Aerosol device comprising at least an acrylic associative polymer and at least a fixing polymer

0001The present invention relates to an aerosol device containing at least one associative acrylic polymer and at least one fixing polymer, as well as a styling method using such a device.

0002The 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 surveillance, especially in the United States, following the recent awareness of public opinion to ecological problems resulting from the emission of volatile organic products in the atmosphere.

0003One solution to reduce the amount of alcohol, or even completely remove alcohol from the formulas, is to replace it with an equivalent amount of water. This introduction of large quantities of water into aerosol sprays intended for fixing the hair, such as hairsprays, however leads to an undesirable significant modification of the shape of the hair and to a degradation of the cosmetic properties. Furthermore, most propellants of the hydrocarbon type are incompatible with water and their use in compositions with a high water content is therefore generally impossible.

0004Styling products are usually used to provide lasting hold to the hairstyle.

0005For this, fixing polymers are introduced into a hydroalcoholic medium.

0006The packaging in aerosol form allows a regular distribution on the whole of the hair.

0007The fixing of the hairstyle is then almost immediate and it is not easy, even impossible to structure the hairstyle with the hands because the hair is frozen instantly.

0008The problem posed by the invention is to provide a cosmetic hair composition suitably fixing the hair, providing good cosmetic properties with, in particular, a reduction in the sticky and drying effect in a reasonable time, while being distributed uniformly and rapidly. on the hair.

0009The subject of the present invention is a composition packaged in an aerosol device, containing:<ul id="ul0001" list-style="none" compact="compact"><li>(a) at least 20% at least one propellant and</li><li>(b) a styling composition comprising at least (i) an anionic or nonionic non-polyurethane fixing polymer and (ii) at least one acrylic anionic associative polymer.</li></ul>

0010The subject of the invention is also a styling method consisting in spraying the mixture contained in said aerosol device onto the shaped hair and allowing the hair thus treated to dry.

STYLISH COMPOSITION

0011All the anionic, nonionic fixing polymers and their mixtures used in the art can be used in the compositions according to the present application.

0012For the purposes of the present invention, the term “fixing polymer” means any polymer capable of providing maintenance of the hair in a given form.

FIXING POLYMERS

ANIONIC FIXING POLYMERS

0013The fixing polymers may be soluble in the cosmetically acceptable medium or insoluble in this same medium and used in this case in the form of dispersions of solid or liquid particles of polymer (latex or pseudolatex).

0014The anionic fixing polymers generally used are polymers comprising groups derived from carboxylic, sulphonic or phosphoric acid and have a number average molecular weight of between approximately 500 and 5,000,000.

0015The carboxylic groups are provided by mono or unsaturated dicarboxylic acid monomers such as those corresponding to the formula:<chemistry id="chem0001" num="0001"><img file="EP1634579B1_D0001.tif" /></chemistry>where n is an integer from 0 to 10, A₁ 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 oxygen or sulfur, R₇ denotes a hydrogen atom, a phenyl or benzyl group, R₈ denotes a hydrogen atom, a lower alkyl or carboxyl group, R₉ denotes a hydrogen atom, a lower alkyl group, a -CH group₂-COOH, phenyl or benzyl.

0016In the above formula, a lower alkyl group preferably denotes a group having 1 to 4 carbon atoms and in particular, methyl and ethyl groups.

0017The preferred anionic fixing polymers with carboxylic groups according to the invention are:<ol id="ol0001" ol-style=""><li>A) Homo- or copolymers of acrylic or methacrylic acid or their salts and in particular the products sold under the names VERSICOL^® E or K by ALLIED COLLOID and ULTRAHOLD^® by the company BASF, the copolymers of acrylic acid and of acrylamide sold in the form of their sodium salts under the names RETEN 421, 423 or 425 by the company HERCULES, the sodium salts of polyhydroxycarboxylic acids;</li><li>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 on a polyalkylene glycol such as polyethylene glycol, and possibly crosslinked. Such polymers are described in particular in the<patcit id="pcit0001" dnum="FR1222944"><text>French patent n ° 1 222 944</text></patcit> and demand <patcit id="pcit0002" dnum="DE2330956"><text>German No. 2 330 956</text></patcit>, copolymers of this type comprising in their chain an optionally N-alkylated and / or hydroxyalkylated acrylamide unit as described in particular in Luxembourg patent applications n^bone 75370 and 75371 or offered under the name QUADRAMER by the company AMERICAN CYANAMID. Mention may also be made of copolymers of acrylic acid and of C 1 alkyl methacrylate.₁-VS₄ and terpolymers of vinylpyrrolidone, acrylic acid and C-alkyl methacrylate₁-VS₂₀, for example, lauryl, such as that sold by the company ISP under the name ACRYLIDONE^® LM and methacrylic acid / ethyl acrylate / tert-butyl acrylate terpolymers such as the product sold under the name LUVIMER^® 100 P by the company BASF; Mention may also be made of the methacrylic acid / acrylic acid / ethyl acrylate / methyl methacrylate copolymers in aqueous dispersion, sold under the name AMERHOLD® DR 25 by the company AMERCHOL;</li><li>C) Copolymers of crotonic acid, such as those comprising vinyl acetate or propionate units in their chain, and optionally other monomers such as the allyl or methallyl esters, vinyl ether or vinyl ester of a saturated carboxylic acid, linear or branched, with a long hydrocarbon chain, such as those containing at least 5 carbon atoms, these polymers possibly being grafted or crosslinked, or even another vinyl ester monomer, allylic or methallylic of an α- or β-cyclic carboxylic acid. Such polymers are described inter alia in French patents n^bone 1 222 944, 1 580 545, 2 265 782, 2 265 781, 1 564 110 and 2 439 798. Commercial products falling into this class are resins 28-29-30, 26-13-14 and 28-13- 10 sold by National Starch;</li><li>D) Copolymers of C-monounsaturated carboxylic acids or anhydrides₄-VS₈ chosen from:<ul id="ul0002" list-style="dash" compact="compact"><li>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, 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 patents<patcit id="pcit0003" dnum="US2047398A"><text>US nos 2,047,398</text></patcit>, <patcit id="pcit0004" dnum="US2723248A"><text>2 723 248</text></patcit>, <patcit id="pcit0005" dnum="US2102113A"><text>2 102 113</text></patcit>, the patent <patcit id="pcit0006" dnum="GB839805A"><text>GB n ° 839 805</text></patcit>. Commercial products are in particular those sold under the names GANTREZ^® AN or ES by ISP;</li></ul>copolymers comprising (i) one or more maleic, citraconic, itaconic anhydride units and (ii) one or more monomers chosen from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, α-olefin groups, acrylic or methacrylic esters, acrylic or methacrylic or vinylpyrrolidone acids in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. These polymers are for example described in the patents <patcit id="pcit0007" dnum="FR2350384"><text>French nos 2 350 384</text></patcit> and <patcit id="pcit0008" dnum="FR2357241"><text>2 357 241 </text></patcit>the plaintiff;</li><li>E) Polyacrylamides containing carboxylate groups. Homopolymers and copolymers comprising sulfonic groups are polymers comprising vinylsulfonic, styrene-sulfonic, naphthalene-sulfonic or acrylamido-alkylsulfonic units.</li></ol>

0018These polymers can in particular be chosen from:<ul id="ul0003" list-style="dash"><li>salts of polyvinylsulfonic acid having a molecular weight of between approximately 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, ethers vinyl and vinylpyrrolidone;</li><li>the salts of polystyrene-sulfonic acid such as the sodium salts sold for example under the name Flexan^® 500 and Flexan^® 130 by National Starch. These compounds are described in the patent<patcit id="pcit0009" dnum="FR2198719"><text>FR 2 198 719</text></patcit> ; mentioned in the patent<patcit id="pcit0010" dnum="US4128631A"><text>US 4,128,631</text></patcit>, and more particularly polyacrylamidoethylpropane-sulfonic acid sold under the name COSMEDIA POLYMER HSP 1180 by HENKEL.</li></ul>

0019As another anionic fixing polymer which can be used according to the invention, mention may be made of the branched block anionic polymer sold under the name Fixate G-100 by the company NOVEON.

0020According to the invention, the anionic fixing polymers are preferably chosen from acrylic acid copolymers such as acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers sold in particular under the name ULTRAHOLD^® STRONG by the company BASF, the copolymers derived from crotonic acid such as the vinyl acetate / vinyl tert-butylbenzoate / crotonic acid terpolymers and the 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 methylvinyl ether / maleic anhydride copolymers sold, for example, under the name GANTREZ^® by ISP, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT^® L by the company ROHM PHARMA, the copolymers of methacrylic acid and ethyl acrylate sold under the name LUVIMER^® MAEX or MAE by the company BASF and the vinyl acetate / crotonic acid copolymers sold 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 polymer sold under the name Fixate G-100 by the company NOVEON.

0021Among the anionic fixing polymers mentioned above, it is more particularly preferred to use, in the context of the present invention, the monoesterified methylvinyl ether / maleic anhydride copolymers sold under the name GANTREZ^® ES 425 by the company ISP, the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers sold under the name ULTRAHOLD^® STRONG by BASF, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT^® L by the company ROHM PHARMA, the vinyl acetate / vinyl tert-butyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company NATIONAL STARCH, the copolymers of methacrylic acid and ethyl acrylate sold under the name LUVIMER^® MAEX OR MAE by BASF, the vinylpyrrolidone / acrylic acid / lauryl methacrylate terpolymers sold under the name ACRYLIDONE^® LM by the company ISP, the polymer sold under the name Fixate G-100 by the company NOVEON.

NON-IONIC FIXING POLYMERS

0022The nonionic fixing polymers which can be used according to the present invention are chosen, for example, from:<ul id="ul0004" list-style="dash" compact="compact"><li>polyalkyloxazolines;</li><li>vinyl acetate homopolymers;</li><li>vinyl acetate copolymers such as, for example, vinyl acetate and acrylic ester copolymers, vinyl acetate and ethylene copolymers, or vinyl acetate and ester copolymers maleic, for example, dibutyl maleate;</li><li>homopolymers and copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and alkyl methacrylates such as the products offered by the company ROHM &amp; HAAS under the names PRIMAL^® AC-261 K and EUDRAGIT^® NE 30 D, by the company BASF under the name 8845, by the company HOECHST under the name APPRETAN^® N9212;</li><li>copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; mention may be made of the products offered under the name CJ 0601 B by the company ROHM &amp; HAAS;</li><li>homopolymers of styrene;</li><li>styrene copolymers such as, for example, styrene and alkyl (meth) acrylate copolymers such as MOWILITH products^® LDM 6911, MOWILITH^® DM 611 and MOWILITH^® LDM 6070 offered by HOECHST, RHODOPAS products^® SD 215 and RHODOPAS^® DS 910 offered by RHONE POULENC; copolymers of styrene, alkyl methacrylate and alkyl acrylate; copolymers of styrene and butadiene; or copolymers of styrene, butadiene and vinylpyridine;</li><li>polyamides;</li><li>homopolymers of vinyllactam other than homopolymers of vinylpyrrolidone, such as polyvinylcaprolactam sold under the name Luviskol^® PLUS by BASF; and</li><li>vinyllactam copolymers such as a poly (vinylpyrrolidone / vinyllactam) copolymer sold under the trade name Luvitec^® VPC 55K65W by BASF, poly (vinylpyrrolidone / vinyl acetate) copolymers such as those marketed 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 sold under the name Luviskol^® VAP 343 by BASF.</li></ul>

0023The alkyl groups of the above-mentioned nonionic polymers preferably have from 1 to 6 carbon atoms.

0024According to the invention, it is also possible to use fixing polymers of the grafted silicone type, anionic or nonionic, 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.

0025These polymers are for example described in patent applications <patcit id="pcit0011" dnum="EP0412704A"><text>EP-A-0 412 704</text></patcit>, <patcit id="pcit0012" dnum="EP0412707A"><text>EP-A-0 412 707</text></patcit>, <patcit id="pcit0013" dnum="EP0640105A"><text>EP-A-0 640 105</text></patcit> and <patcit id="pcit0014" dnum="WO9500578A"><text>WO 95/00578</text></patcit>, <patcit id="pcit0015" dnum="EP0582152A"><text>EP-A-0 582 152</text></patcit> and <patcit id="pcit0016" dnum="WO9323009A"><text>WO 93/23009</text></patcit> and patents <patcit id="pcit0017" dnum="US4693935A"><text>US 4,693,935</text></patcit>, <patcit id="pcit0018" dnum="US4728571A"><text>US 4,728,571</text></patcit> and <patcit id="pcit0019" dnum="US4972037A"><text>US 4,972,037</text></patcit>.

0026Such polymers are, for example, the copolymers capable of being obtained by radical polymerization from the mixture of monomers formed:<ol id="ol0002" compact="compact" ol-style=""><li>a) from 50 to 90% by weight of tert-butyl acrylate,</li><li>b) from 0 to 40% by weight of acrylic acid,</li><li>c) from 5 to 40% by weight of a silicone macromer of formula<chemistry id="chem0002" num="0002"><img file="EP1634579B1_D0002.tif" /></chemistry>where v is a number ranging from 5 to 700, the percentages by weight being calculated relative to the total weight of the monomers.</li></ol>

0027Other examples of grafted silicone polymers are in particular polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, mixed polymer units of the poly ((meth) acrylic acid) type and poly ((meth) acrylate) type, and polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene type connecting link, polymeric units of the isobutyl poly (meth) acrylate type .

0028As another type of silicone fixing polymers, mention may be made of the product Luviflex^® Silk marketed by BASF.

0029The concentration of fixing polymer (s) used in the compositions according to the present invention is between 0.1 and 20%, preferably between 0.5 and 10% by weight relative to the total weight of the total composition contained in the aerosol device (propellant + styling composition).

ASSOCIATIVE ANIONIC ACRYLIC POLYMERS

0030For the purposes of the present invention, the term associative polymer means any amphiphilic polymer comprising at least one fatty chain, therefore a hydrophobic part, and at least one hydrophilic part.

0031The molecules of these polymers are capable of associating with each other or with molecules of associativity agents such as surfactants, which leads to particular properties.

0032The hydrophobic part can be reduced in number with respect to the rest of the polymer chain, and can be located laterally to the chain and be distributed randomly (random copolymers) or distributed in the form of blocks or grafts (block copolymers or block copolymers).

0033Water-soluble or water-dispersible polymers can be used. Preferably, the amphiphilic polymers useful according to the invention are not crosslinked.

0034The associative polymers of the invention are anionic and comprise, as monomers, at least one unsaturated carboxylic acid. The unsaturated carboxylic acids which can be used in the polymers of the invention are preferably chosen from the group of acrylic, methacrylic, crotonic, itaconic and maleic acids.

0035By the expression "fatty chain" is meant according to the invention, a linear or branched hydrocarbon group having from 8 to 30 carbon atoms.

0036Among the anionic acrylic associative polymers according to the invention, there may be mentioned:<ul id="ul0005" list-style="dash" compact="compact"><li>copolymers comprising at least one hydrophilic unit, and at least one fatty chain allyl ether unit, the hydrophilic unit of which consists of a vinyl carboxylic acid and very particularly of an acrylic acid or a methacrylic acid or mixtures thereof ci, and whose fatty chain allyl ether unit corresponds to the monomer of formula (V) below:         CH2 = CR 'CH2 O Bn R (V) in which :<ul id="ul0006" list-style="dash" compact="compact"><li>R 'denotes H or CH₃ ;</li><li>B denotes the ethyleneoxy radical;</li><li>n is zero or denotes an integer ranging from 1 to 100;</li><li>R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl, cycloalkyl radicals, comprising from 8 to 30 carbon atoms, preferably 10 to 24, and more particularly still from 12 to 18 carbon atoms.</li></ul></li></ul>

0037A unit of formula (V) which is more particularly preferred is a unit in which R ′ denotes H, n is equal to 10 and R denotes a stearyl radical (C₁₈).

0038Anionic associative polymers of this type are described and prepared, according to an emulsion polymerization process, in the patent. <patcit id="pcit0020" dnum="EP0216479A"><text>EP-0 216 479</text></patcit>.

0039Among these polymers, the polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of alkyl (meth) acrylates, are particularly preferred according to the invention. lower, from 2 to 50% by weight of fatty chain allyl ether of formula (V) and from 0 to 1% by weight of a crosslinking agent which is a well known copolymerizable polyethylene unsaturated monomer, such as phthalate diallyl, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate and methylene-bis-acrylamide.

0040Among the latter, very particularly preferred are the crosslinked terpolymers sold by the company ALLIED COLLOIDS under the names SALCARE SC 80® and SALCARE SC90® which are aqueous emulsions containing 30% of a crosslinked terpolymer of methacrylic acid, of acrylate d ethyl and steareth-10-allyl ether (40/50/10).

0041Mention may also be made, as polymers belonging to this family, of the RHOEVIS -CR, -CR3 and -CRX products offered by the company ALLIED COOLOIDS;<ul id="ul0007" list-style="dash" compact="compact"><li>methacrylic acid / alkyl acrylate / polyoxyethylenated lauryl acrylate terpolymers such as the product RHEO 2000 sold by COATEX;</li><li>methacrylic acid / C1-C8 alkyl acrylate / polyoxyethylenated stearyl methacrylate copolymers such as the products ACRYSOL 22, (or ACULYN 22 or ACRYSOL ICS) ACRYSOL25 and DW-1206A sold by the company ROHM &amp; HAAS;</li><li>methacrylic acid / alkyl acrylate / polyoxyethylenated nonylphenol acrylate copolymers such as the product RHEO 3000 sold by COATEX;</li><li>methacrylic acid / butyl acrylate / hydrophobic monomer copolymers comprising a fatty chain such as the product 8069-146A marketed by NATIONAL STARCH;</li><li>copolymers comprising at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit of C10-C30 alkyl ester type of unsaturated carboxylic acid.</li></ul>

0042Preferably, these polymers are chosen from those whose hydrophilic unit of olefinic unsaturated carboxylic acid type corresponds to the monomer of the following formula:<chemistry id="chem0003" num="0003"><img file="EP1634579B1_D0003.tif" /></chemistry>in which R1 denotes H or CH3 or C2H5, that is to say acrylic acid, methacrylic acid or ethacrylic acid units, and in which the hydrophobic unit of alkyl ester type (C₁₀-VS₃₀) unsaturated carboxylic acid corresponds to the monomer of the following formula<chemistry id="chem0004" num="0004"><img file="EP1634579B1_D0004.tif" /></chemistry>in which :<ul id="ul0008" list-style="dash" compact="compact"><li>R₂ denotes H or CH₃ or C₂H₅, that is to say acrylate, methacrylate or ethacrylate units, and preferably H (acrylate units) or CH₃ (methacrylate motifs);</li><li>R₃ denoting a C 1 alkyl radical₁₀-VS₃₀, and preferably in C₁₂-VS₂₂.</li></ul>

0043Alkyl esters (C₁₀-VS₃₀) of unsaturated carboxylic acids in accordance with the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates , lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

0044Anionic polymers of this type are for example described and prepared, according to the patents <patcit id="pcit0021" dnum="US3915921A"><text>US-3,915,921</text></patcit> and <patcit id="pcit0022" dnum="US4509949A"><text>4 509 949</text></patcit>.

0045Among this type of anionic associative polymers, use will be made more particularly of polymers formed from a mixture of monomers comprising:<ol id="ol0003" compact="compact" ol-style=""><li>(i) acrylic acid;</li><li>(ii) an ester of formula (VII) described above and in which R₂ denotes H or CH₃, R₃ denoting an alkyl radical having from 12 to 22 carbon atoms;</li><li>(iii) and a crosslinking agent, which is a well-known polyethylene copolymerizable unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.</li></ol>

0046Among this type of anionic associative polymers, use will be made more particularly of those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), from 4 to 40% by weight of C 1 alkyl acrylate.₁₀-VS₃₀ (hydrophobic unit), and from 0 to 6% by weight of crosslinking polymerizable monomer, or else those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), from 1 to 4% by weight of acrylate C alkyl₁₀-VS₃₀ (hydrophobic unit), and from 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

0047Among the above polymers, very particularly preferred according to the present invention, the products sold by the company GOODRICH under the trade names PEMULEN TR1 ®, PEMULEN TR2 ®, CARBOPOL 1382 ®, and even more preferably PEMULEN TR1 ®, and the product sold by SEPPIC under the name COATEX SX ®.

0048Mention may also be made of (meth) acrylic acid / ethyl acrylate / alkyl acrylate C8-C22 copolymers such as the product ACUSOL 823 offered by the company ROHOM &amp; HAAS and the product IMPERON R sold by the company HOECHST.<ul id="ul0009" list-style="dash" compact="compact"><li>acrylic acid / alkyl acrylate C8-C30 terpolymers. preferably C15 / polyethylene glycol acrylate (preferably 20 to 30 mounds of ethylene oxide) such as the product DAPRAL GE 202 sold by the company AKZO;</li><li>maleic anhydride / α-olefin terpolymers₃₀-VS₃₈ / alkyl maleate such as the product (maleic anhydride / α-olefin C copolymer₃₀-VS₃₈ / isopropyl maleate) sold under the name PERFORMA V 1608® by the company NEWPHASE TECHNOLOGIES.</li><li>acrylic copolymers with polyurethane pattern (s) such as acrylic terpolymers comprising:<ol id="ol0004" compact="compact" ol-style=""><li>(a) about 20% to 70% by weight of an α, β-monoethylenically unsaturated carboxylic acid;</li><li>(b) about 20 to 80% by weight of a non-surfactant α, β-monoethylenically unsaturated monomer other than (a);</li><li>(c) about 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate;</li></ol>such as those described in the request for <patcit id="pcit0023" dnum="EP0173109A"><text>patent EP-A-0 173 109</text></patcit> and more particularly that described in Example 3, namely, a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate teroxolymer of ethoxylated behenyl alcohol (40 EO) in 25% aqueous dispersion.</li></ul>

0049As analogous product, mention may be made of the product ADDITOL VXW 1312 sold by HOECHST.

0050Among the associative polymers, we prefer:<ul id="ul0010" list-style="dash" compact="compact"><li>acrylic acid / C1-C8 ethyl acrylate terpolymers polyoxyethylenated stearyl methacrylate, for example using 20 moles of ethylene oxide such as the product sold under the name "ACRYSOL ICS or ACRYSOL ZZ or ACULYN 22 "by the company ROHM &amp; HAAS,</li></ul>

0051Depending on their nature, the associative polymers according to the invention can be used in the form of aqueous solutions or in the form of aqueous dispersions.

0052Depending on their nature, the associative polymers according to the invention can be used in the form of aqueous solutions or in the form of aqueous dispersions.

AEROSOL

0053The propellant can be any liquefiable gas usually used in aerosol devices such as dimethyl ether, C alkanes_3-5, 1,1-difluoroethane, mixtures of dimethyl ether and C alkanes_3-5, and mixtures of 1,1-difluoroethane and dimethyl ether and / or C alkanes_3-5. It is particularly preferred to use dimethyl ether as propellant. The propellant is present in an amount of more than 20%, and preferably between 20 and 70% and even more preferably between 20 and 50 of the total weight of the mixture (propellant (a) + styling composition (b)) contained in the aerosol device.

0054Although the styling compositions contained in the aerosol device of the present invention are preferably free of lower alcohols, they can contain up to 50% and preferably up to 25% by weight, based on the total weight of the mixture contained in the aerosol device, one or more lower alcohols such as ethanol or isopropanol.

0055The styling composition according to the invention may also contain at least one adjuvant chosen from silicones in soluble, dispersed, micro-dispersed form, nonionic, anionic, cationic and amphoteric surfactants, additional polymers other than fixing polymers and associative polymers used in the compositions according to the invention, ies ceramides and pseudo-ceramides, vitamins and pro-vitamins including panthenol, vegetable and animal oils, mineral and synthetic, waxes other than ceramides and pseudo-ceramides, water-soluble and liposoluble, silicone or non-silicone sun filters, solid particles such as for example mineral and organic pigments, colored or non-colored, pearlescent agents and opacifiers , flakes, active particles, dyes, sequestering agents, plasticizing agents, solubilizing agents, acidifying agents, basifying agents, neutralizing agents, mineral and organic thickening agents, antioxidants, hydroxy acids, penetrating agents, perfumes and preservatives.

0056These additives are 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.

0057In the styling compositions contained in the aerosol device, the water represents from 20 to 80% by weight, relative to the total weight of the mixture contained in the aerosol device.

0058Of course, those skilled in the art will take care to choose this or these optional additional additives and / or their quantities so that the advantageous properties intrinsic to the invention are not affected by the addition or additions envisaged.

0059Used under the conditions of the invention described above, that is to say in an aerosol device, the associative polymers of the invention facilitate the spreading of the styling solution on the hair and reduces the sticky effect of the fixing polymers of the invention.

0060This particular association makes it possible to obtain shaping of the hairstyle by working with the fingers without obtaining the instant hardening and freezing conventionally encountered with fixing products. The application can be done on both damp and dry hair.

0061As part of an application to damp hair, drying in the open air or brushing can be carried out. The hairstyle result is supple and natural.

0062The introduction of specific additives of the polyol type into this type of formulation makes it possible, for example, to obtain an effect qualified as "wet", that is to say giving the hair a type of appearance "out of the shower" in a sustainable manner. in time.

0063The hairstyle result is supple and natural.

0064The formulation example illustrates the present invention without however limiting it.

Example:

0065Hydroalcoholic aerosol spray comprising in g / 100g and active ingredient:<ul id="ul0011" list-style="none" compact="compact"><li>PVP: 2.27</li><li>Aculyn 22: 0.65</li><li>2 Amino2methyl 1 propanol: 0.06</li><li>Water: 36.40</li><li>Glycerol: 10.40</li><li>Ethanol: 15.22</li><li>DME: 35</li></ul>

0066Sprayed on damp natural hair, the above composition is easily distributed over the hair without sticking the fingers and gives it after drying a supple and natural lasting hold with a wet effect.