FR2834514A1 - Aerosol device useful for hair styling includes a film-forming polymer dissolved or finely dispersed in a water-in-oil emulsion containing a silicone emulsifier - Google Patents

Abstract

Aerosol device comprises a propellant and a hair styling composition comprising a film-forming polymer dissolved or finely dispersed in a water-in-oil emulsion containing a silicone emulsifier. An Independent claim is also included for a hair styling method comprising spraying the contents of the above device onto shaped hair and allowing it to dry.

Description

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Aerosol device containing a water-in-oil emulsion stabilized with a silicone emulsifier
The present invention relates to an aerosol device containing a propellant and a water-in-oil emulsion stabilized with a silicone emulsifying agent, and a capping process using such a device.

 Styling compositions packaged in the form of an aerosol spray generally contain a large fraction of alcohol. However, cosmetic products with a high alcohol content are subject to special monitoring, particularly in the United States, following the recent public awareness of the environmental problems resulting from the emission of volatile organic compounds into the environment. atmosphere.

 A solution to reduce the amount of alcohol, or even completely eliminate alcohol formulas, is the replacement by an equivalent amount of water. This introduction of large amounts of water into aerosol sprays for fixing the hair, such as lacquers, however, leads to undesirable major deformation of the hair and degradation of the cosmetic properties. Furthermore, most hydrocarbon propellants are incompatible with water and their use in compositions with high water content is therefore generally impossible.

 The Applicant has made the surprising discovery that the use of silicone surfactants as emulsifiers for stabilizing water-in-oil emulsions, packaged in an aerosol device, made it possible to prepare hair styling compositions with reduced alcohol content or alcohol free which have a relatively low wetting effect and give deposits with excellent cosmetic properties.

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 The reduction of the wetting effect by using a water-oil emulsion is accompanied by a lower deformation of the hair during the spraying of the compositions on the hair.

 The presence of an oily phase and a silicone emulsifying agent facilitates the disentangling of the hair and makes the hair soft and smooth. The fixed hair remains flexible and unraveling the hairstyle at the end of the day is very easy.

 Moreover, the presence of an oily phase makes it possible to use, as propellant, non-halogenated hydrocarbons which are miscible with it, such as butane or propane, which is very advantageous for economic point of view.

 The subject of the present invention is therefore an aerosol device containing (a) at least one propellant and (b) a styling composition containing at least one fixing, dissolved or finely dispersed film-forming polymer in a cosmetically acceptable water-in-oil emulsion comprising water, at least one oil and at least one silicone emulsifier.

 The invention also relates to a styling process of vaporizing the mixture contained in said aerosol device on the hair shaped and to let the hair so treated.

 The fixing film-forming polymers that can be used in the hair styling compositions of the present invention are well known to those skilled in the art. They can be of natural origin, and possibly be modified, or of synthetic origin.

These polymers may be chosen, for example, from the cationic, anionic, nonionic or amphoteric fixing polymers listed below:
The cationic fixing polymers that may be used according to the present invention are preferably chosen from polymers containing primary, secondary, tertiary and / or quaternary amine groups.

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 part of the polymer chain or directly connected thereto, and having a number average molecular weight of between 500 and about 5,000,000, and preferably between 1,000 and 3,000,000.

dans lesquelles :
RI et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle en CI-6 ;
R3 désigne un atome d'hydrogène ou un groupe CH3 ;
A est un groupe alkyle linéaire ou ramifié, comportant de 1 à 6 atomes de carbone ou un groupe hydroxyalkyle comportant de 1 à 4 atomes de carbone ; Rt, R$, R6 représentent indépendamment chacun un groupe alkyle ayant de 1 à 18 atomes de carbone ou un groupe benzyle ;
X désigne un anion méthosulfate ou halogénure tel que chlorure ou bromure. Among these polymers, mention may be made more particularly of the following cationic polymers: (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising units corresponding to at least one of the following formulas:

in which :
R1 and R2 each independently represent a hydrogen atom or a C1-C6 alkyl group;
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; Rt, R6, R6 are each independently an alkyl group having 1 to 18 carbon atoms or a benzyl group;
X denotes a methosulphate or halide anion such as chloride or bromide.

 The copolymers of family (1) also contain one or more units derived from comonomers selected from the family of acrylamides, methacrylamides, diacetone-acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyl groups,

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 (meth) acrylics or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

éthyle quatemisés au sulfate de diméthyle ou avec un halogénure de méthyle tels que celui vendu sous la dénomination HERCOFLOCO par la société HERCULES, - les copolymères d'acrylamide et de chlorure de méthacryloyloxy- éthyltriméthylammonium décrits, par exemple, dans la demande de brevet EPA-080976 et vendus sous la dénomination BINA QUARTO P100 par la société CIBA GEIGY, - le copolymère d'acrylamide et de méthosulfate de méthacryloyloxy- éthyltriméthylammonium vendu sous la dénomination RETENS vendu par la société HERCULES, - les copolymères vinylpyrrolidone/acrylate ou méthacrylate de

dialkylaminoalkyle quatemisés ou non, tels que les produits vendus sous la dénomination GAFQUATO par la société ISP comme, par exemple, GAFQUATO 734 ou GAFQUATO 755, ou bien les produits dénommés "COPOLYMER 845, 958 et 937". Ces polymères sont décrits en détail dans les brevets français FR 2 077 143 et FR 2 393 573, - les terpolymères méthacrylate de diméthylaminoéthyle/ vinylcaprolactame/vinylpyrrolidone tels que le produit commercialisé sous la dénomination GAFFIXO VC 713 par la société ISP, et - les copolymères vinylpyrrolidone/méthacrylamide de diméthyl- aminopropyle quatemisé tels que notamment le produit commercialisé sous la dénomination GAFQUATO HS 100 par la société ISP. Thus, among these copolymers of the family (1), mention may be made of: copolymers of acrylamide and of dimethylamino methacrylate;

ethyl quaternized with dimethyl sulfate or with a methyl halide such as that sold under the name HERCOFLOCO by the company HERCULES, - copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described, for example, in the patent application EPA- 080976 and sold under the name BINA QUARTO P100 by the company CIBA GEIGY, the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate sold under the name RETENS sold by the company HERCULES, the vinylpyrrolidone / acrylate or methacrylate copolymers of

quaternized or non-quaternized dialkylaminoalkyl, such as the products sold under the name GAFQUATO by ISP, for example GAFQUATO 734 or GAFQUATO 755, or the products designated "COPOLYMER 845, 958 and 937". These polymers are described in detail in French patents FR 2,077,143 and FR 2,393,573, dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIXO VC 713 by the company ISP, and copolymers quaternized dimethylaminopropyl vinylpyrrolidone / methacrylamide, such as in particular the product sold under the name GAFQUATO HS 100 by the company ISP.

 (2) quaternized polysaccharides described more particularly in US Pat. Nos. 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups. Such products are sold in particular under the names Jaguar C13 S, Jaguar C 15, and Jaguar C 17 by the company Meyhall.

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 (3) quaternary copolymers of vinylpyrrolidone and of vinylimidazole, such as the products sold by BASF under the name LUVIQUAT TFC.

 (4) chitosans and their salts such as chitosan acetate, lactate, glutamate, gluconate or pyrrolidone carboxylate.

 Among these compounds, mention may be made of chitosan having a degree of deacetylation of 90.5% by weight sold under the name KYTAN BRUT STANDARD by the company ABER TECHNOLOGIES, the pyrrolidone carboxylate of chitosan sold under the name KYTAMEE PC by the company AMERCHOL .

 (5) cationic cellulose derivatives such as copolymers of cellulose or of cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkylcelluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses grafted in particular with a salt of methacryloyloxyethyltrimethylammonium, methacrylamidoproyltrimethylammonium or dimethyldiallylammonium salt.

 These polymers are sold in particular under the names CELQUATO L200 and CELQUATO H100 by the company NATIONAL STARCH.

 The anionic fixing polymers generally used are polymers containing groups derived from carboxylic acid, sulphonic acid or phosphoric acid and have a number-average molecular weight of between about 500 and 5,000,000.

 The carboxylic groups are provided by unsaturated mono- or di-carboxylic acid monomers, such as those corresponding to the formula:

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dans laquelle n est un nombre entier de 0 à 10, Al désigne un groupement méthylène, éventuellement relié à l'atome de carbone du groupement insaturé ou au groupement méthylène voisin lorsque n est supérieur à 1, par l'intermédiaire d'un hétéroatome tel que oxygène ou soufre, R ? désigne un atome d'hydrogène, un groupement phényle ou benzyle, Rs désigne un atome d'hydrogène, un groupement alkyle inférieur ou carboxyle, et

R9 désigne un atome d'hydrogène, un groupement alkyle inférieur, un groupement-CH-COOH, phényle ou benzyle.

in which n is an integer from 0 to 10, Al denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1, via a heteroatom such as that oxygen or sulfur, R? denotes a hydrogen atom, a phenyl or benzyl group, Rs denotes a hydrogen atom, a lower alkyl or carboxyl group, and

R9 denotes a hydrogen atom, a lower alkyl group, a -CH-COOH group, phenyl or benzyl group.

 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 with preferred carboxylic groups according to the invention are:
A) Homo-or copolymers of acrylic or methacrylic acid or their salts and in particular the products sold under the names VERSICOLO E or K by ALLIED COLLOID and ULTRAHOLDO by BASF, copolymers of acrylic acid and acrylamide sold in the form of sodium salt under the names RETENS 421, 423 or 425 by the company HERCULES, and 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. Such polymers are described in particular in the French patent

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dans les demandes de brevets luxembourgeois n 75370 et 75371 et proposés sous la dénomination QUADRAMEE par la société AMERICAN CYANAMID. On peut également citer les copolymères d'acide acrylique et de méthacrylate d'alkyle en Ci-C4 et les terpolymères de vinylpyrrolidone, d'acide acrylique et de méthacrylate d'alkyle en C1-C20, par exemple, de lauryle, tels que celui commercialisé par la société ISP sous la dénomination ACRYLIDONEO LM et les terpolymères acide méthacrylique/acrylate d'éthyle/acrylate de tertiobutyle tels que le produit commercialisé sous la dénomination LUVINER 100 P par la société BASF. FR 1 222 944 and the German patent application DE 2 330 956, copolymers of this type comprising in their chain an acrylamide unit optionally N-alkylated and / or N-hydroxyalkylated such as described in particular

in the Luxembourg patent applications No. 75370 and 75371 and offered under the name QUADRAMEE by the company AMERICAN CYANAMID. Mention may also be made of copolymers of acrylic acid and of C 1 -C 4 alkyl methacrylate and terpolymers of vinylpyrrolidone, of acrylic acid and of C 1 -C 20 alkyl methacrylate, for example lauryl, such as sold by ISP under the name ACRYLIDONEO LM and methacrylic acid / ethyl acrylate / tertiobutyl acrylate terpolymers such as the product marketed under the name LUVINER 100 P by the company BASF.

 C) Copolymers derived from crotonic acid, 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 and crosslinked, or another vinyl ester monomer, allyl or methallylique a carboxylic acid α-ouzo cyclic. Such polymers are described inter alia in the French patents 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 entering this class are the resins 28-29-30,26-13-14 and 28-13-10 marketed by the company National Starch.

 D) copolymers derived from 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 selected from the group consisting of vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. Such polymers are described in particular in US Pat. Nos. 2,047,398, 2,723,248 and 2,102,113, and GB 839,805.

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 are especially those sold under the names GANTIEZ 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 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. -
These polymers are for example described in the French patents FR 2350384 and FR 2357241 of the applicant.

 E) Polyacrylamides having carboxylate groups.

 The polymers comprising the sulphonic groups are polymers comprising vinylsulphonic, styrene-sulphonic, naphthalenesulphonic or acrylamido-alkylsulphonic units.

 These polymers may be chosen in particular from: - the salts of polyvinylsulphonic acid having a molecular mass 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.

 the salts of polystyrene-sulphonic acid, such as the sodium salts sold, for example, under the names FLEXANO 130 and FLEXANO 500 by the company National Starch. These compounds are described in patent FR 2 198 719.

 the polyacrylamidesulfonic acid salts 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 the company HENKEL.

 The amphoteric fixing polymers that may be used in the styling foams of the present invention 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 atom.

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 basic nitrogen and C denotes a unit derived from a monomer having one or more carboxylic or sulfonic groups. The amphoteric fixing polymers may also comprise zwitterionic units of the carboxybetaine or sulfbbetaine type.

 It may also be cationic main chain polymers comprising primary, secondary, tertiary or quaternary amine groups, among which at least one gate, via a hydrocarbon radical, a carboxylic acid or sulfonic acid group. The amphoteric fixing polymers may also have an anionic chain derived from α, β-unsaturated carboxylic acids, wherein one of the carboxyl groups has been reacted with a polyamine having one or more primary amine groups.

 The amphoteric fixing polymers as defined above are chosen in particular from the following polymers: (1) the polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying 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 substituent esters of acrylic and methacrylic acids, and the quaternization product of dimethylaminoethyl methacrylate with the sulfate dimethyl or diethyl.

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 The N-substituted acrylamides or methacrylamides are in particular the compounds in which the alkyl groups contain from 2 to 12 carbon atoms, and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

 The acidic 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.

AMPHOMER ou LOVOCRYLO 47 par la société NATIONAL STARCH. The copolymers whose CTFA (4th Ed., 1991) name is octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer, such as the products sold under the name, are particularly used.

AMPHOMER or LOVOCRYLO 47 by the company NATIONAL STARCH.

dans laquelle Rio représente un groupe divalent dérivé d'un acide dicarboxylique saturé, d'un acide aliphatique mono ou dicarboxylique à double liaison éthylénique, d'un ester d'un alcanol inférieur ayant 1 à 6 atome de carbone de ces acides ou d'un groupe dérivant de l'addition de l'un quelconque desdits acides avec une amine bis-primaire ou bis-secondaire, et Z désigne un groupe dérivant d'une polyalkylène-polyamine bis-primaire, mono-ou bissecondaire et de préférence représente : (i) dans les proportions de 60 à 100 % en moles, le groupe

où x = 2 et p = 2 ou 3, ou bien x = 3 et p = 2 (3) the partially or completely crosslinked and partially alkylated polyaminoamides derived from polyaminoamides of general formula:

wherein Rio represents a divalent group derived from a saturated dicarboxylic acid, an ethylenically double-bonded mono or dicarboxylic aliphatic acid, an 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 or bis-secondary amine, and Z denotes a group derived from a bis-primary, mono-or bissecondary polyalkylene polyamine and preferably represents: (i) in the proportions of 60 to 100 mol%, the group

where x = 2 and p = 2 or 3, or x = 3 and p = 2

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(iii) dans les proportions de 0 à 20 % en moles, le groupe - NH- (CH2) 6-NH- dérivant de l'hexaméthylènediamine, ces polyaminoamides étant réticulés par réaction d'addition d'un agent réticulant bifonctionnel choisi parmi les épihalohydrines, les diépoxydes, les dianhydrides, les dérivés bis-insaturés, au moyen de 0,025 à 0,35 mole d'agent réticulant par groupement amine du polyaminoamide, et alcoyles par action d'acide acrylique, d'acide chloracétique ou d'une alcane-sultone ou de leurs sels. this group derived from diethylene triamine, triethylene tetraamine or dipropylene triamine; (ii) in the proportions of 0 to 40 mol%, the group - NH- [(CH2) x -NH] p- where x = 2 and p = 1 and which is derived from ethylene diamine, or the group derived from piperazine:

(iii) 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 moles of crosslinking agent per amine group of the polyaminoamide, and alkyls by the action of acrylic acid, chloroacetic acid or a alkane-sultone or their salts.

 The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic acid, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic acid, terephthalic acid, and double acids. ethylenic bond such as, for example, acrylic, methacrylic, itaconic acids.

 The alkane sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

(4) polymers having zwitterionic units of formula:

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 in which R1 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z each represent an integer from 1 to 3, R12 and R13 represent a hydrogen atom, a methyl, ethyl or propyl, RI 4 and RI represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R14 and Ris does not exceed 10.

 Polymers comprising such units may also include units derived from non-zwitterionic monomers such as 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 / dimethylcarboxymethylammonioethyl methacrylate copolymers, such as the product sold under the name DIAFORMEE Z301 by Sandoz.

le motif (A) étant présent dans des proportions comprises entre 0 et 30%, le motif (B) dans des proportions comprises entre 5 et 50% et le motif (C) dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif (C), R16 représente un groupe de formule : (5) polymers derived from chitosan having monomeric units corresponding to the following formulas:

the unit (A) being present in proportions of between 0 and 30%, the unit (B) in proportions of between 5 and 50% and the unit (C) in proportions of between 30 and 90%, it being understood that in this unit (C), R16 represents a group of formula:

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dans laquelle si q = 0, R17, R. et et ruz identiques ou différents, représentent chacun un atome d'hydrogène, un reste méthyle, hydroxyle, acétoxy ou amino, un reste monoalcoylamine ou un reste dialcoylamine éventuellement interrompus par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes amine, hydroxyle, carboxyle, alcoylthio, sulfonique, un reste alcoylthio dont le groupe alcoyle porte un reste amino, l'un au moins des groupes R17, Rig et RI9 étant dans ce cas un atome d'hydrogène ; ou si q = 1, Rl7, Ris et RI9 représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides.

in which if q = 0, R 17, R 4 and the same or different ruz, each represents 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 optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulfonic acid, an alkylthio radical whose alkyl group carries an amino residue, at least one of the groups R17, Rig and RI9 being in this case a hydrogen atom; or if q = 1, R17, R17 and R19 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

 (6) The polymers obtained by N-carboxylation of chitosan such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under the name EX ALS by JAN DEKKER.

dans laquelle R20 représente un atome d'hydrogène ou un groupe CHsO, CH3CH2O ou phényle, R21 désigne un atome d'hydrogène ou un groupe alkyle inférieur tel que méthyle et éthyle, R22 désigne un atome d'hydrogène ou un (7) The polymers described in French Patent FR 1 400 366 and corresponding to the formula

in which R 20 represents a hydrogen atom or a CH 3 O, CH 3 CH 2 O or phenyl group, R 21 denotes a hydrogen atom or a lower alkyl group such as methyl and ethyl, R 22 denotes a hydrogen atom or a

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groupe alkyle inférieur en CI-C6 tel que méthyle et éthyle, R23 désigne un groupe alkyle inférieur en Cl-C6 tel que méthyle, éthyle ou un groupe répondant à la formule :-R24-N (R22) 2, R24 représentant un groupement - CH2-CH2-,-CH2-CH2-CH2-,-CH2-CH (CH3)-, et R22 ayant les significations mentionnées ci-dessus.

C1-C6 lower alkyl group such as methyl and 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 - CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, -CH 2 -CH (CH 3) -, and R 22 having the meanings mentioned above.

et X désigne le symbole E ou E', E ou E'identiques ou différents désignent un groupe bivalent qui est un groupe alkylène à chaîne droite ou ramifiée, comportant jusqu'à 7 atomes de carbone dans la chaîne principale non substituée ou substituée par des groupements hydroxyle et pouvant comporter en outre des atomes d'oxygène, d'azote, de soufre, 1 à 3 cycles aromatiques et/ou hétérocycliques ; les atomes d'oxygène, d'azote et de soufre étant présents sous forme de groupements éther, thioéther, sulfoxyde, sulfone, sulfonium, alkylamine, alcénylamine, des groupements hydroxyle, benzylamine, oxyde d'amine, ammonium quaternaire, amide, imide, alcool, ester et/ou uréthanne. (8) Amphoteric polymers of the -DXDX type chosen from: (a) polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula: - DXDXD- where D denotes a group

and X denotes the symbol E or E ', E or E' the same or different denotes a bivalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the unsubstituted or substituted primary chain. hydroxyl groups and 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 formula: - D-X-D-X- where D denotes a group

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et X désigne le symbole E ou E'et au moins une fois E' ; E ayant la signification indiquée ci-dessus et E'est un groupe bivalent qui est un groupe alkylène à chaîne droite ou ramifiée, ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs groupes hydroxyle et comportant un ou plusieurs atomes d'azote, l'atome d'azote étant substitué par une chaîne alkyle interrompue éventuellement par un atome d'oxygène et comportant obligatoirement une ou plusieurs fonctions carboxyle ou une ou plusieurs fonctions hydroxyle et bétaïnisées par réaction avec l'acide chloracétique ou du chloroacétate de soude.

and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E is a bivalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the main chain, whether or not substituted with one or more hydroxyl groups and having 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) Alkyl-C-vinyl ether / maleic anhydride copolymers partially modified by half-amidification with N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with N, N-dialkanolamine. These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam.

sous la dénomination APPRETAN EM par la société HOECHST ou le produit proposé sous le nom de RHODOPAS A 012 par la société RHONE POULENC, - les copolymères d'acétate de vinyle et d'ester acrylique tels que le produit proposé sous le nom de RHODOPASO AD 310 de la société
RHONE POULENC, The nonionic fixing polymers are chosen, for example, from: vinylpyrrolidone, copolymers of vinylpyrrolidone and of vinyl acetate, polyalkyloxazolines such as the polyethyloxazolines proposed by Dow Chemical under the names PEOXO 50 000, PEOXO 200,000 and PEOXO 500,000, - vinyl acetate homopolymers such as the proposed product

under the name APPRETAN EM by the company HOECHST or the product sold under the name RHODOPAS A 012 by the company RHONE POULENC, - copolymers of vinyl acetate and acrylic ester such as the product sold under the name RHODOPASO AD 310 of society
RHONE POULENC,

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dénominations PRIMAL AC-261 K et EUDRAGITO NE 30 D, par la société BASF sous les dénominations ACRONALO 601, LUHYDRAN LR 8833 ou 8845, par la société HOECHST sous les dénominations APPRET N9212 et N9213 ; - les copolymères d'acrylonitrile et d'un monomère non ionique choisis, par exemple, parmi le butadiène et les (méth) acrylates d'alkyle ; on peut citer les produits proposés sous les dénominations NIPOL# LX 531 B par la société NIPPON ZEON ou ceux proposés sous la dénomination CJ 0601 B par la société ROHM & HAAS,

- les polyuréthannes tels que les produits proposés sous les dénominations ACRYSOL RM 1020 ou ACRYSOLO RM 2020 par la société ROHM & HAAS, les produits URAFLEXO XP 401 et URAFLEXO XP 402 UZ par la société DSM RESINS, - les polyamides tels que le produit ESTAPOE LO 11 proposé par la société RHONE POULENC, - les gommes de guar non ioniques chimiquement modifiées ou non modifiées. Les gommes de guar non modifiées sont par exemple les produits vendus sous la dénomination VIDOGLIMO GH 175 par la société UNIPECTINE et sous la dénomination JAGUAR C par la société MEYHALL. Les gommes de guar modifiées sont de copolymers of vinyl acetate and of ethylene, such as the product sold under the name APPRETANE TV by the company
Hoechst, copolymers of vinyl acetate and of maleic ester, for example dibutyl maleate such as the product sold under the name APPRETANO MB EXTRA by HOECHST, copolymers of polyethylene and maleic anhydride polyalkyl acrylate and polyalkyl methacrylate, such as the product sold under the name MICROPEARLO RQ 750 by the company MATSUMOTO or the product sold under the name LUHYDRANO A 848 S by the company BASF; 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

PRIMAL AC-261 K and EUDRAGITO NE 30 D denominations, by the company BASF under the names ACRONALO 601, LUHYDRAN LR 8833 or 8845, by HOECHST under the names PRIMES N9212 and N9213; 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 names NIPOL # LX 531 B by the company NIPPON ZEON or those sold under the name CJ 0601 B by the company ROHM & HAAS,

polyurethanes such as the products sold under the names ACRYSOL RM 1020 or ACRYSOLO RM 2020 by the company ROHM & HAAS, the products URAFLEXO XP 401 and URAFLEXO XP 402 UZ by the company DSM RESINS, polyamides such as the product ESTAPOE LO 11 proposed by the company RHONE POULENC, - non-ionic guar gums chemically modified or unmodified. The unmodified guar gums are, for example, the products sold under the name VIDOGLIMO GH 175 by the company UNIPECTINE and under the name JAGUAR C by MEYHALL. The modified guar gums are

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sont par exemple vendues sous les dénominations commerciales JAGUAR HP8, JAGUARs HP60, JAGUAR HP120, JAGUAR DC 293 et JAGUAR HP 105 par la société MEYHALL, ou sous la dénomination GALACTOSOLO 4H4FD2 par la société
AQUALON. Preferably they are modified with C 1 -C 6 hydroxyalkyl groups, preferably with hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. Such nonionic guar gums optionally modified with hydroxyalkyl groups

are for example sold under the trade names JAGUAR HP8, JAGUAR HP60, JAGUAR HP120, JAGUAR DC 293 and JAGUAR HP 105 by the company MEYHALL, or under the name GALACTOSOLO 4H4FD2 by the company
Aqualon.

 It is also possible to use, as fixing polymers, grafted silicone-type film-forming polymers comprising a polysiloxane part and a part consisting of a non-silicone organic chain, one of the two parts constituting the main chain of the polymer and the other being grafted onto said main chain.

 These polymers are for example described in patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0582 152 and WO 93 / 23009 and US Patents 4,693, 935, US 4,728,571 and US 4,972,037.

 These polymers are preferably anionic or nonionic.

où v est un nombre allant de 5 à 700, les pourcentages en poids étant calculés par rapport au poids total des monomères. Such polymers are, for example, the copolymers that can be obtained by radical polymerization from the monomer mixture formed a) from 50 to 90% by weight of tert-butyl acrylate, b) from 0 to 40% by weight of acid acrylic, c) from 5 to 40% by weight of a silicone macromer of formula

where v is a number from 5 to 700, the percentages by weight being calculated with respect to the total weight of the monomers.

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 Other examples of grafted silicone polymers are in particular polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connection link, mixed polymeric units of the poly (meth) acrylic acid and poly type. alkyl (meth) acrylate and polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connecting link, polymeric units of the poly (meth) acrylate isobutyl type.

 Urethane-containing polymers may also be used. These polyurethanes can be functionalized or not, silicone or not. The polyurethanes particularly targeted are those described in applications EP 0 751 162, EP 0 637 600, EP 0 648 485 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 of BASF, and in applications EP 0 619 111 from the company National Starch. As polyurethanes that are particularly suitable for the present invention, mention may be made of the products sold under the names LUVISETPUIC and LUVISETO Si PUR by the company BASF.

 As indicated above, these fixing film-forming polymers are either in the dissolved state in one of the two phases forming the water-in-oil emulsion, or finely dispersed in the aqueous or oily phase or in both.

 In a preferred embodiment of the aerosol devices of the present invention the fixing polymer is in finely dispersed form in one of the emulsion phases. The advantage of the dispersed form lies in the low viscosity of the compositions obtained, which allows a fine and regular nebulization without risk of clogging of the spray device.

 The fixing film-forming polymer (s) used in the capping compositions of the present invention are preferably present in a proportion of 0.05 to 10% by weight relative to the total weight of the styling composition.

 The term "oil" in the present invention means a water-immiscible fatty phase which is liquid at ambient temperature.

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 The oils that can be used in the outer phase of the water-in-oil emulsion of the hair styling compositions of the present invention are preferably chosen from the group formed by: animal or vegetable oils consisting of fatty acids and polyols, in particular liquid triglycerides, for example sunflower, corn, soya, avocado, jojoba, squash, grape seed, sesame, hazelnut, fish, tricaprocaprylate of glycerol or vegetable or animal oils of formula RaCOORb wherein Ra represents the residue of a fatty acid having from 7 to 29 carbon atoms and Rb represents a linear or branched hydrocarbon chain containing from 3 to 30 carbon atoms carbon, in particular an alkyl or alkenyl chain. An example of such an oil is Purcellin oil or liquid jojoba wax.

 natural or synthetic essential oils such as, for example, eucalyptus, lavandin, lavender, vetiver, litsea cubeba, lemon, sandalwood, rosemary, chamomile, savory, nutmeg oils , cinnamon, hyssop, caraway, orange, geraniol, cade and bergamot, - synthetic oils, in particular poly-α-olefins such as polybutene, hydrogenated or not, and preferably hydrogenated polyisobutene or not, - mineral oils such as hexadecane and paraffin oil, - halogenated oils, especially fluorocarbons such as fluoroamines, such as perfluorotributylamine, fluorinated hydrocarbons, for example perfluorodecahydronaphthalene, fluoroesters and fluoroethers; esters of mineral acids and fatty alcohols; esters of mono-, di-, tri- or tetracarboxylic carboxylic acids having a total number of carbon atoms greater than or equal to at 10 Preferably, the monoesters of linear or branched, saturated or unsaturated aliphatic acids of C 26 and of saturated or unsaturated aliphatic alcohols, linear or branched, with a C total of carbon atoms greater than or equal to 10. Mention may be made, for example, of ethyl palmitate, isopropyl palmitate and palmitate.

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 of 2-ethylhexyl, 2-octyldecyl palmitate, isopropyl myristate, butyl myristate, cetyl myristate, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, stearate, isobutyl, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate and cetyl octanoate, volatile or non-volatile silicone oils.

The propellant may be any liquefiable gas typically used in aerosol devices such as dimethyl ether, C3-5 alkanes, 1,1-difluoroethane, mixtures of dimethyl ether and C3-s alkanes, and mixtures of 1,1-difluoroethane and dimethyl ether and / or C3-s alkanes,
C3-alkanes, and in particular propane, n-butane and isobutane, are particularly preferably used as propellants.

 As indicated above, the hair styling compositions of the present invention contain a large fraction of water which is emulsified, with the aid of a silicone emulsifier, in an oily outer phase formed mainly by one or more of the oils mentioned herein. -above.

 The proportion of the dispersed aqueous phase in the total mixture contained in the aerosol device (propellant (a) + composition (b)) is preferably between 20 and 70% by weight.

 The propellant is preferably present in a proportion of 35 to 70%, of the total weight of the mixture (propellant (a) + styling composition (b)) contained in the aerosol device.

 The oils preferably represent from 0.1 to 30% of the total weight of the mixture (propellant (a) + composition (b)) contained in the aerosol device of the present invention.

 An essential component of the hair styling compositions of the present invention is a silicone emulsifier, that is to say a surfactant comprising at least one polydiorganosiloxane hydrophobic portion.

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 These silicone emulsifying agents are preferably nonionic emulsifying agents comprising at least one polydimethylsiloxane block and at least one polyoxyalkylene chain, preferably polyoxyethylenated and / or polyoxypropylenated. Such polyoxyalkylenated silicone emulsifiers are described, for example, in US Pat. Nos. 5,364,633 and 4,695,451.

dans laquelle chaque R représente indépendamment un radical alkyle en CI-6. ou un groupe - (CH2) x- (OC2H4) y- (C3H6) z-OR', où R'représente un atome d'hydrogène, un radical alkyle en CI-6 ou un radical acyle en C2-6, au moins un des symboles R ne représentant pas un radical alkyle en CI-6, a représente un nombre entier compris entre 0 et 200, b représente un nombre entier compris entre 0 et 50, à condition que a et b ne soient pas égaux à zéro en même temps, x représente un nombre entier allant de 1 à 6, y représente un nombre entier allant de 1 à 30, et z représente un nombre entier allant de 0 à 5. Examples that may be mentioned include the compounds corresponding to the following formula:

wherein each R independently represents a C 1-6 alkyl radical. or a group - (CH2) x- (OC2H4) y- (C3H6) z-OR ', where R' represents a hydrogen atom, a C1-C6 alkyl radical or a C2-6 acyl radical, at least one of the symbols R not representing an alkyl radical at CI-6, a represents an integer between 0 and 200, b represents an integer between 0 and 50, provided that a and b are not equal to zero in At the same time, x represents an integer from 1 to 6, y represents an integer from 1 to 30, and z represents an integer from 0 to 5.

 A group of preferred silicone emulsifying agents of this family corresponds to the following formula (Ia):

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dans laquelle a représente un nombre entier compris entre 20 et 105, b représente un nombre entier compris entre 2 et 10, et y représente un nombre entier compris entre 10 et 20.

wherein a represents an integer from 20 to 105, b represents an integer from 2 to 10, and y represents an integer from 10 to 20.

dans laquelle a et y représentent chacun indépendamment un nombre entier compris entre 10 et 20. Another group of preferred silicone emulsifying agents of this family (I) may be represented by the following formula (Ib):

wherein a and y each independently represent an integer from 10 to 20.

DC 5329 (composé de formule (la) avec a = 22, b = 2 et y = 12), DC 7439-146 (composé de formule (la) avec a = 103, b = 10 et y = 12), DC-2-5695 (composé de formule (la) avec a = 27, b = 3 et y = 12) et Q4-3667 (composé de formule (Ib) avec a = 15 et y = 13). The silicone emulsifying agents of formula (1), (la) and (Ib) are sold, for example, by the company Dow Corning under the names

DC 5329 (compound of formula (la) with a = 22, b = 2 and y = 12), DC 7439-146 (compound of formula (la) with a = 103, b = 10 and y = 12), DC- 2-5695 (compound of formula (la) with a = 27, b = 3 and y = 12) and Q4-3667 (compound of formula (Ib) with a = 15 and y = 13).

 Another group of silicone emulsifying agents that can be used in the hair styling compositions of the present invention can be represented by formulas (II) and (III) below:

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dans lesquelles Ri représente un groupement alkyle enC12-20, de préférence en C12-18, linéaire ou ramifié, R2 représente un groupe-CnH2n- (OC2H4) x- (OC3H6) y-0-R3, où R3 représente un atome d'hydrogène ou un radical alkyle en Cl l2, linéaire ou ramifié, a représente un nombre entier compris entre 0 et 500, b représente un nombre entier compris entre 0 et 500, c représente un nombre entier compris entre 1 et 500, n est un nombre entier allant de 2 à 12, x et y désignent chacun un nombre entier allant de 0 à environ 50, la somme x + y étant supérieure ou égale à 1.

in which R 1 represents a linear or branched C 12-20, preferably C 12-18, alkyl group, R 2 represents a group-C n H 2 n- (OC 2 H 4) x- (OC 3 H 6) y-O-R 3, where R 3 represents an atom of hydrogen or a linear or branched C1-12 alkyl radical, a represents an integer between 0 and 500, b represents an integer between 0 and 500, c represents an integer between 1 and 500, n is a number integer ranging from 2 to 12, x and y each denote an integer from 0 to about 50, the sum x + y being greater than or equal to 1.

 Among the preferred silicone emulsifiers of this family, mention may be made of those of formula (II) in which a is an integer ranging from 2 to 450, b is zero, c is an integer ranging from 2 to 40, n is a number integer ranging from 2 to 5, x is an integer from 1 to 30, y is an integer from 0 to 30, with x> y. Among these silicone emulsifiers, it is more particularly possible to use the mixture of cyclomethicone and dimethicone copolyol (CTFA name) such as the product sold by Dow Coming under the trade name Silicone DC 3225 C or the product sold by Goldschmidt under the name the name Abil EM 97.

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Aid, ou encore le cétyl diméthicone copolyol (dénomination CTFA, 7' édition, 1997) vendu par exemple par la société Goldschmidt sous les dénominations Abil WE09 et Abil EM 90. Another group of preferred silicone emulsifiers is formed by those of formula (II) in which a is zero and b is different from zero, such as laurylmethicone polyol (CTFA name, 7th edition, 1997) sold by Dow Coming under the trade name Q2-5200 Formulation

Aid, or else cetyl dimethicone copolyol (CTFA name, 7th edition, 1997) sold for example by Goldschmidt under the names Abil WE09 and Abil EM 90.

 The concentration of the silicone emulsifying agent in the total mixture contained in the device of the present invention is preferably between 0.1 and 10% by weight.

 The styling compositions of the present invention may contain, in addition to the silicone emulsifying agent described above or a mixture of such emulsifiers, one or more other anionic, nonionic, cationic or zwitterionic non-silicone surfactants. known, usually used in hair compositions.

 In a preferred embodiment, however, the styling compositions of the present invention are free of such a nonsilicone surfactant.

 Although the styling compositions contained in the aerosol device of the present invention are preferably free of lower alcohols, they may contain up to 15% by weight, based on the total weight of the mixture contained in the aerosol device, of a or of several lower alcohols such as ethanol or isopropanol.

 The styling compositions contained in the aerosol device of the present invention may further contain one or more cosmetic or formulation ingredients, usually used in the cosmetics field. Examples of such ingredients include UV filters, perfumes, preservatives, pigments and dyes, solubilizing agents, non-alcoholic solvents such as volatile silicones,

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 linear or cyclic, anti-foam agents, vitamins, conditioning agents and organic or inorganic, synthetic or naturally occurring particles.

 Of course, those skilled in the art will take care to choose this or these additional additives and / or their amounts so that the advantageous properties intrinsic to the invention are not affected by the addition or additions envisaged.

 The aerosol devices of the present invention preferably contain hair lacquers.

 The formulation examples illustrate the present invention without however limiting it.

Example 1
The following ingredients are packaged in an aerosol device:

<Tb>
<tb> Myristate <SEP> isopropyl <SEP> 6 <SEP>% <SEP> in <SEP> weight
<tb> DC <SEP> 2-5225 <SEP> C <SEP> (Dow <SEP> Coming) <SEP> 4 <SEP>% <SEP> in <SEP> Weight
<tb> Antarono <SEP> V-216 <SEP> (ISP) <SEP> b) <SEP> 1 <SEP>% <SEP> in <SEP> weight
<tb> Water <SEP> 44 <SEP>% <SEP> in <SEP> weight
<tb> Butane <SEP> 45 <SEP>% <SEP> in <SEP> weight
<Tb>

a a) 10 parties de polydiméthyl/méthylsiloxane à 18 moles d'oxyde d'éthylène et 18 moles d'oxyde de propylène dans 90 parties de cyclopentasiloxane b) polyvinylpyrrolidone greffée à 80 % avec des motifs hexadécényle
La laque ainsi obtenue, exempte d'alcool, est facile à pulvériser et l'application d'une fine couche de cette laque déforme peu les cheveux séchés et mis en forme. Les cheveux, après séchage, ont un aspect brillant et sont faciles à démêler.

aa) 10 parts of polydimethyl / methylsiloxane with 18 moles of ethylene oxide and 18 moles of propylene oxide in 90 parts of cyclopentasiloxane b) polyvinylpyrrolidone grafted to 80% with hexadecenyl units
The lacquer thus obtained, free from alcohol, is easy to spray and the application of a thin layer of this lacquer deforms the hair dried and shaped. The hair, after drying, has a shiny appearance and is easy to disentangle.

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EXAMPLE 2 The following ingredients are packaged in an aerosol device:

<Tb>
<tb> Myristate <SEP> isopropyl <SEP> 6 <SEP>% <SEP> in <SEP> weight
<tb> Q-2-5200 <SEP> Formulation <SEP> Aid <SEP> (Dow <SEP> Coming) <SEP> c) <SEP> 4 <SEP>% <SEP> in <SEP> weight
<tb> Luviset <SEP> If <SEP> Pure <SEP> (ISP) <SEP> d) <SEP> 1 <SEP>% <SEP> into <SEP> Weight
<tb> Water <SEP> 44 <SEP>% <SEP> in <SEP> weight
<tb> Butane <SEP> 45 <SEP>% <SEP> in <SEP> weight
<Tb>

c polyméthyllauryl/diméthylsiloxane à 18 motifs OE et 18 motifs OP dans 9 parties d'alcool isostéarylique copolymère bloc polyuréthanne-silicone (nom INCI : polyurethane-6)
La laque ainsi obtenue, exempte d'alcool, est facile à pulvériser et l'application d'une fine couche de cette laque déforme peu les cheveux séchés et mis en forme. Les cheveux, après séchage, ont un aspect brillant et sont faciles à démêler.

c polymethyllauryl / dimethylsiloxane with 18 EO units and 18 OP units in 9 parts of isostearyl alcohol polyurethane-silicone block copolymer (INCI name: polyurethane-6)
The lacquer thus obtained, free from alcohol, is easy to spray and the application of a thin layer of this lacquer deforms the hair dried and shaped. The hair, after drying, has a shiny appearance and is easy to disentangle.

Claims (12)

An aerosol device, containing (a) at least one propellant and (b) a styling composition comprising at least one fixing, dissolved or finely dispersed film-forming polymer in a cosmetically acceptable water-in-oil emulsion comprising water, at less an oil and at least one silicone emulsifier.  2. Device according to Claim 1, characterized in that the silicone emulsifying agent is a nonionic emulsifying agent comprising at least one polydimethylsiloxane block and at least one polyoxyalkylene chain.  3. Device according to claim 2, characterized in that the silicone emulsifying agent is chosen from those corresponding to the following formula:

 wherein each R is independently C1-C6 alkyl, or - (CH2) x- (OC2H4) y- (C3H6) z-OR ', where R' is hydrogen, alkyl is C1-6 or a C2-6 acyl radical, at least one of R being not C1-C6alkyl, a is an integer from 0 to 200, b is an integer from 0 to 50 , provided that a and b are not zero at the same time, x is an integer from 1 to 6, y is an integer from 1 to 30, and z is an integer from 0 to 5; . <Desc / Clms Page number 28>  4. Device according to claim 3, characterized in that the silicone emulsifying agent corresponds to the following formula:

 wherein a represents an integer from 20 to 105, b represents an integer from 2 to 10, and y represents an integer from 10 to 20.  5. Device according to claim 3, characterized in that the silicone emulsifier corresponds to the following formula (Ib):

 wherein a and y each independently represent an integer from 10 to 20.  6. Device according to Claim 2, characterized in that the silicone emulsifier is chosen from those corresponding to one of the following formulas (II) and (III): <Desc / Clms Page number 29>

 in which R 1 represents a C 12-20 alkyl group, preferably a linear or branched C 12-20 alkyl group, R 2 represents a group-C n H 2 n- (OC 2 H 4) x- (OC 3 H 6) y-O-R 3, where R 3 represents a hydrogen atom or a linear or branched C 1 -C 12 alkyl radical, a represents an integer between 0 and 500, b represents an integer between 0 and 500, c represents an integer between 1 and 500, n is an integer from 2 to 12, x and y each denote an integer from 0 to about 50, the sum x + y being greater than or equal to 1.  7. Device according to any one of the preceding claims, characterized in that the silicone emulsifier is present in a proportion of 0.1 to 10% by weight, based on the total weight of the mixture contained in the aerosol device.  8. Device according to any one of the preceding claims, characterized in that the water is from 20 to 70% by weight, based on the total weight of the mixture contained in the aerosol device.  9. Device according to any one of the preceding claims, characterized in that the oil is chosen from animal or vegetable oils consisting of esters of fatty acids and polyols, vegetable or animal oils of formula RCOORB in which Ra represents the residue of a fatty acid <Desc / Clms Page number 30>  having from 7 to 29 carbon atoms and Rb represents a linear or branched hydrocarbon chain containing from 3 to 30 carbon atoms, natural or synthetic essential oils, synthetic oils, mineral oils, halogenated oils, esters of mono-, di-, tri- or tetracarboxylic carboxylic acids having a total number of carbon atoms greater than or equal to 10, and silicone oils.  10. Device according to claim 9, characterized in that the oil in the outer phase of the water-in-oil emulsion is a monoester of a saturated or unsaturated aliphatic acid, linear or branched C-26 and d a saturated or unsaturated, linear or branched C 1-20 aliphatic alcohol having a total number of carbon atoms greater than or equal to 10.  11. Device according to claim 10, characterized in that the oil is chosen from ethyl palmitate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, isopropyl myristate. , butyl myristate, cetyl myristate, 2octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate, hexyl laurate, 2-hexyldecyl laurate, isononanoate, isononyl and cetyl octanoate.  2. Device according to any one of the preceding claims, characterized in that the oil represents from 0.1 to 30% of the total weight of the mixture contained in the aerosol device.  3. Device according to any one of the preceding claims, characterized in that the propellant (a) represents from 35% to 70% of the total weight of the mixture contained in the aerosol device.  4. Device according to any one of the preceding claims, characterized in that the propellant is chosen from propane, n-butane and isobutane.  5. Device according to any one of the preceding claims, characterized in that the fixing film-forming polymer is chosen from anionic, cationic, nonionic and amphoteric fixing film-forming polymers.  6. Device according to any one of the preceding claims, characterized in that the fixing film-forming polymer is present in <Desc / Clms Page number 31>  from 0.05 to 10% by weight relative to the total weight of the mixture contained in the aerosol device.  7. Device according to any one of the preceding claims, characterized in that it contains a hairspray.  18. A hair styling method of vaporizing the mixture contained in the aerosol device according to any one of the preceding claims on the shaped hair and allowing the hair so treated to dry.