FR2968541A1 - Two-compartment aerosol device comprises in first compartment, a hair styling composition comprising carboxylic anionic polymer without urethane unit in alcoholic or aqueous-alcoholic medium, and in a second compartment, a compressed gas - Google Patents

Abstract

The present invention relates to a dual compartment aerosol device comprising a styling composition in a first compartment and a compressed gas selected from air, nitrogen, carbon dioxide and mixtures thereof in a second compartment. Said styling composition comprises at least one carboxylic anionic polymer without urethane unit in an alcoholic or aqueous-alcoholic medium which comprises at least 5% by weight relative to the weight of said composition, of a monohydric alcohol containing C -C. This aerosol device may constitute a hairspray. The invention also relates to a styling method implementing the device of the invention.

Description

The present invention relates to a dual compartment aerosol device comprising a styling composition and a particular compressed gas, and to a styling process. BACKGROUND OF THE INVENTION The present invention relates to a dual compartment aerosol device comprising a styling composition and a particular compressed gas, and to a styling process. Hair styling compositions, such as lacquers and sprays, packaged in the form of an aerosol spray are generally composed of a liquid phase comprising, in an aqueous, cosmetically acceptable medium, alcoholic or aqueous-alcoholic, at least one fixing polymer, and a propellant which is a liquefied gas under reduced pressure or dissolved in the liquid phase.

Other aerosol devices including such a liquid phase exist, but they include compressed gases to propel the liquid phase. However, these compressed gas devices have the disadvantage of a loss of pressure of the gases over time. Indeed, there is a leak of compressed gases over time or during improper use of the container, that is to say when it is upside down. This disadvantage leads to less and less good propulsion of the liquid phase over time and consequently a less and less good distribution of the liquid phase on the hair.

Another factor that can lead to a bad distribution of the liquid phase from these devices is the quality of the spray which is degraded when one seeks to obtain the most important fixation possible, that is to say when the it is sought to increase the amount of polymer that can be dissolved in said liquid phase.

The Applicant has made the surprising discovery that the mechanical separation of the liquid phase of the compressed gas providing the propulsion, and the use of a particular compressed gas and a carboxylic anionic polymer without a urethane unit in the propellated composition made it possible to solve the problems of leakage and distribution of the liquid phase on the hair. This particular combination thus makes it possible to obtain fixation and / or shaping with a level of fixation which can not be achieved usually with this type of product.

The invention therefore relates to a two-compartment aerosol device comprising a styling composition which comprises at least one carboxylic anionic polymer without urethane unit, and at least one compressed gas as described below. Another object of the present invention is a styling method using this device. Other objects, features, aspects and advantages of the invention will emerge even more clearly on reading the description and the various examples which follow.

The two-compartment aerosol device according to the invention comprises: (a) in a first compartment, a styling composition comprising at least one urethane-free carboxylic anionic polymer in an alcoholic or aqueous-alcoholic medium which comprises at least 5% by weight, by relative to the total weight of said composition, of a C 1 -C 4 monohydric alcohol, and (b) in a second compartment, a compressed gas selected from air, nitrogen, carbon dioxide and mixtures thereof, air being particularly preferred. Said compressed gas is preferably used at a pressure of between 1 and 12 bar, more preferably between 9 and 11 bar. In what follows or precedes the expression "at least one" is equivalent to "one or more".

NON-POLYURETHANE CARBOXYLIC ANIONIC FIXING POLYMER (without urethane unit) The anionic fixing polymers used according to the invention are polymers containing groups derived from carboxylic acid, and which preferably have a number-average molecular mass of between about 500 and 5,000. The carboxylic groups are provided by unsaturated mono- or di-carboxylic acid monomers such as those of the formula: wherein n is an integer from 0 to 10, Al denotes a methylene group, optionally connected to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1, through a heteroatom such as oxygen or sulfur, R7 denotes an atom of hydrogen, a phenyl or benzyl group, R8 denotes a hydrogen atom, a lower alkyl or carboxyl group, R9 denotes a hydrogen atom, a group lower alkyl, -CH 2 -COOH, phenyl or benzyl. In the abovementioned formula, a lower alkyl group preferably denotes a group having 1 to 4 carbon atoms and in particular the methyl and ethyl groups. The anionic fixing polymers containing carboxylic groups may be: A) copolymers of acrylic acid and of acrylamide, such as those sold in the form of their sodium salts under the names RETEN 421, 423 or 425 by the company HERCULES; sodium salts of polyhydroxycarboxylic acids; B) copolymers of acrylic or methacrylic acid with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted onto a polyalkylene glycol such as polyethylene glycol, and optionally crosslinked. Such polymers are described in particular in the applications FR 1 222 944 and DE 2 330 956, the copolymers of this type comprising in their chain an acrylamide unit, optionally N-alkylated and / or hydroxyalkylated, as described in particular in the LU patent applications. 75370 and LU 75371 or offered under the name QUADRAMER by AMERICAN CYANAMID. Mention may also be made of methacrylic acid / ethyl acrylate / tertiobutyl acrylate terpolymers, such as the product marketed under the name LUVIMER® 100 P by the company BASF. Mention may also be made of methacrylic acid / acrylic acid / ethyl acrylate / methyl methacrylate copolymers in aqueous dispersion, sold under the name AMERHOLD® DR 25 by the company Amerchol. Mention may also be made of polymers of the FIXATE G 100 type. C) Crotonic acid copolymers, such as those comprising, in their chain, acetate or vinyl propionate units, and optionally other monomers such as the allyl or methallyl esters, vinyl ether or vinyl ester of a saturated carboxylic acid, linear or branched, long hydrocarbon chain, such as those comprising at least 5 carbon atoms, these polymers may optionally be grafted or crosslinked, or another monomer vinyl ester, allylic or These polymers are described, inter alia, in the applications FR 1 222 944, FR 1 580 545, FR 2 265 782, FR 2 265 781, FR 1 564 110 and FR. 2,439,798. Commercial products in this class are the resins 28-29-30, 26-13-14 and 28-13-10 marketed by National Starch D) copolymers of carboxylic acids or anhydrides 10 monounsaturated C4-C8 compounds chosen from: - copolymers comprising (i) one or more maleic, fumaric, itaconic acids or anhydrides and (ii) at least one monomer chosen from vinyl esters, vinyl ethers, vinyl halides, derivatives thereof phenylvinyl, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. Such polymers are described in particular in the applications US 2,047,398, US 2,723,248, US 2,102,113, and GB 839,805. Commercial products are in particular those sold under the names GANTREZ® AN or ES by the company ISP; Copolymers comprising (i) one or more maleic, citraconic and itaconic anhydride units and (ii) one or more monomers chosen from allylic or methallyl esters optionally containing one or more acrylamide, methacrylamide, α-olefin or acrylic ester groups; methacrylic, acrylic or methacrylic acid or vinylpyrrolidone in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.

These polymers are for example described in applications FR 2 350 384 and FR 2 357 241 of the applicant. E) polyacrylamides having carboxylate groups. Preferably, the anionic carboxylic fixing polymers are chosen from acrylic acid copolymers such as acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers sold in particular under the name ULTRAHOLD® STRONG by BASF, the copolymers derived therefrom. crotonic acid such as vinyl acetate terpolymers / vinyl tert-butylbenzoate / crotonic acid and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold in particular under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, such as the monoesterified methyl vinyl ether / maleic anhydride copolymers sold , for example, under the name GANTREZ® by the company ISP, co polymers of methacrylic acid and of methyl methacrylate sold under the name EUDRAGIT® L by the company ROHM PHARMA, the copolymers of methacrylic acid and of ethyl acrylate sold under the name Luvimer® MAEX or MAE by the company BASF and vinyl acetate / crotonic acid copolymers sold in particular under the name LUVISET CA 66 by the company BASF and the vinyl acetate / crotonic acid copolymers grafted with polyethylene glycol sold under the name ARISTOFLEX® A by the company BASF.

The fixing polymers of the invention may also be polymers with silicone skeletons bearing non-silicone grafts or non-silicone polymers with silicone grafts bearing carboxylic groups, such as the VS80 polymer from the company 3M.

Among the anionic fixing polymers mentioned above, the monoesterified methyl vinyl ether / maleic anhydride copolymers sold under the name Gantrez® ES 425 by the company ISP are more particularly preferred, the terpolymers of acrylic acid / ethyl acrylate / N-tert-butylacrylamide sold under the name ULTRAHOLD® STRONG designation by BASF, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT® L by the company ROHM PHARMA, terpolymers vinyl acetate / vinyl tert-butylbenzoate / crotonic acid and terpolymers crotonic acid vinyl acetate / vinyl neododecanoate sold under the name Resin 28-29-30 by the company National Starch, the copolymers of methacrylic acid and of ethyl acrylate sold under the name Luvimer® MAEX or MAE by the company BASF . The anionic carboxylic fixing polymer or polymers are preferably present in an amount ranging from 0.5 to 20% by weight, more preferably from 1 to 12% by weight relative to the total weight of the styling composition.

COSMETIC MEDIUM The compositions of the invention comprise at least one C1-4 monohydric alcohol. Monohydric means an alcohol comprising only one hydroxyl function.

The monohydric alcohols of the invention are preferably chosen from ethanol, isopropanol, n-propanol, t-butanol or their mixtures. They are preferably chosen from ethanol, isopropanol or their mixtures. Even more preferentially, the C1-C4 monohydric alcohol is ethanol. The medium comprises at least 5% by weight, preferably from 5 to 99.9% by weight, more preferably from 10 to 99% by weight and even more preferably from 20 to 98% by weight relative to the total weight of said composition. of one or more monohydric C1-4 alcohols. In a hydroalcoholic medium, the proportion of water may vary from 1 to 95%, and preferably from 10 to 90% of the total weight of the composition.

According to a particular embodiment, the composition according to the invention may further comprise one or more additional fixing polymers. For the purposes of the present invention, the term "fixing polymer" is intended to mean any polymer which makes it possible to impart a shape or maintain a given shape or hairstyle. The synthetic fixing polymers are generally chosen from cationic, amphoteric, nonionic and anionic polymers other than those of the invention, and mixtures thereof. For the purpose of the present invention, the term "cationic polymer" is intended to mean any polymer comprising cationic groups and / or ionizable groups in cationic groups. The cationic fixing polymers may be chosen from polymers containing primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly connected thereto, and having a number-average molecular mass of between 500 and approximately 5,000,000, and preferably between 1,000 and 3,000,000. Among these polymers, mention may be made more particularly of the following cationic polymers: (1) homopolymers or copolymers of acrylic or methacrylic esters or amides, with functions amino acids, having at least one of the following units of formula 1+ RNR, [X] R5 or [X] in which: R1 and R2, identical or different, each represent a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; R3 denotes a hydrogen atom or a CH3 group; A is a linear or branched alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms; R4, R5, R6, which may be identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl group; X denotes a methosulphate anion or a halide such as chloride or bromide. These copolymers also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone-acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyl groups (Cl-4), groups derived from acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters. Thus, among these copolymers, mention may be made of: the copolymers of dimethylaminoethyl acrylamide and methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as that sold under the name HERCOFLOC® by the company HERCULES, copolymers acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company Ciba Geigy, the copolymers of acrylamide and methacryloyloxyethyltrimethylammonium methosulphate, such as the product sold under the name RETEN by Hercules, - vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate quaternized or otherwise, such as the products sold under the name "GAFQUAT®" by ISP, such as, for example, "GAFQUAT ® 734 'or' GAFQUAT® 755 ', or the products called' COPOLYMER® 845, 958 and 937 ". These polymers are described in detail in Applications FR 2 077 143 and FR 2 393 573, dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX® VC 713 by the company ISP, and copolymers quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide, such as in particular the product sold under the name "GAFQUAT® HS 100" by the company ISP; (2) quaternary copolymers of vinylpyrrolidone and vinylimidazole.

The amphoteric fixing polymers may be chosen from polymers comprising units B and C statistically distributed in the polymer chain where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit derived from a acidic monomer having one or more carboxylic or sulfonic groups, or B and C may denote groups derived from zwitterionic monomers of carboxybetaines or sulfobetaines; B and C may also designate a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group connected via a hydrocarbon group, or B and C are part of a chain of an ethylene-α, β-dicarboxylic polymer having one of the carboxylic groups reacted with a polyamine having one or more primary or secondary amine groups. amphoteric fixing polymers as defined above may be chosen from the following polymers: (1) copolymers with acidic vinyl units and basic vinyl units, such as those resulting from the copolymerization of a monomer derived from a compound vinyl bearing a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US Pat. No. 3,836,537, (2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom by an alkyl group, b ) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as primary, secondary, tertiary and quaternary amine substituted esters of acrylic and methacrylic acids, and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. The N-substituted acrylamides or methacrylamides that are more particularly used are the compounds whose alkyl groups contain from 2 to 12 carbon atoms, and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides. The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides. Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. It is more particularly the copolymers whose CTFA name (4th Ed., 1991) is octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, such as the products sold under the name AMPHOMER® or LOVOCRYL® 47 by the company National Starch. (3) polyamino amides crosslinked and partially or completely acylated derived from polyaminoamides of general formula CO-R ~ o CO-Z (XVII) in which R10 represents a divalent group derived from a saturated dicarboxylic acid, a monohydric aliphatic acid or ethylenically double bonded dicarboxylic acid ester of a lower alkanol having 1 to 6 carbon atoms of these acids or a group derived from the addition of any of said acids with a bis-primary amine or bis -secondary, and Z denotes a group derived from a bis-primary, mono- or bis-secondary polyalkylenepolyamine and preferably represents

a) in the proportions of 60 to 100 mol%, the NH group DCH2) X NH P (XVIII) where x = 2 and p = 2 or 3, or x = 3 and p = 2 this group derived from diethylene triamine, triethylenetetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol%, the group (XVIII) above, in which x = 2 and p = 1 and which is derived from ethylene diamine, or the group derived from piperazine: c) in the proportions of 0 to 20 mol%, the -NH- (CH 2) 6 -NH- group derived from hexamethylenediamine, these polyaminoamides being crosslinked by addition reaction of a bifunctional crosslinking agent chosen from epihalohydrins; , diepoxides, dianhydrides, bis-unsaturated derivatives, by means of 0.025 to 0.35 mole of crosslinking agent per amine group of the polyaminoamide, and acylated by the action of acrylic acid, chloroacetic acid or an alkane - sultone or their salts. The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms, such as adipic, trimethyl-2,2,4-adipic and trimethyl-2,4,4-adipic acids, terephthalic acids, and double acids. ethylenic bond such as, for example, acrylic, methacrylic, itaconic acids. The alkane sultones used in the acylation are preferably propane or butane sultone, the salts of the acylating agents are preferably the sodium or potassium salts. (4) polymers comprising zwitterionic units of formula: in which R 11 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer of 1 to 3, R 12 and R 13 represent a hydrogen atom, a methyl, ethyl or propyl group, R14 and R15 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R14 and R15 does not exceed 10. The polymers comprising such patterns may also include units derived from non-zwitterionic monomers such as R14

N- (CH 2) Z C -O R 13 dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate. By way of example, mention may be made of methyl methacrylate / methyl dimethylcarboxymethylammonioethylmethacrylate copolymers, such as the product sold under the name DIAFORMER Z301 by Sandoz. (5) polymers derived from chitosan having monomeric units corresponding to the following formulas: CHZOH CHZOH the unit (D) being present in proportions of between 0 and 30%, the unit (E) in proportions of between 5 and 50% and the unit (F) in proportions of between 30 and 90%, it being understood that in this unit (F), R16 represents a group of formula: 18 ¶19 R1 C (O) q C

in which if q = 0, R 17, R 18 and R 19, which may be identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or more atoms nitrogen and / or 0 -O (D) H NHCOCH 3 O -OH (E) H NH 2 HH R 16 -COOH optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio radical whose alkyl group carries an amino residue, at least one of the groups R17, R18 and R19 being in this case a hydrogen atom; or if q = 1, R 17, R 18 and R 19 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids. (6) polymers comprising units corresponding to the general formula (XIX) which are, for example, described in patent FR 1 400 366: 120 (CH-CH 2) CH CH 1 1 COOH CO 1 N R 21 R 24 1 R 23 R 22 (XIX) wherein R20 is hydrogen, CH3O, CH3CH2O, phenyl, R21 is hydrogen or lower alkyl such as methyl, ethyl, R22 is hydrogen or alkyl C1-C6 lower alkyl group such as methyl, ethyl, R23 denotes a C1-C6 lower alkyl group such as methyl, ethyl or a group corresponding to the formula: -R24-N (R22) 2, R24 representing a group - CH2- CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH 2 -CH (CH 3) -, R 22 having the meanings mentioned above. (7) polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan, sold under the name "Evalsan" by the company Jan Dekker. (8) amphoteric polymers of the -DXDX type chosen from: a) the polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula: -DXDXD- (XX) where D denotes a group / \ -NN \ / and X denotes the symbol E or E ', E or E' identical or different designating a divalent group which is a straight or branched chain alkylene group, having up to 7 carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups and which may further comprise oxygen, nitrogen, sulfur, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulphoxide, sulphone, sulphonium, alkylamine, alkenylamine, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide groups, alcohol, ester and / or urethane. b) Polymers of the formula: D-X-D-X- (XXI ') where D denotes a group and X denotes the symbol E or E' and at least once E '; E having the meaning indicated above and E 'being a bivalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the main chain, substituted or unsubstituted by one or more hydroxyl groups and comprising one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betaineized by reaction with the acid; chloroacetic acid or sodium chloroacetate. (9) (C 1 -C 5) vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with an N, N-dialkylaminoalkanol. These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam. Among the amphoteric fixing polymers described above, the most particularly preferred are those of the family (3), such as the copolymers whose CTFA name is octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer, such as the products sold under the names AMPHOMER®. , AMPHOMER® LV 71 or LOVOCRYL® 47 by NATIONAL STARCH and those of the family (4) such as methyl methacrylate / dimethylcarboxymethylammonioethylmethacrylate copolymers sold for example under the name DIAFORMER® Z301 by SANDOZ. The nonionic fixing polymers that can be used according to the present invention are chosen, for example, from: polyalkyloxazolines; homopolymers of vinyl acetate; vinyl acetate copolymers such as, for example, copolymers of vinyl acetate and acrylic ester, copolymers of vinyl acetate and ethylene, or copolymers of vinyl acetate and of maleic ester, for example, dibutyl maleate; homopolymers and copolymers of acrylic esters, such as, for example, copolymers of alkyl acrylates and of alkyl methacrylates such as the products offered by the company Rohm & Haas under the names PRIMAL® AC-261 K and EUDRAGIT® NE 30D, by the company BASF under the name 8845, by the company HOECHST under the name APPRETAN® N9212; copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; mention may be made of the products sold under the name CJ 0601 B by the company Rohm &Haas; homopolymers of styrene; styrene copolymers such as, for example, styrene and alkyl (meth) acrylate copolymers such as Mowilith® LDM 6911, Mowilith® DM 611 and Mowilith® LDM 6070 products supplied by the company Hoechst, the RHODOPAS products ® SD 215 and RHODOPAS® DS 910 offered by RHODIA CHIMIE; copolymers of styrene, alkyl methacrylate and alkyl acrylate; copolymers of styrene and butadiene; or copolymers of styrene, butadiene and vinylpyridine; polyamides; homopolymers of vinyllactam such as polyvinylpyrrolidone; and copolymers of vinyllactam such as a poly (vinylpyrrolidone / vinyllactam) copolymer sold under the trade name Luvitec® VPC 55K65W by the company BASF, polyvinylpyrrolidone / vinyl acetate copolymers, such as those sold under the name PVPVA® S630L by ISP, Luviskol® VA 73, VA 64, VA 55, VA 37 and VA 28 by BASF; and poly (vinylpyrrolidone / vinyl acetate / vinyl propionate) terpolymers such as, for example, that marketed under the name Luviskol® VAP 343 by the company BASF.

The alkyl groups of the nonionic polymers mentioned above preferably have from 1 to 6 carbon atoms. The additional fixing anionic polymers are different from the carboxylic polymers of the invention. They possess anionic units derived from sulphonic or phosphoric acids and more preferably from sulphonic acids. Homopolymers and copolymers comprising sulphonic groups are polymers comprising vinylsulphonic, styrene-sulphonic, naphthalenesulphonic or acrylamido-alkylsulphonic units. They are different from the urethane-free carboxylic anionic polymers of the invention. These polymers may especially be chosen from: - the salts of polyvinylsulphonic acid having a molecular weight of between about 1,000 and 100,000, as well as copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and their esters, as well as acrylamide or its derivatives, vinyl ethers and vinylpyrrolidone; salts of polystyrene-sulphonic acid, such as the sodium salts sold, for example, under the names Flexan® 500 and Flexan® 130 by National Starch. These compounds are described in patent FR 2 198 719. - The salts of polyacrylamidesulfonic acids such as those mentioned in US Pat. No. 4,128,631, and more particularly the polyacrylamidoethylpropanesulphonic acid sold under the name COSMEDIA POLYMER HSP 1180 by Henkel . branched sulphonic polyesters, such as the product sold under the name AQ 1350; linear sulphonic polyesters, such as those known under the name INCI Diglycol / CHDM / Isophthalates / SIP, and sold under the trade names Eastman AQ polymer ( AQ35S, AQ38S, AQ55S, AQ48 Ultra) by Eastman Chemical. It is also possible to use, as fixing polymers, functionalized or non-silicone or non-silicone, cationic, nonionic, anionic or amphoteric polyurethanes, or mixtures thereof. The polyurethanes particularly targeted by the present invention are those described in applications EP 0 751 162, EP 0 637 600, EP 0 648 20 485 and FR 2 743 297 of which the applicant is the holder, as well as in applications EP 0 656 021 and WO 94/03510 from BASF, and EP 0 619 111 from National Starch. Polyurethanes which are particularly suitable for the present invention include the products sold under the names LUVISET PUR® and LUVISET® Si PUR by BASF.

Preferably the additional fixing polymer or polymers are not polyurethanes.

Preferably, the additional fixing polymer or polymers are anionic or nonionic. When present, the additional fixing polymer or polymers represent from 0.1 to 20% by weight, more preferably from 0.5 to 10% by weight relative to the total weight of the composition. The styling composition may furthermore comprise additives such as silicones in soluble, dispersed, micro-dispersed form, treating active ingredients, moisturizing agents such as glycerol, UV filters, acids, bases, plasticizing agents, solubilizing agents, preserving agents, vitamins and provitamines, dyes, pigments, anionic, cationic, nonionic or amphoteric surfactants, perfumes, anti-corrosion agents, and mixtures thereof. Those skilled in the art will be careful to select any additives and their amount so that they do not adversely affect the properties of the compositions of the present invention. These additives are especially present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition. Preferably, the two-compartment aerosol device is constituted by an external aerosol can comprising an internal bag hermetically sealed to a valve. The composition is introduced into the inner bag and a compressed gas is introduced between the bag and the can at a pressure sufficient to release the product as a spray through the orifice of a nozzle. Such a device is marketed under the name EP SPRAY by the company EP-SPRAY SYSTEM SA. The aerosol devices of the invention are preferably hair lacquers. The present invention also relates to a styling process which consists in that the styling composition contained in the aerosol device according to the invention is vaporized on wet hair or not and that the hair is generally dried with a heating device ( hair dryer, helmet, ...) or let them dry spontaneously ..

The following example is given by way of non-limiting example of the present invention. All amounts are indicated in percent by weight of active ingredients relative to the total weight of the composition.

Example 1

A styling composition was prepared from the following ingredients: Copolymer vinyl acetate / crotonic acid (90/10) 5.00 (Luviset CA 66 supplier BASF) Amino methyl propanol Qsp 95-100% neutralization perfume 0.10 Ethyl alcohol qs 100 introduced the composition prepared above in an aerosol dispensing device marketed under the name EP SPRAY 20 by the company EP SPRAY SYSTEM SA described above. A reference valve 6001 format D6 is attached to a conventional aerosol can, and the diffuser is a diffuser with a swirl nozzle. The bag is filled with the composition as indicated above. Compressed air is introduced between the bag and the can.

The composition was sprayed on dry hair. Spraying is in the form of a mild spray of very good quality. After drying, hair is obtained which has a very good hold. The aerosol device does not become clogged with applications.5

Claims (13)

REVENDICATIONS1. A two-compartment aerosol device comprising: a) in a first compartment, a styling composition comprising at least one urethane-free carboxylic anionic polymer in an alcoholic or aqueous-alcoholic medium which comprises at least 5% by weight relative to the weight of said composition , a monohydric alcohol C1-C4, and b) in a second compartment, a compressed gas selected from air, nitrogen, carbon dioxide and mixtures thereof. Aerosol device according to claim 1, characterized in that the compressed gas is air. 3. aerosol device according to claim 1 or 2, characterized in that the pressure of the compressed gas is between 1 and 12 bar. 4. aerosol device according to claim 3, characterized in that the pressure of the compressed gas is between 9 and 11 bar. 5. Device according to any one of the preceding claims, characterized in that the anionic polymer is chosen from: A) copolymers of acrylic acid and acrylamide, the sodium salts of polyhydroxycarboxylic acids; B) copolymers of acrylic or methacrylic acid with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted onto a polyalkylene glycol such as polyethylene glycol, and optionally crosslinked. C) Crotonic acid copolymers, such as those comprising in their chain vinyl acetate or propionate units, and optionally other monomers such as allyl or methallyl esters, vinyl ethers or vinyl esters of a saturated carboxylic acid, linear or branched, long hydrocarbon chain, such as those comprising at least 5 carbon atoms, these polymers may optionally be grafted or crosslinked, or another vinyl ester monomer, allyl or methallylique a carboxylic acid a- or R-cyclic D) copolymers of C 4 -C 8 monounsaturated carboxylic acids or anhydrides chosen from: copolymers comprising (i) one or more maleic, fumaric, itaconic acids or anhydrides and (ii) at least one monomer chosen from esters vinyl ethers, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these opolymers being optionally monoesterified or monoamidified. copolymers comprising (i) one or more maleic, citraconic and itaconic anhydride units and (ii) one or more monomers chosen from allyl or methallyl esters optionally containing one or more acrylamide, methacrylamide, α-olefin or acrylic or methacrylic ester groups; acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. E) polyacrylamides having carboxylate groups. 6. aerosol device according to any one of claims 1 to 5, characterized in that the anionic polymer is selected from acrylic acid copolymers such as terpolymers acrylic acid / ethyl acrylate / N-tert-butylacrylamide, copolymers derived from crotonic acid such as vinyl acetate terpolymers / vinyl tert-butylbenzoate / crotonic acid and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers, polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as monoesterified methyl vinyl ether / maleic anhydride copolymers, methacrylic acid and methyl methacrylate copolymers, methacrylic acid copolymers and ethyl acrylate and vinyl acetate / crotonic acid copolymers and copolymers vinyl acetate / crotonic acid grafted with polyethylene glycol. 7. Aerosol device according to any one of the preceding claims, characterized in that the anionic or carboxylic polymers without urethane unit are present in an amount ranging from 0.5 to 20% by weight relative to the total weight of the composition. 8. Aerosol device according to any one of the preceding claims, characterized in that the anionic or carboxylic polymers without urethane unit are present in an amount ranging from 1 to 12% by weight relative to the total weight of the composition. 30 9. aerosol device according to any one of the preceding claims, characterized in that the monohydric alcohol of the invention is preferably selected from ethanol, isopropanol, n propanol, tert-butanol or mixtures thereof preferably from ethanol, isopropanol or their mixtures even more preferably is ethanol. 10. Aerosol device according to any one of the preceding claims, characterized in that the composition comprises from 5 to 99.9% by weight, more preferably from 10 to 99% by weight and even more preferably from 20 to 98% by weight. relative to the total weight of said composition, one or more C1-4 monohydric alcohols. 11. aerosol device according to any one of the preceding claims, characterized in that the composition comprises from 1 to 95%, and preferably from 10 to 90% water by weight relative to the total weight of the composition. 12. aerosol device according to any one of the preceding claims, characterized in that the styling composition further comprises one or more additional fixing polymers different from the anionic polymers without urethane unit of the invention and can be anionic, cationic, amphoteric or nonionic, preferably anionic or nonionic. 13, Use of the aerosol device according to any one of the preceding claims for a hairspray. Styling process, characterized in that the styling composition contained in the aerosol device according to any one of Claims 1 to 12 is vaporized on wet hair or not.