. In another embodiment, the polyglucose polymer is at least about 70% neutralized, and in yet another embodiment, the fixation polymer is 100% neutralized. Suitable basic neutralizing agents compatible with the composition may be used, even inorganic substances such as sodium or potassium hydroxide. Typically, organic amines or alkanolamines are readily used to neutralize. In an embodiment, the neutralizing agents include, but are not limited to, ammonia; primary, secondary and tertiary amines; alkanolamines and hydroxyamines, such as 2-amino-2-methylpropanol and 2-amino-2-methyl-1,3-propanediol, mono-, di- and tri-long chain fatty amines containing a C ₄ -C ₂₄ hydrocarbon chain, ethoxylated and propoxylated long chain (C ₄ -C ₂₄ -) fatty amines and mixtures thereof. In another embodiment, neutralizing agents include aminomethyl propanol and dimethyl stearamine, inorganic substances such as sodium hydroxide and potassium hydroxide, and triethanolamine. In an embodiment of the invention, the neutralizing agent is an organic amine or alkanolamine. In an embodiment, combinations of neutralizing agents may also be used.

In an embodiment, the compositions for fixing hair have a spray rate in the range of about 0.3 to 1.5 grams / second in a system with 80% VOC at 3.5% solid phase and 40% DME, in another embodiment, preferably from about 0.5 grams / second to 1.2 grams / second, and in another embodiment, more preferably 0.75 to about 0.9 grams / second.

In addition to the above solvent systems, the present invention may further optionally include one or more propellants. In an embodiment of the invention, where the composition for fixing the hair is applied by spray, the polyglucose polymer is compatible with the propellant. By compatible is meant that the polyglucose polymer in the solvent system does not undergo phase separation when the solution is mixed with the propellant. In an embodiment, the polyglucose polymer is preferably compatible with dimethyl ether as a propellant. For the purposes of the present invention, the term “compatible” is that up to about 10 weight percent of the polyglucose polymer is soluble in a hair fixation composition that includes a propellant. In another embodiment, the polyglucose polymer is preferably soluble in a hair fixing composition that includes a propellant in an amount of from about 1 to 10 weight percent and in yet another embodiment, from about 2 to 8 weight percent, and in a further embodiment, from about 3 up to 6 weight percent.

Spray applications of the present invention require a mechanical device or aerosol can under pressure to form an aerosol. The devices may be manually controlled, such as a spray bottle or an easily compressible bottle, or may be a typical aerosol device, such as a container with a valve or a pressure can. If a pressurized balloon is used, the hair styling compositions of the present invention may further include a propellant. Such propellants include, but are not limited to, ethers, such as dimethyl ether; one or more low boiling hydrocarbons, such as C ₃ -C ₆ linear or branched hydrocarbons, for example propane, butane and isobutane; halogenated hydrocarbons such as hydrofluorocarbons, for example trichlorofluoromethane, dichlorodifluoromethane, 1,1-difluoroethane and 1,1,1,2-tetrafluoroethane, present as a liquefied gas; and compressed gases, for example nitrogen, air and carbon dioxide, as well as mixtures of these propellants. In an embodiment of the invention, the propellant is present in an amount of about 25% to about 80% by weight of the hair fixation composition comprising a solvent system. In a further embodiment, the propellant is present in an amount of about 30% to about 60 weight%. Alternatively, for some spray applications, such as spray application from a valve container or spray application, such optional propellants are not required. Compositions for fixing hair include, but are not limited to, aerosol and non-aerosol hairsprays.

In general, in another aspect of the invention, a method for preparing the aerosol hair spray compositions of the present invention includes dissolving, suspending or diluting the polyglucose polymer with selected solvents, adding any modifying agents depending on the desired properties, and then combining the resulting solution with the selected aerosol propellant.

As for the amounts of the various components, in an embodiment, the final hair fixation compositions may comprise a polyglucose starch ester polymer in a concentration ranging from about 1 to 10% by weight; an alcohol-based solvent in a concentration ranging from about 30 to 90 mass%; and, if included, an optional propellant with a concentration ranging from about 20 to 75 weight%. In another embodiment, the final hair fixation compositions may comprise a polyglucose polymer in a concentration ranging from about 2 to 8 weight%; the solvent in a concentration ranging from about 25 to 55 mass%; and, if included, an optional propellant with a concentration ranging from about 25 to 55% by weight.

In yet another aspect, the present invention relates to the use of a polyglucose polymer based on carboxylated starch esters, as defined herein, as a hair fixing polymer in a hair fixation composition, and to a hair styling method comprising applying a polyglucose polymer based on carboxylated starch esters as here defined on the hair. In one embodiment, the composition for fixing hair exists in the form of a varnish, in one embodiment, the varnish exists in the form of an aerosol varnish, in one embodiment, the varnish exists in the form of a non-aerosol varnish. In one embodiment, the composition for fixing hair exists in the form of a mousse. In one embodiment, the composition for fixing hair exists in gel form.

Applying the compositions for fixing the hair of the present invention is possible before, during or after reaching the desired hairstyle.

Optionally, cosmetically acceptable additives may be included in the hair fixation compositions of this invention in order to modify some of their properties. One of these optional additives may be, in addition to the polyglucose polymer, a second polymer, such as a hair fixing polymer. Non-limiting examples of these additional hair-fixing polymers include: Akzo Nobel Surface Chemistry LLC, AMPHOMER® 4961, AMPHOMER® and AMPHOMER® LV-71 (octyl acrylamide / acrylate / butylaminoethyl methacrylate copolymer), AMPHOMER® HC polymer (acrylate / octyl acrylate copolymer) BALANCE® CR (acrylate copolymer), BALANCE® 47 polymer (octyl acrylamide / acrylate / butylaminoethyl methacrylate copolymer), RESYN® 28-2930 polymer (VA / crotonates / vinyl neodecanoate copolymer), RESYN® 28-1310 polymer (VA copolymer / croton polymers FLEXAN® (sodium polystyrenesulfonate), DynamX polymer (copolymer polyurethane-14 (s) AMP-acrylates), RESYN® XP polymer (acrylate / octyl acrylamide copolymer), STRUCTURE® 2001 (acrylate / itaconate stearet-20 copolymer) and STRUCTURE® 3001 (acrylate / itaconate ceteta-20 copolymer); from Ashland Inc., OMNIREZ-2000® (PVM copolymer / MA ethyl ester), GANEX P-904® (bottled PVP), GANEX V-216® (PVP / hexadecene copolymer), GANEX® V-220 (PVP copolymer / eicosene), GANEX® WP-660 (tricontanil PVP), GANTREZ® A425 (butyl ester copolymer PVM / MA), PVM / MA copolymer GANTREZ® AN-119, GANTREZ® ES 225 (ethyl ester copolymer PVM / MA) GANTREZ® ES425 (butyl ester copolymer PVM / MA copolymer), GAFFIX® VC-713 (vinylcaprolactam / PVP / dimethylaminoethyl methacrylate copolymer), GAFQUAT® 755 (polyquaternium-11), GAFQUAT® HS-100 (polyquaternium-28) XL-30 (polyimide-1), AQUAFLEX® SF-40 (PVP / vinylcaprolactam / a copolymer DMAPA crylates), AQUAFLEX® FX-64 (isobutylene / ethyl maleimide / hydroxyethyl maleimide copolymer), ALLIANZ® LT-120 (acrylate copolymer / C1-2 succinates / hydroxyacrylates), STYLEZE® CC-10 (PVP copolymer / DMAPZA acrylates), ® 2000 (copolymer VP / acrylates / lauryl methacrylate), STYLEZE® W-20 (polyquaternium-55), a series of copolymers (copolymer PVP / dimethylaminoethylmethacrylate), ADVANTAGE® S and ADVANTAGE® LCA (copolymer vinylcaprolactam NP / dimethylaminoethyl), copolymer VA / butyl maleate / isobornyl acrylate); from BASF, The Chemical Company, ULTRAHOLD STRONG (acrylic acid / ethyl acrylate / tert-butyl acrylamide), LUVIMER® 100P (tert-butyl acrylate / ethyl acrylate / methacrylic acid), LUVIMER® 36D (ethyl acrylate / tert-butyl acrylate / methacrylic I-nitride-55 (L-55UV-IIQUAT) 16), LUVIQUAT® HOLD (polyquaternium-16), LUVISKOL® K30 (PVP) LUVISKOL® K90 (PVP), LUVISKOL® VA 64 (PVP / VA copolymer), LUVISKOL® VA73W (PVP / VA copolymer), LUVISKOL® VA, LUVISET® PUR (polyurethane-1), LUVISET® Clear (VP / methacrylamide / vinylimidazole copolymer), LUVIFLEX® SOFT (acrylate copolymer), ULTRAHOLD® 8 (acrylate / acrylamide copolymer), LUVISKOL® Plus (polyvinylXyl®, polyvinyl vinyl) copolymer PEG / PPG-25/25 dimethicone / acrylates); from The Dow Chemical Company, ACUDYNE® 180, ACUDYNE® 1000 and ACUDYNE® DHR (copolymer of acrylates / acrylates of hydroxyesters), ACUDYNE® SCP (copolymer of ethylene carboxyamide / AMPSA / methacrylates) and rheological modifiers ACULYN®; from Mitsubishi and distributed by Clariant Corporation, DIAFORMER® Z-301, DIAFORMER® Z-SM and DIAFORMER® Z-400 (methacryloyl ethyl betaine / acrylate copolymer), from Nalco Company, FIXOMER® A-30 and FIXOMER® N-28 (INCI name) : methacrylic acid / sodium acrylamidomethyl propanesulfonate copolymer); from The Lubrizol Corporation, FIXATE® G-100 (AMP-Acrylates copolymer / allyl methacrylate copolymer), FIXATE PLUS® (polyacrylate-14), FIXATE® SUPERHOLD (polyacrylate crosspolymer-2) and FIXATE® FREESTYLE (acrylates crosspolymer-3), CARBOPOL ® Ultrez 10 (carbomer), CARBOPOL® Ultrez 20 (acrylate / C10-30 alkyl acrylate copolymer), AVALURE® AC series (acrylate copolymer), AVALURE® UR series (polyurethane-2, polyurethane-4, PPG-17 / IPDI copolymer / DMPA); polyethylene glycol; water soluble acrylics; water soluble polyesters; polyacrylamides; polyamines; polyamines containing quaternary ammonium groups; styrene maleic anhydride resin (SMA); polyethyleneamine and another conventional polymer that is soluble in a polar solvent or which can be made soluble by neutralization with an appropriate base. It is also contemplated that a combination of one or more of the above hair-fixing polymers is within the scope of the present invention. According to an embodiment of the invention, the hair-fixing polymer is preferably selected from octyl acrylamide / acrylate / butylaminoethyl methacrylate copolymers, acrylate / octyl acrylamide copolymers, acrylate copolymers, octyl acrylamide / acrylates / butylaminoethyl methacrylate copolymers, VA copolymerne sulfonate-copolymer copolymers, 14 (s) AMP acrylates, acrylate / octyl acrylamide copolymers, acrylate / itaconate stearet-20 copolymers, acrylate copolymers / itaconate cetet A-20 and combinations thereof.

In an embodiment of the invention, an optional hair fixing polymer may be present in the composition for fixing hair in an amount of about 0.1 to 10% by weight based on the total weight of the composition. In a further embodiment, the hair-fixing polymer is present in an amount of from about 1 to 10 mass%, and in another embodiment, in an amount of from about 1 to 7 mass%.

In addition, optional cosmetically acceptable additives may also include: plasticizers, such as glycols, phthalate esters and glycerin; silicones; emollients, lubricants and penetrants, such as lanolin compounds, protein hydrolysates and other protein derivatives, ethylene oxide adducts and polyoxyethylene cholesterol; UV absorbers; dyes and other coloring matter; and perfumes. Mixtures of these optional additives may also be included. As noted previously, the polymeric binders of this invention do not exhibit at all or show a slight tendency to negative chemical interaction with such additives.

Additional optional ingredients may include, but are not limited to, preservatives, coloring agents, flavoring agents, viscosity modifiers, vitamins, herbal extracts such as sterols, triterpenes, flavonoids, coumarins, non-glycoside diterpenes (sterebins), spatulenol, decanoic acid, 8,11,14-eicosatrienoic acid, 2-methyl-octadecane, pentacosan, octacosan, stigmasterol, b-sitosterol, a- and b-amyrin, lupeol, b-amirinacetate and pentacyclic triterpene, include sunscreen active ingredients, Which as p-aminobenzoate or methoxycinnamate (UVB-absorber), or Benzone, or anthranilate (UVA-absorber), medicaments, moisturizers, anti-itch ingredients, and anti-dandruff, and the like.

The resulting hair-fixing compositions have the characteristics required for such a product. They have good antistatic properties, adhere well to hair, are easily removed with soapy water or shampoo, make it easy to comb hair again, do not turn yellow during aging, do not become sticky when exposed to high humidity, and are characterized by excellent curl fixation in high humidity conditions.

The method for preparing the hair fixation compositions of the present invention can be carried out in various ways and depending on the polyglucose polymer used. Moreover, in a further aspect of the invention, the invention relates to a non-limiting method of obtaining a composition for fixing hair. The method includes suspending or dissolving the polyglucose polymer in alcohol-based solvent systems, for example comprising one or more C ₁ -C ₆ alcohols. In an embodiment, the method also includes neutralizing the solution with a neutralizing agent, such as aminomethylpropanol. In an embodiment, one or more alcohols may include ethanol in combination with isopropanol or n-propanol, optionally in a weight ratio of ethanol and isopropanol from about 80:20 to 20:80. In yet another embodiment, optionally, the method further includes the step of adding a propellant to the composition. In a further optional step, the method may also include adding water to the composition before, during or after suspending the polyglucose polymer in alcohol or after the neutralization step.

In an embodiment, the polyglucose polymers of the present invention are suitable for use in hair fixation compositions such as hair sprays, mousses or gels.

The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the invention in any way. The breadth and scope of the invention should be limited solely by the claims appended hereto.

Examples

General methods for the synthesis of polyglucose polymers

Polymers Acetate (or Propionate) Succinate Starch Succinate

The reaction vessel, equipped with a stirrer and a condenser, kept in a nitrogen atmosphere and immersed in an oil bath for heating, is charged with the indicated amount (see table 2) of starch, acetic acid, sodium acetate (or sodium hydroxide) and acetic anhydride (or propionic anhydride). The amount of acetic (or propionic) anhydride is controlled in such a way as to maintain the level of moisture normally found in starch. The mixture is heated to 125-130 ° C with stirring until the completion of the interaction, controlled by IR on the disappearance of the anhydride peak. As soon as all the acetic (or propionic) anhydride has reacted, the reaction mixture is cooled to approximately 100-110 ° C, OSA is added and stirring is continued at 110-115 ° C until completion of the reaction, monitored by IR for the disappearance of the anhydride peak belonging to OSA. Then succinic acid is added to the reaction mixture and stirring is continued at 110-115 ° C until all succinic anhydride reacts, which is controlled by IR. Then the reaction mixture is cooled to 70 ° C and then poured into vigorously stirred water (approximately 5 times the mass of the reaction mixture) at ambient temperature. After stirring for 30 minutes, the solid was separated by filtration, washed with water until all residual acetic acid was washed off, and dried in an oven at 45 ° C. overnight to give a solid.

Some other starch acetate (or propionate) succinate starch succinate polymers are prepared using different starch sources, using essentially the same procedure as mentioned above, but using different amounts of raw materials, as described in detail in Table 2 (Examples 1-13 and 16-26 )

Polymers of Acetate-Stenyl Succinate Phthalates

They are prepared using essentially the same procedure as mentioned above, except that after all the acetic anhydride has reacted, the indicated amount of phthalic anhydride is added, followed by OSA 2 hours after the addition of phthalic anhydride. Details regarding the raw materials for the manufacture of these products are described in detail in table 2, examples 14, 15 and 27.

Table 1 summarizes various examples of polyglucose polymers synthesized according to the present invention.

Table 1
Examples of polyglucose polymers ^a Example No. Used starch ^b Values DS (theoretical) ^c The acidity value meq / g Compatible in Spray intensity Acetic Anhydride Propionic Anhydride Succinic anhydride OSA Phthalic anhydride Ethanol system with 80% VOC 40% DME system one A 1,62 0 0 0.52 0 1.76 Insoluble - - 2 A 1,6 0 1,58 0 0 3.79 Soluble Insoluble - 3 A 0 1.7 1,07 0 0 2,56 Soluble Insoluble - four A 2.19 0 1.05 0 0 2.70 Soluble Insoluble - 5 A 2.19 0 0.63 0 0 1.92 Soluble Insoluble - 6 A 2.19 0 0.42 0.21 0 2.20 Soluble Soluble 0.80 7 A 2.19 0 0.21 0.42 0 2.28 Soluble Soluble 0.83 8 A 2.19 0 0 0.63 0 2.04 Soluble Soluble 0.76 9 A 2.19 0 0.32 0.32 0 1.98 Soluble Soluble 0.89 10 A 2.19 0 0.32 0.52 0 2,52 Soluble Soluble 0.86 A 2.19 0 0.21 0.42 0 2.02 Soluble Soluble 0.84 A 2.19 0 0.21 0.52 0 2,34 Soluble Soluble 0.79 A 2.19 0 0.32 0.32 0 1.94 Soluble Soluble 0.78 fourteen A 2.1 0 0 0 0.6 1.55 Soluble Soluble - fifteen A 2.1 0 0 0.3 0.4 2.80 Soluble Soluble 0.71 16 A 2.1 0 0 0.2 0.5 2.67 Soluble Soluble 0.79 17 B 1.8 0 1,54 0 0 3.72 Soluble Insoluble - eighteen B 0 1.8 1,54 0 0 2.66 Insoluble - - 19 B 0 1.84 1.05 0 0 2,36 Soluble Insoluble - twenty B 2,32 0 0.41 0.2 0 2.24 Soluble Soluble 0.79 21 B 2,32 0 0.2 0.41 0 2.24 Soluble Soluble 0.80 C 1,6 0 0 0.6 0 1.97 Insoluble - - C 2.18 0 0.21 0.42 0 2.08 Insoluble - - C 2.18 0 0.21 0.52 0 2.03 Soluble Soluble 0.69 C 1.89 0 0.21 0.52 0 2.14 Soluble Soluble 0.62 C 1.89 0 0.32 0.52 0 2,38 Soluble Soluble 0.74 27 C 2.1 0 0 0 0.6 1.99 Soluble Insoluble - a) Unless otherwise indicated, all interactions are carried out using sodium acetate as a catalyst.
b) A = Glucidex 1, potato-based maltodextrin with DE 5 max from Roquette;
B = Glucidex-2, maltodextrin based on waxy maize with DE 5 max from Roquette;
C = Star Dri-1, maltodextrin based on waxy corn with DE 1 from Tate & Lyle.
c) The amount of anhydride used to produce theoretically calculated degrees of substitution (DS) on starch. Actually, the obtained values were not measured.
d) Compatibility of 3.5 wt.% polymer in the ethanol: water system 80:20 wt.% at a 90% level of neutralization using AMP, at temp. the environment
e) Compatibility of 3.5 wt.% polymer in an ethanol system with 80% with 40% DME, at temp. the environment
f) Use of NaOH instead of NaOAc as a catalyst.

table 2
Detailed descriptions of the raw materials used to make polyglucose polymers ^a Example No. Starch Acetic acid Sodium Acetate ^B Acetic Anhydride Propionic Anhydride Succinic anhydride OSA Phthalic anhydride one thirty 45 12.1 37.1 0 0 19,4 0 2 29.5 41 11.2 37.1 0 27.3 0 0 3 19.1 19 7.2 0 30.6 11.8 0 0 four 32,4 32 12.3 51 0 twenty 0 0 5 32,4 32 12.3 51 0 12 0 0 6 32,4 32 12.3 51 0 8 8,416.8 0 7 32,4 32 12.3 51 0 four 16.8 0 8 32,4 32 12.3 51 0 0 26.2 0 9 64.8 64 24.6 102 0 12 25,2 0 10 64.8 64 24.6 102 0 12 42 0 eleven 64.8 thirty 6 ^c 117.3 0 8 33.6 0 12 64.8 thirty 6 ^c 117.3 0 8 42 0 13 64.8 thirty 6 ^c 117.3 0 12 25,2 0 fourteen 50.7 thirty 7.4 76.3 0 0 0 26.6 fifteen 50.7 thirty 7.4 76.3 0 0 18.9 17.8 16 50.7 thirty 7.4 76.3 0 0 12.6 22.2 17 32,4 45 12.3 40.8 0 thirty 0 0 eighteen 32,4 32 12.3 0 52 thirty 0 0 19 19.1 19 7.2 0 31,2 11.8 0 0 twenty 32,4 32 12.3 51 0 8 8.4 0 21 32,4 32 12.3 51 0 four 16.8 0 22 64.8 36 6 ^c 94.5 0 0 48.1 0 23 64.8 thirty 6 ^c 117.3 0 8 33.6 0 24 64.8 thirty 6 ^c 117.3 0 8 42 0 25 64.8 twenty 6 ^c 106.1 0 8 42 0 26 64.8 twenty 6 ^c 106.1 0 12 42 0 27 51.6 80 7.4 81.5 0 0 0 26.6 a) The indicated weights are given in grams.
b) Unless otherwise indicated, sodium acetate is used as the catalyst.
c) Sodium hydroxide is used as a catalyst instead of sodium acetate.

A. SUBJECTIVE TEST METHODS

Subjective assessments are carried out as shown in the examples when compared with the polymer AMPHOMER®, in each example, 3.5 wt.% Of polymers are used using an ethanol-water system with 80 wt.% VOC and 40 wt.% DME or otherwise determined using statistical calculation method at a 95% confidence level. The results of the subjective evaluations are shown in the tables, which, as indicated, are presented below.

The following methods are used to evaluate the subjective quality of the polyglucose polymers of the present invention.

Shine:

Carefully sort out the strands with your hands so as not to destroy the films. Visually inspect the strand to determine which has more shine / gloss.

Rigidity:

Carefully sort the strands with your hands and feel the differences in stiffness. Using two fingers, hold the middle of the strand in a horizontal position - does one bend more than the other? Choose the one that is tougher .

Elasticity:

Holding the strand in one hand, carefully pull the edge towards you with your other hand only three times. Look for spring and rebound. The greater the elasticity, the better the elasticity.

Weaving:

While holding the strand with both hands, gently pull outward toward the edges for approx. 4 sec (Do this only three times to avoid damage to the clutch. If the clutch is broken, dry combing may make it easier to comb). The more uniform the bundle, the better the weaving.

Dry combing :

Comb each strand (5) times and appreciate the ease of combing. Choose one that is easier to comb.

Cereals:

Visually check both strands after combing. Check flange teeth for flocs. Holding the strand by the connected end, slide your fingernail down the length of the curl, then check. Choose one with more cereal.

Antistatic properties:

Holding the strand by its tied end, vigorously comb it 10 times, then evaluate the degree of expansion caused. Choose one with a stronger fly.

Tactile sensations:

Sort the strands with your hands and set the preference. Choose the one you feel more silky / clean.

Table 3
The subjective assessment of ^a polyglucose polymers according to examples 6-16, 20, 21 and 24-26 in comparison with the polymer AMPHOMER® using 3.5 wt.% Polymer using the ethanol-water system with 80 wt.% VOC and 40 wt.% DME, at 95% confidence level Example No. Shine Rigidity Elasticity Weaving Dry combing Cereals Antistatic properties Tactile sensations Based polymers Glucidex-1 6 - = = = = = + - 7 = = - - = = = = 8 - - = = = - = = 9 - = = = + + + = 10 = = = = = = = = eleven - = - - = = = = 12 - - - = + + = + 13 - = = = = = + + 15 ^b - - - - = = = = 15 ^s = - - = + = + = 16 ^b = - - = + - = = 16 ^c - = - = = - + = Based polymers Glucidex-2 twenty = = - = + = = + 21 = - - = + = = = Star Dri-1 Polymers 24 - - - = = + = + 25 - = - = = = + = 26 - = = = = = + = a) Unless otherwise specified, all polymers are neutralized to 90% level using AMP.
b) 100% neutralized.
c) 70% neutralized.
= not statistically different; + better; - worse

Based on the results shown in table 3, it is believed that all samples provide appropriate subjective quality, justifying further research on objective quality.

Table 9
Shampoo washability of characteristic starch polymers compared to AMPHOMER® polymer Sample Hardness after shampooing Flakes after shampooing Dry feeling after shampooing Example 17 + + + Example 20 + = = = not statistically different; + better; - worse

Based on the results of subjective tests shown in Table 9, it is believed that all samples provide complete, statistically superior shampoo wash-offs compared to AMPHOMER® polymer

B. DETERMINATION OF SPRAY INTENSITY

MATERIALS / EQUIPMENT:

Ventilation extractor

Protective glasses

Top-loading balance (accuracy 0.01 grams)

Stopwatch

METHODOLOGY: perform duplicating

AEROSOL HAIR VARNISH

1. Weigh the can of hairspray and write down the mass.

2. Place the can in the fume hood. Using constant pressure, depress the valve for ten seconds.

3. Re-weigh the can and record the mass.

Calculation: initial mass - mass after spraying = gram / second

Note: if duplicates do not converge within 0.03 g / second, repeat the procedure

NONAEROSOL HAIR VARNISH

1. Weigh the hairspray dispenser bottle and note the weight.

2. Place the bottle in the fume hood. Sequentially and fully depress the valve ten times (“emissions”).

3. Weigh the dispenser bottle again and record the weight.

Calculation: initial mass - mass after spraying = gram / “ejection”

Note: if duplicates do not converge within 0.03 grams / “ejection”, repeat the procedure

Valve specification (purchased from a company called Aptar)

Product VX-81

Case: VX Barbed .013 NOVT ARIAN

Stock: VX80 .343 FC 1 x .013 ORIFICE

GASKET: VX .045 BUTYL CODE 501

ELASTICITY: STAINLESS STEEL VS .018 OPEN C

CAP: HIPRO BNA PGFR GSK AL EP T / B D

TUBA: .122 ID

TUBE LENGTH: 09 00/16 ”

Valve Control Specification (from Aptar)

REF No: XL002838

PRODUCT: XL200 SHIP OUT

TAG NUMBER: XL200 VX MISTY TAP .023 MISTY

BUTTON: VX XL 200 MISTY TAP WHITE

INSERT: .023 MISTY BLACK

C. METHOD FOR DETERMINING HIGH HUMIDITY WAVE FIXING (HHCR)

To assess the objective consumer quality of the polyglucose polymers of the present invention, determined by fixing the perm in high humidity, the following methods are used. Evaluate the properties of fixing curls at high humidity of hair styling compositions comprising the polyglucose polymers of the present invention. Each test is carried out at 72 ° F (22 ° C) and 90% relative humidity for a period of 24 hours. The tests are performed on strands of natural European brown hair 10 inches (25.4 cm) x 2 gram long (9 duplicate strands per sample). The curl fixation test is carried out in a chamber with a variable air humidity set to 70 ° F / 90% relative humidity, for a total of 24 hours. Indications% fixation of the curl is read and recorded at time intervals of 15, 30, 60, 90 minutes, 2, 3, 4, 5 and 24 hours. Hair styling compositions are examined by the following methods:

1. Comb a damp lock of hair to remove tangles and wring out excess water (skip the lock between thumb and forefinger).

2. Apply the sample to the strand, gently “rub” into the strand and comb through.

3. Screw the strand onto a 1/2 inch (1.27 cm) Teflon sheath. Carefully remove the wound strand from the sheath and secure with two hair clips.

4. Place the curls on the tray and dry in an oven overnight.

5. Remove the dried curls from the oven and allow to cool to room temperature.

6. Hang the curls by the tied end of the strand onto sequentially loose, transparent plates to hold the curls.

7. Remove the hair clips from the curls and carefully unwind with a glass rod, trying to “break” the curl.

8. Read the initial curl lengths before placing the plates and curls in an artificial climate chamber (70 ° F, 90% relative humidity).

9. Record curl lengths at time intervals of 15, 30, 60, 90 min, 2, 3, 4, 5, and 24 hours.

10. At the end of the test, remove the plates and curls from the chamber.

11. Remove used hair strands.

12. Calculate the% fixation of the curl and compare the samples.

Samples are prepared as follows:

HHCR is performed in a chamber with constant temperature and humidity. Curls are wound on a teflon shell and allowed to dry overnight. Then the curls are sprayed with polymer solutions (3.5 wt.% Polymer using an ethanol system with 80% VOC and 40% DME) and allowed to dry. After that, the curls are suspended on a plate placed in an oven, and the percentage of loss of curls is monitored after 24 hours.

The high-moisture-fixing properties of the perm in the hair styling compositions comprising the polyglucose polymers of the present invention, according to the examples given in the tables below, were measured as indicated and compared with the use of the AMPHOMER® polymer in the same hair styling composition.

Table 4
HHCR results for Glucidex-1-based starch acetate succinate, stenyl succinates according to Examples 6-10, obtained using NaOAc as a catalyst (using 3.5 wt.% Polymer), at a 90% level of neutralization, compared to the polymer AMPHOMER®, s using 3.5 wt.% polymer and ethanol-water system with 80 wt.% VOC and 40% DME, with a 95% confidence level Example No. 5 hour 24 hour Example 6 82 (=) 82 (=) Example 7 82 (=) 80 (=) Example 8 83 (=) 81 (=) Example 9 81 (=) 78 (=) Example 10 73 (=) 71 (=) Amphomer 76 74 = not statistically different; + better; - worse

As shown in table 4, all examples provide statistically equal HHCR quality in comparison with the polymer AMPHOMER®.

Table 5
HHCR results for Glucidex-1-based starch acetate succinate, stenyl succinates according to Examples 11-13, obtained using NaOH as a catalyst (using 3.5 wt.% Polymer), at a 90% level of neutralization, compared to the polymer AMPHOMER®, with using 3.5 wt.% polymer and ethanol-water system with 80 wt.% VOC and 40% DME, with a 95% confidence level Example No. 5 hour 24 hour Example 11 71 (=) 67 (=) Example 12 79 (=) 72 (=) Example 13 72 (=) 70 (=) Amphomer 72 66 = not statistically different; + better; - worse

As shown in table 5, all examples provide statistically equal HHCR quality in comparison with the polymer AMPHOMER®.

Table 6
HHCR Results for Glucidex-1-based Starch Acetate Phthalate Ttenyl Succinates of Examples 15 and 16 Obtained Using NaOAc as a Catalyst (Using 4 wt.% Polymer) Compared to AMPHOMER® Polymer Using 4.0% Polymer and System ethanol-water with 80 wt.% VOC and 40% DME, at 95% confidence level Example No. 5 hour 24 hour Example 15 ^a 31 (-) 22 (-) Example 15 ^b 84 (=) 83 (=) Example 16 ^a 31 (-) 25 (-) Example 16 ^b 83 (=) 81 (=) Amphomer 90 89 a) The polymer is neutralized to 100% level using AMP.
b) 70% neutralized.
= not statistically different; + better; - worse

As shown in table 6, examples with 70% neutralization give statistically equal HHCR quality in comparison with the polymer AMPHOMER®. On the other hand, examples with 100% neutralization have poor HHCR quality.

Table 7
HHCR results for Glucidex-2 based starch acetate succinate and stenyl succinates in Examples 20 and 21 (using a 3.5 wt.% Polymer), at a 90% neutralization level, compared to an AMPHOMER® polymer, using 3.5 wt.% Polymer and ethanol-water systems with 80 wt.% VOC and 40% DME, with a 95% confidence level Example No. 5 hour 24 hour Example 20 thirty (-) 19 (-) Example 21 64 (=) 56 (-) Amphomer 76 74 = not statistically different; + better; - worse

As shown in table 7, the polymer of example 20 has poor HHCR quality compared to the AMPHOMER® polymer at 5 hours, each of the polymers of examples 20 and 21 has poor HHCR quality compared to the AMPHOMER® polymer at 24 hours.

Table 8
HHCR results for Star Dri-1 based starch acetate succinate and stenyl succinates according to Examples 24-26 (using 3.5 wt.% Polymer), at a 90% neutralization level, compared to AMPHOMER® polymer, using 3.5 wt.% polymer and ethanol-water systems with 80 wt.% VOC and 40% DME, at 95% confidence level Example No. 5 hour 24 hour Example 24 52 (-) 45 (-) Example 25 52 (-) 48 (-) Example 26 66 (=) 63 (=) Amphomer 71 69

As shown in table 8, the polymers of examples 24 and 25 have poor HHCR quality compared to the polymer AMPHOMER® at 5 hours, while the polymer of example 26 has a quality that is statistically equal to the quality of the polymer AMPHOMER®.

All documents referred to in the detailed description of the invention, in relevant part, are incorporated herein by reference; reference to any document should not be construed as an assumption that it is a prior art in relation to the present invention. On the contrary, various modifications are possible in specific details within the range and scope of equivalents of the claims without departing from the spirit and scope of the invention.

Claims (27)

1. Composition for fixing hair, including: at least one carboxylated starch ester polyglucose polymer obtained by reacting at least one starch ester with at least two cyclic anhydrides; an alcohol-based solvent system, wherein the alcohol-based solvent system includes at least one C ₁ -C ₆ linear alcohol, a C ₃ -C ₆ branched alcohol, or a mixture thereof in an amount of 15 weight percent or more; and at least one cosmetically acceptable additive where at least one carboxylated starch ester polyglucose polymer is soluble in an alcohol based solvent system, and moreover, at least one polyglucose polymer based on carboxylated starch esters has the following structure (I):

(I) in which R = H, R _H or R _A, or combinations thereof, where at least one R is R _A and where R _H is: –CO – R ¹ , where R ¹ is C ₁ –C _{21 is an} alkyl group; and R _A represents: a) –CO – CH ₂ –CH (R ² ) –COOH, where R ² = H or C ₆ –C _{18 is an} alkenyl group, or b) –CO – CH = CH – COOH; or c) –CO – CH – C (= CH ₂ ) –COOH; or d) –CO — C ₆ H ₄ —COOH, or e) –CO — C ₆ H ₈ —COOH; and where n = 10–500. 2. The composition of claim 1, wherein the at least one starch ester is a starch ester with at least one acyclic anhydride. 3. The composition according to claim 1 or 2, where at least two cyclic anhydrides are selected from the group consisting of succinic anhydride, alkenyl succinic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and combinations thereof. 4. The composition of claim 2, wherein the at least one acyclic anhydride is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, and a mixture thereof. 5. The composition according to claim 1 or 2, where at least one starch ester is selected from the group consisting of starch acetate, starch propionate, starch butyrate, starch acetate butyrate, starch acetate propionate and combinations thereof. 6. The composition of claim 1 or 2, wherein the alcohol-based solvent system further comprises water, one or more propellants, or one or more non-alcoholic, non-aqueous solvents, or a mixture thereof. 7. The composition according to p. 1 or 2, where at least one polyglucose polymer based on carboxylated starch esters is present in the composition for fixing hair in an amount of from 1 mass percent to 10 mass percent based on the weight of the composition for fixing hair. 8. The composition according to p. 1 or 2, where at least one ester of starch is an ester of an oligosaccharide, polysaccharide or hydrogenated oligosaccharide. 9. The composition according to claim 1 or 2, where at least one ester of starch is an ester of maltodextrin, corn syrup or pyrodextrin. 10. The composition according to p. 9, where the starch is maltodextrin with dextrose equivalence from 1 to 25. 11. The composition according to p. 1 or 2, where at least one polyglucose polymer based on carboxylated starch esters is neutralized by at least 50%. 12. The composition according to p. 1 or 2, where the composition for fixing the hair is an aerosol hair spray or non-aerosol hair spray. 13. The composition according to p. 1 or 2, where at least one cosmetically acceptable additive is selected from the group consisting of one or more second hair-fixing polymer, plasticizers, UV absorbers, dyes, fragrances, preservatives, modifiers, vitamins, active sunscreens, moisturizers, anti-itch and anti-dandruff ingredients and mixtures thereof. 14. A method of obtaining a composition for fixing hair according to any one of claims 1 to 13, including: reacting at least one starch ester with at least two cyclic anhydrides to form a polyglucose polymer based on carboxylated starch esters, and dissolving or suspending the resulting at least one polyglucose polymer based on carboxylated starch esters in an alcohol based solvent system; optionally neutralizing at least one polyglucose polymer based on carboxylated starch esters; and optionally reacting starch with at least one acyclic anhydride to form at least one starch ester; and adding at least one cosmetically acceptable additive. 15. The use of a polyglucose polymer based on carboxylated starch esters as defined in any one of paragraphs. 1-13, as a hair fixing polymer in a hair fixing composition.