COSMETIC COMPOSITION COMPRISING AN ANIONIC OR NONIONIC ASSOCIATIVE POLYMER, FIXING POLYMER AND AT LEAST 2% OF A SURFACTANT The present invention relates to a cosmetic composition for treating keratin fibres, in particular human keratin fibres such as the hair, comprising at least one anionic or nonionic associative polymer, at least one fixing polymer and at least one particular surfactant, to a use of this composition for treating the hair and also to a cosmetic treatment process using it.

In the field of styling, in particular among hair products intended for shaping and/or holding the hairstyle, hair compositions generally consist of a solution, which is usually alcohol-based or water-based, and of one or more fixing polymers as a mixture with various cosmetic adjuvants.

These compositions may be in the form of hair gels, lotions, mousses or sprays, which are generally applied to wet hair before blow-drying or drying.

In particular, head gels consist especially of one or more thickening polymers or gelling agents in combination with one or more fixing polymers which usually served to form a film of the surface of the keratin fibres to be fixed in order to produce welds between them, thus structuring or constructing the hairstyle and giving it hold.

Document US 2007/0 134 191 describes, for example, several styling gel compositions, one of the compositions comprising a fixing polymer, a nonionic amphiphilic polymer and an emulsifier, in particular 4% of isoceteth-20. Document WO 201 1/062 805 also describes examples of styling gel compositions comprising a fixing polymer combined with an anionic associative polymer, one of the compositions comprising 0.25% of laureth-30.

Styling gels generally have moderate to very strong hair-fixing properties. Within this fixing range, the hold of the hairstyle over time often depends on the starting level of fixing of the gel, but in all cases remains largely insufficient. The reason for this is that the locks of hair obtained by applying a gel are subject to mechanical stresses throughout the day, such as the wearing of a helmet, passage of the hands or the wind, the removal of clothing, etc.

Moreover, styling gels are often difficult to remove from the hair and above all from the hands at the time of application. Soap or a shampoo are systematically required in order to cleanse the hands and the hair thoroughly.

There is thus a real need to find cosmetic compositions, especially for styling, which allow long-lasting hairstyle hold and which are easily removed on washing.

Surprisingly and advantageously, the Applicant has just discovered that by combining a particular surfactant in particular proportions with an anionic or nonionic associative polymer and a fixing polymer, a styling gel is obtained that has improved hairstyle hold over time and that is easily removed from the hands and the hair with water, without shampoo or soap. A subject of the present invention is thus especially a cosmetic composition, especially a hair composition, comprising at least one anionic or nonionic associative polymer, at least one fixing polymer and at least one anionic, cationic or amphoteric surfactant, the weight content of anionic, cationic or amphoteric surfactants in the composition being greater than or equal to 2%.

A combination according to the invention specifically makes it possible to obtain a styling gel with very strong fixing power, which has extreme hold over time and when subjected to mechanical stresses, especially the wearing of a helmet or passage of the hands. It also makes it possible to clean the hands and the hair after rinsing with water.

According to another of its aspects, the present invention relates to a process for treating keratin fibres, especially for shaping the hair, in which a cosmetic composition, especially a hair composition, comprising at least one anionic or nonionic associative polymer, at least one fixing polymer and at least one anionic, cationic or amphoteric surfactant is applied to the keratin fibres, the weight content of anionic, cationic or amphoteric surfactants in the composition being greater than or equal to 2%.

According to another aspect, the present invention relates to the use for treating keratin fibres, especially for holding and/or fixing the hair, of a cosmetic composition as defined previously.

The expression "at least one" is equivalent to the expression "one or more".

The term "hair composition" means a composition that is applied to the hair, i.e. especially for holding and/or fixing the hairstyle, caring for the hair, making up the hair or colouring the hair.

The term "styling composition" means a composition for giving the head of hair a shape and/or for holding the acquired shape of the head of hair.

For the purposes of the present invention, the term "fixing polymer" thus means a polymer that is capable of giving a head of hair a shape and/or of holding the acquired shape of the head of hair.

For the purposes of the invention, the term "associative polymers" means amphiphilic polymers comprising both a) one or more hydrophobic units each consisting of one or more fatty chains and b) one or more hydrophilic units. These polymers result from a polymerization using at least one monomer other than an alkylene oxide or glycidol. They may be obtained, for example, via radical polymerization reactions, polycondensation reactions or grafting reactions onto prepolymers.

According to the invention, the term "fatty chain" means a linear or branched, optionally hydroxylated alkyl or alkenyl chain containing from 8 to 30 and preferably from 10 to 30 carbon atoms.

The associative polymers of the composition according to the invention are of anionic or nonionic type. They may be crosslinked or non-crosslinked. Among the associative polymers of anionic type that may be mentioned are:

- (I) those comprising at least one hydrophilic unit and at least one fatty- chain allyl ether unit, more particularly those whose hydrophilic unit is formed by an ethylenic unsaturated anionic monomer, more particularly a vinylcarboxylic acid and most particularly an acrylic acid or a methacrylic acid or mixtures thereof, the fatty-chain allyl ether unit of which corresponds to the monomer of formula (I) below:

CH ₂ = CR'CH ₂ O B _n R (I)

in which R' denotes H or CH ₃ , B denotes an ethylenoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon-based radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising from 8 to 30 carbon atoms, preferably 10 to 24 and even more particularly from 12 to 18 carbon atoms. A unit of formula (I) that is more particularly preferred is a unit in which R' denotes H, n is equal to 10, and R denotes a stearyl radical (Cis).

Anionic associative polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479.

Among these anionic associative polymers, those that are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of Ci-C ₄ alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (I), and from 0 to 1 % by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

Among the latter polymers, those most particularly preferred are crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), in particular those sold by the company Ciba under the names Salcare SC 80® and Salcare SC 90®, which are aqueous 30% emulsions of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10);

- (II) those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of (Cio-C3o)alkyl ester of unsaturated carboxylic acid type.

These polymers are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (II) below:

Γ.Η Γ. C OH

I II ^(M '

R ₁ O

in which Ri denotes H or CH ₃ or C ₅ H ₅ , i.e. acrylic acid, methacrylic acid or ethacrylic acid units, and whose hydrophobic unit of the type such as a (Cio- C30) alkyl ester of an unsaturated carboxylic acid corresponds to the monomer of formula (III) below:

CH ₂ C C OR ₃

I II (i ll)

R ₂ O '

in which R ₂ denotes H or CH ₃ or C2H ₅ (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH ₃ (methacrylate units), R3 denoting a C 10-C30 and preferably C12-C22 alkyl radical.

(C10-C30) alkyl esters of unsaturated carboxylic acids according to the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic polymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509 949.

Among the anionic associative polymers of this type that will be used more particularly are polymers formed from a monomer mixture comprising:

(i) essentially acrylic acid,

(ii) an ester of formula (III) described above in which R ₂ denotes H or CH ₃ , R3 denoting an alkyl radical containing from 12 to 22 carbon atoms, and

(iii) a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl

(meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

Among anionic associative polymers of this type that will be used more particularly are those consisting of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10-C30 alkyl acrylate (hydrophobic unit) and 0% to 6% by weight of crosslinking polymerizable monomer, or alternatively those consisting of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1 % to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among the said above polymers, those most particularly preferred according to the present invention are the products sold by the company Lubrizol under the trade names Pemulen TR1 ®, Pemulen TR2® and Carbopol 1382®, and even more preferentially Pemulen TR1 ®, and the product sold by the company SEPPIC under the name Coatex SX®.

- (Ill) maleic anhydride/C3o-C38 cc-olefin/alkyl maleate terpolymers, such as the product (maleic anhydride/C3o-C38 cc-olefin/isopropyl maleate copolymer) sold under the name Performa V 1608® by the company Newphase Technologies.

-(IV) acrylic terpolymers comprising: (a) about 20% to 70% by weight of a carboxylic acid containing α,β- monoethylenic unsaturation,

(b) about 20% to 80% by weight of a non-surfactant monomer containing α,β-monoethylenic unsaturation other than (a),

(c) about 0.5% to 60% by weight of a nonionic monourethane which is the product of reaction of a monohydric surfactant with a monoisocyanate containing monoethylenic unsaturation,

such as those described in patent application EP-A-0 173 109 and more particularly the terpolymer described in Example 3, namely a methacrylic acid/methyl acrylate/behenyl alcohol dimethyl-meta- isopropenylbenzylisocyanate ethoxylated (40 EO) terpolymer, as an aqueous 25% dispersion.

- (V) copolymers comprising among their monomers an α,β- monoethylenically unsaturated carboxylic acid and an ester of an α,β- monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise as monomer an ester of an α,β-monoethylenically unsaturated carboxylic acid and of a Ci-C ₄ alcohol.

An example of a compound of this type that may be mentioned is Aculyn 22® and Aculyn 88® sold by the company Rohm & Haas, which are methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymers.

Mention may also be made of Synthalen W400 sold by the company 3V- Sigma, which is an acrylate copolymer in aqueous emulsion, and Synthalen W2000 sold by the company 3V-Sigma, which is an acrylate/polyoxyethylenated (25 OE) Ci2-24 alcohol acrylate copolymer in aqueous emulsion.

Mention may also be made of the product Structure 2001 sold by the company Akzo Nobel, which is an acrylic acid/oxyethylenated (20 OE) monostearyl itaconate copolymer as a 30% aqueous dispersion.

Mention will also be made of the products sold by the company Lubrizol under the trade references Carbopol Ultrez 21 , which is an acrylic polymer (acrylates/Cio-30 alkyl acrylate crosspolymer) and Novethix L-10, which is an acrylates/Beheneth-25 methacrylate copolymer.

According to the invention, the associative polymers of nonionic type are preferably chosen from:

-(1 ) celluloses modified with groups comprising at least one fatty chain.

Examples that may be mentioned include:

- hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, for instance the product Natrosol Plus Grade 330 CS® (C16 alkyls) sold by the company Aqualon, or the product Bermocoll EHM 100® sold by the company Berol Nobel, - hydroxyethyl celluloses modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500® (polyethylene glycol (15) nonylphenyl ether) sold by the company Amerchol,

-(2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22® (C22 alkyl chain) sold by the company Lamberti, and the products RE210-18® (CM alkyl chain) and RE205- 1 ® (C20 alkyl chain) sold by the company Rhodia Chimie.

-(3) inulins modified with groups comprising at least one fatty chain, such as inulin alkyl carbamates and in particular the inulin lauryl carbamate sold by the company Orafti under the name Inutec SP1 .

-(4) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers; examples that may be mentioned include:

the products Antaron V216® or Ganex V216® (vinyl pyrrol idone/hexadecene copolymer) sold by the company I.S.P.

- the products Antaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer) sold by the company ISP,

-(5) copolymers of C1 -C6 alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain, such as, for example, the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208®.

-(6) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer,

-(7) polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;

-(8) polymers with an aminoplast ether backbone containing at least one fatty chain, such as the Pure Thix® compounds sold by the company Sud- Chemie.

Preferably, the polyurethane polyethers comprise at least two hydrocarbon-based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be included. In addition, the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.

The polyurethane polyethers may be multiblock, in particular in triblock form. The hydrophobic blocks may be at each end of the chain (for example: triblock copolymer containing a hydrophilic central block) or distributed both at the ends and in the chain (for example multiblock copolymer). These same polymers may also be graft polymers or star polymers.

The nonionic fatty-chain polyurethane polyethers may be triblock copolymers in which the hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylene groups. The nonionic polyurethane polyethers comprise a urethane bond between the hydrophilic blocks, whence arises the name.

By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.

As examples of nonionic fatty-chain polyurethane polyethers that may be used in the invention, it is also possible to use Rheolate FX 1 100 (Steareth- 100/PEG 136/HDI copolymer), Rheolate 205® containing a urea function, sold by the company Elementis, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®.

Mention may also be made of the product Elfacos T210® containing a C12- Ci4 alkyl chain, and the product Elfacos T212® containing a C18 alkyl chain, from Akzo.

The product DW 1206B® from Rohm & Haas containing a C20 alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.

It is also possible to use solutions or dispersions of these polymers, in particular in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned are Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Elementis. The products DW 1206F and DW 1206J sold by the company Rohm & Haas may also be used.

The polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci. 271 , 380-389 (1993).

Even more particularly, according to the invention, it is also preferred to use a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.

Such polyurethane polyethers are sold especially by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %); Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].

According to one preferred embodiment of the invention, the associative polymer(s) are chosen from anionic associative polymers. Even more preferentially, the associative polymers are chosen from methacrylic acid/ethyl acrylate/oxyethylenated stearyl methacrylate terpolymers. According to another embodiment of the invention, the associative polymers are fatty-chain nonionic polyurethane polyethers.

The associative polymer(s) of the composition are present in a concentration ranging from 0.01 % to 30% by weight, preferably in a concentration ranging from 0.1 % to 20% by weight, and even more preferentially ranging from 0.5% to 10% by weight, relative to the total weight of the composition.

All the anionic, cationic, amphoteric and nonionic fixing polymers and mixtures thereof used in the art may be used in the compositions according to the present application.

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

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

The anionic fixing polymers containing carboxylic groups that are preferred according to the invention are:

A) 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;

B) copolymers of acrylic or methacrylic acid with a monoethylenic monomer such as ethylene, styrene, vinyl esters, acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glycol such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1 222 944 and German patent application 2 330 956, the copolymers of this type comprising an optionally N-alkylated and/or hydroxyalkylated acrylamide unit in their chain as described in particular in Luxembourg patent applications 75370 and 75371 or sold under the name Quadramer by the company American Cyanamid. Mention may also be made of the acrylic acid/ethyl acrylate/N-terf-butylacrylamide terpolymers such as Ultrahold Strong sold by the company BASF. Mention may also be made of copolymers of acrylic acid and of Ci-C ₄ alkyl methacrylate and terpolymers of vinylpyrrolidone, of acrylic acid and of methacrylate of C ₁ -C ₂ 0 alkyl, for example of lauryl, such as the product 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 acrylate/hydroxy ester acrylate copolymers, such as Acudyne 180 sold by the company Dow Chemical.

Mention may also be made of methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers as an aqueous dispersion, sold under the name Amerhold® DR 25 by the company Amerchol; C) crotonic acid copolymers, such as those comprising vinyl acetate or propionate units in their chain and optionally other monomers such as allyl esters or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon-based chain, such as those containing at least 5 carbon atoms, it being possible for these polymers optionally to be grafted or crosslinked, or alternatively another vinyl, allyl or methallyl ester monomer of an a- or β-cyclic carboxylic acid. Such polymers are described, inter alia, in French patents 1 222 944, 1 580 545, 2 265 782, 2 265 781 , 1 564 1 10 and 2 439 798. Commercial products that come under this category are the resins 28-29-30, 26-13-14 and 28-13-10 sold by the company Akzo Nobel;

D) copolymers derived from C ₄ -Cs monounsaturated carboxylic acids or anhydrides chosen from:

- copolymers comprising (i) one or more maleic, fumaric or itaconic acids or anhydrides and (ii) at least one monomer selected from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers optionally being monoesterified or monoamidated. Such polymers are described, in particular, in US patents 2 047 398, 2 723 248 and 2 102 1 13, and GB patent 839 805. Commercial products are especially those sold under the names Gantrez® AN or ES by the company ISP;

- copolymers comprising (i) one or more maleic, citraconic or itaconic anhydride units and (ii) one or more monomers selected from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, cc-olefin, acrylic or methacrylic ester, acrylic or methacrylic acid or vinylpyrrolidone groups in their chain,

the anhydride functions of these copolymers optionally being monoesterified or monoamidated.

These polymers are described, for example, in French patents 2 350 384 and 2 357 241 by the Applicant.

E) Polyacrylamides comprising carboxylate groups.

F) Homopolymers and copolymers comprising sulfonic groups such as polymers comprising vinylsulfonic, styrenesulfonic, naphthalenesulfonic or acrylamidoalkylsulfonic units.

These polymers may be chosen especially from:

- polyvinylsulfonic acid salts having a molecular weight of approximately between 1000 and 100 000, and also the copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and their esters, and also acrylamide or its derivatives, vinyl ethers and vinylpyrrolidone;

- polystyrenesulfonic acid salts such as the sodium salts that are sold for example under the names Flexan ^® 500 and Flexan ^® 130 by Akzo Nobel. These compounds are described in patent FR 2 198 719; - polyacrylamidesulfonic acid salts, such as those mentioned in patent US 4 128 631 and more particularly polyacrylamidoethylpropanesulfonic acid sold under the name Cosmedia Polymer HSP 1 180 by Henkel.

As another anionic fixing polymer that 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 Lubrizol.

According to the invention, the anionic fixing polymers are preferably chosen from copolymers of acrylic acid or of acrylic esters, such as the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold especially under the name Ultrahold ^® Strong by the company BASF, copolymers derived from crotonic acid, such as vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold especially under the name Resin 28-29-30 by the company Akzo Nobel, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives and acrylic acid and esters thereof, such as the methyl vinyl ether/monoesterified maleic anhydride copolymers sold, for example, under the name Gantrez ^® by the company ISP, the copolymers 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, the vinyl acetate/crotonic acid copolymers sold under the name Luviset CA 66 by the company BASF, the vinyl acetate/crotonic acid copolymers grafted with polyethylene glycol sold under the name Aristoflex ^® A by the company BASF, and the polymer sold under the name Fixate G-100 L by the company Lubrizol.

The cationic fixing film-forming polymers that can be used according to the present invention are preferably selected from polymers comprising primary, secondary, tertiary and/or quaternary amine groups forming part of the polymer chain or directly attached thereto, and having a molecular weight of between 500 and about 5 000 000 and preferably between 1000 and 3 000 000.

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 at least one of the units of the following formulae: in which:

R3 denotes a hydrogen atom or a CH ₃ radical;

A is a linear or branched alkyl group comprising 1 to 6 carbon atoms or a hydroxyalkyl group comprising 1 to 4 carbon atoms;

R ₄ , R ₅ and R6, which may be identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical;

Ri and R2, which may be identical or different, each represent a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms;

X denotes a methosulfate anion or a halide such as chloride or bromide.

The copolymers of the family (1 ) also contain one or more units derived from comonomers that may be selected from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (Ci-C ₄ ) alkyl groups, groups derived from acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among these copolymers of the family (1 ), mention may be made of:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Hercofloc® by the company Hercules,

- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, described, for example, in patent application EP-A-080 976 and sold under the name Bina Quat P 100 by the company Ciba Geigy,

- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, such as the product sold under the name Reten by the company

Hercules,

- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat® by the company ISP, such as, for example, Gafquat® 734 or Gafquat® 755, or alternatively the products known as Copolymer® 845, 958 and 937. These polymers are described in detail in French patents 2 077 143 and 2 393 573,

- fatty-chain polymers containing a vinylpyrrolidone unit, such as the products sold under the name Styleze W20 and Styleze W10 by the company ISP, dimethylaminoethyl methacrylate/vinylcaprolactann/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP, and

- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, such as the products sold under the name Gafquat® HS 100 by the company ISP;

(2) non-cellulosic cationic polysaccharides, preferably containing quaternary ammonium, such as those described in US patents 3 589 578 and 4 031 307, such as guar gums containing trialkylammonium cationic groups. Such products are sold in particular under the trade names Jaguar C13 S, Jaguar C 15 and Jaguar C 17 by Meyhall;

(3) quaternary copolymers of vinylpyrrolidone and of vinylimidazole;

(4) chitosans or salts thereof; the salts that can be used are, in particular, chitosan acetate, lactate, glutamate, gluconate or pyrrol idonecarboxylate.

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, and chitosan pyrrol idonecarboxylate sold under the name Kytamer® 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 disclosed in particular in patent US 4 131 576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted in particular with a methacryloyloxyethyltrimethylammonium,

methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.

The commercial products corresponding to this definition are, more particularly, the products sold as Celquat L 200 and Celquat H 100 by the company Akzo Nobel.

(6) partially hydrolysed polyvinylformamide polymers, such as the products sold under the names Lupamin 9095, Lupamin 9010 and Lupamin 9030 and the company BASF.

The amphoteric fixing polymers that can be used in accordance with the invention may be selected from polymers comprising units B and C distributed randomly 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 an acid monomer comprising one or more carboxylic or sulfonic groups, or alternatively B and C can denote groups derived from carboxybetaine or sulfobetaine zwitterionic monomers;

B and C can also denote 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 sulfonic group connected via a hydrocarbon group, or alternatively B and C form part of a chain of a polymer comprising an α,β-dicarboxylic ethylene unit in which one of the carboxylic groups has been made to react with a polyamine comprising one or more primary or secondary amine groups.

The amphoteric fixing polymers corresponding to the definition given above that are more particularly preferred are chosen from the following polymers:

(1 ) Copolymers comprising acidic vinyl units and basic vinyl units, such as those resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, a-chloroacrylic acid, and of a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamides and acrylamides. Such compounds are described in patent US 3 836 537.

(2) Polymers comprising units deriving from:

a) at least one monomer selected from acrylamides and 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 esters containing primary, secondary, tertiary and quaternary amine substituents 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 preferred according to the invention are compounds in which the alkyl groups contain from 2 to 12 carbon atoms and more particularly N- ethylacrylamide, N-terf-butylacrylamide, N-terf-octylacrylamide, N- octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers are selected more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acid and alkyl monoesters, having 1 to 4 carbon atoms, of maleic or fumaric acid or anhydride.

The preferred basic comonomers are aminoethyl, butylaminoethyl, Ν,Ν'- dimethylaminoethyl and N-terf-butylaminoethyl methacrylates.

The copolymers whose CTFA (4th edition, 1991 ) name is octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold under the name Amphomer ^® or Lovocryl ^® 47 by the company Akzo Nobel, are particularly used.

(3) Crosslinked and acylated polyamino amides partially or totally deriving from polyamino amides of general formula:

CO R _1fl — CO (IV) in which Rio represents a divalent group derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid containing an ethylenic double bond, an ester of a lower alkanol, having 1 to 6 carbon atoms, of these acids, or a group derived from the addition of any one of the said acids to a bis(primary) or bis(secondary) amine, and Z denotes a group derived from a bis(primary), mono- or bis(secondary) polyalkylene-polyamine and preferably represents: a) in roportions of from 60 to 100 mol%, the group:

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

this group being derived from diethylenetriamine, from triethylenetetramine or from dipropylenetriamine;

b) in proportions of from 0 to 40 mol%, the group (X) above in which x = 2 and p = 1 and which is derived from ethylenediamine, or the group derived from piperazine:

/ \

-N N-

\ /

c) in proportions of from 0 to 20 mol%, the -NH-(CH ₂ )6-NH- group being derived from hexamethylenediamine,

these polyaminoamides being crosslinked by addition reaction of a difunctional crosslinking agent selected from epihalohydrins, diepoxides, dianhydrides and bis-unsaturated derivatives, using from 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide and acylated by the action of acrylic acid, chloroacetic acid or an alkane sultone, or salts thereof.

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

The alkane sultones used in the acylation are preferably propane sultone or butane sultone; the salts of the acylating agents are preferably the sodium or potassium salts.

(4) Polymers comprising zwitterionic units of formula:

R 12 R 14 O

«11 N— (CH ₂ ) — C - O (VI)

^R 13 ^{y R} 15

in which R denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R12 and R13 represent a hydrogen atom, a methyl, ethyl or propyl group, Ri ₄ and R15 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in Ri and R15 does not exceed 10. The polymers comprising such units can also comprise 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 the methyl methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate copolymers such as the product sold as Diaformer Z301 by Sandoz;

(5) Polymers derived from chitosan comprising monomer units corresponding to the following formulae:

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), Ri ₆ represents a group of formula:

in which, if q = 0, R17, R18 and R19, 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 that are optionally interrupted by one or more nitrogen atoms and/or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio residue in which the alkyl group bears an amino residue, at least one of the groups R17, Ris and R19 being, in this case, a hydrogen atom;

or, if q = 1 , R17, R18 and R19 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(6) Polymers with units corresponding to the general formula (VII) are described, for example, in French patent 1 400 366: R 20

(CH— CH ₂ )

COOH CO (VII)

N - R ₂₁

^24

N - R.3

¾2

in which R ₂ o represents a hydrogen atom, a CH ₃ O, CH ₃ CH ₂ O or phenyl group, R21 denotes a hydrogen atom or a lower alkyl group such as methyl or ethyl, R22 denotes a hydrogen atom or a Ci-6 lower alkyl group such as methyl or ethyl, R23 denotes a Ci-6 lower alkyl group such as methyl or ethyl or a group corresponding to the formula: -R24-N(R22)2, R24 representing a -CH ₂ -CH ₂ -, -CH ₂ - CH2-CH2- or -CH ₂ -CH(CH ₃ )- group, R22 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 -D-X-D-X- type chosen from:

a) polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula:

-D-X-D-X-D- (VIII)

where D denotes a

/ \

-N N-

\ /

and X denotes the symbol E or E', E or E', which may be identical or different, denote a divalent group that is an alkylene group with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with hydroxyl groups and which can comprise, in addition to the oxygen, nitrogen and sulfur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups,

b) the polymers of formula:

-D-X-D-X- (IX)

where D denotes a / \

N N

\ /

and X denotes the symbol E or E' and at least once E'; E having the meaning given above and E' is a divalent group that is an alkylene group with a straight or branched chain having up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with one or more hydroxyl groups and containing one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain that is optionally interrupted by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloroacetic acid or sodium chloroacetate.

(9) (Ci-C ₅ )alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an Ν,Ν-dialkylaminoalkylamine such as N,N- dimethylaminopropylamine or by semiesterification with an N,N- dialkylaminoalkanol. These copolymers can also comprise other vinyl comonomers such as vinylcaprolactam.

Among the amphoteric fixing polymers mentioned above, the ones that are most particularly preferred according to the invention are those of family (3), such as the copolymers whose CTFA name is octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold under the names Amphomer ^® , Amphomer ^® LV 71 or Lovocryl ^® 47 by the company Akzo Nobel and those of family (4) such as the copolymers of methyl methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate, sold, for example, under the name Diaformer Z301 by the company Sandoz.

The nonionic fixing polymers that may be used according to the present invention are selected, for example, from:

- polyalkyloxazolines;

- vinyl acetate homopolymers;

- vinyl acetate copolymers, for instance copolymers of vinyl acetate and of acrylic ester; copolymers of vinyl acetate and of ethylene, or copolymers of vinyl acetate and of maleic ester, for example of dibutyl maleate;

- homopolymers and copolymers of acrylic esters, for instance copolymers of alkyl acrylates and of alkyl methacrylates, such as the products sold by the company Rohm & Haas under the names Primal ^® AC-261 K and Eudragit ^® NE 30 D, by the company BASF under the name 8845, or 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;

- styrene homopolymers;

- styrene copolymers, for instance copolymers of styrene and of an alkyl (meth)acrylate, such as the products Mowilith ^® LDM 691 1 , Mowilith ^® DM 61 1 and Mowilith ^® LDM 6070 sold by the company Hoechst, and the products Rhodopas ^® SD 215 and Rhodopas ^® DS 910 sold by the company Rhone- Poulenc; copolymers of styrene, of alkyl methacrylate and of alkyl acrylate; copolymers of styrene and of butadiene; or copolymers of styrene, of butadiene and of vinylpyridine;

- polyamides;

- vinyllactam homopolymers such as vinylpyrrolidone homopolymers and such as the polyvinylcaprolactam sold under the name Luviskol ^® Plus by the company BASF; and

- vinyllactam copolymers such as a poly(vinylpyrrolidone/vinyllactam) copolymer sold under the trade name Luvitec ^® VPC 55K65W by the company BASF, poly(vinylpyrrolidone/vinyl acetate) copolymers, such as those sold under the name PVPVA ^® S630L by the company ISP, Luviskol ^® VA 73, VA 64, VA 55, VA 37 and VA 28 by the company BASF; and poly(vinylpyrrolidone/vinyl acetate/vinyl propionate) terpolymers, for instance the product sold under the name Luviskol ^® VAP 343 by the company BASF.

- non-hydrolysed polyvinylformamide polymers such as the product sold under the name Lupamin 9000 by the company BASF.

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

According to the invention, it is also possible to use fixing polymers of grafted silicone type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer and the other being grafted to the said main chain.

These polymers are described, for example, in patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0 582 152 and WO 93/23009 and patents US 4 693 935, US 4 728 571 and US 4 972 037.

These polymers may be amphoteric, anionic or nonionic, and are preferably anionic or nonionic.

Such polymers are, for example, copolymers that may be obtained by free radical polymerization from the monomer mixture formed from:

a) 50% to 90% by weight of terf-butyl acrylate,

b) 0 to 40% by weight of acrylic acid,

c) 5% to 40% by weight of a silicone macromer of formula: -CH ₃

in which v is a number ranging from 5 to 700, the weight percentages being calculated relative to the total weight of the monomers.

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

Another type of silicone fixing polymer that may be mentioned is the product Luviflex Silk, sold by the company BASF.

As fixing polymers it is also possible to use functionalized or non- functionalized, cationic, nonionic, anionic or amphoteric, silicone or non-silicone polyurethanes, or mixtures thereof.

The polyurethanes particularly intended by the present invention are those disclosed in patents EP 0 751 162, EP 0 637 600, EP 0 648 485 and FR 2 743 297, of which the Applicant is the proprietor, and patents EP 0 656 021 or WO 94/03510 from the company BASF and EP 0 619 1 1 1 from the company Akzo Nobel.

As polyurethanes that are particularly suitable for the present invention, mention may be made of the products sold under the names Luviset Pur and Luviset Si-Pur by the company BASF.

The fixing polymer(s) of the present invention are present in a concentration ranging from 0.1 % to 40%, preferentially ranging from 0.5% to 25% by weight and even more preferentially ranging from 1 % to 10% by weight relative to the total weight of the composition.

The surfactants of the composition according to the invention are of anionic, cationic, amphoteric or zwitterionic type.

For the purposes of the present invention, the term "surfactant" means any compound that reduces the surface tension of a liquid, and in particular of water at 25°C, whose chemical structure a) does not involve a polymerization reaction or b) involves only the polymerization of an alkylene oxide and/or of glycidol.

The surfactants may be linear or branched.

The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the groups -C(O)OH, -C(O)O-, -SO ₃ H, -S(O) ₂ O-, -OS(O) ₂ OH, - OS(O) ₂ O-, -P(O)OH ₂ , -P(O) ₂ O-, -P(O)O ₂ -, -P(OH) ₂ , =P(O)OH, -P(OH)O-, =P(O)O-, =POH, =PO-, the anionic parts comprising a cationic counterion such as an alkali metal, an alkaline-earth metal or an ammonium.

As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyi sulfates, alkyi ether sulfates, alkylamido ether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, a-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkylether sulfosuccinates, alkylamide sulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamat.es, acylisethionates and N-acyltaurates, salts of alkyi monoesters of polyglycoside-polycarboxylic acids, acyllactylates, D-galactoside uronic acid salts, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts; and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds comprising from 6 to 24 carbon atoms and the aryl group denoting a phenyl group.

These compounds can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

The salts of C6-C2 ₄ alkyl monoesters of polyglycoside-polycarboxylic acids can be selected from C6-C2 ₄ alkyl polyglycoside-citrates, C6-C2 ₄ alkyl polyglycoside-tartrates and C6-C2 ₄ alkyl polyglycoside-sulfosuccinates.

When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline-earth metal salts such as the magnesium salts.

Examples of amino alcohol salts that may especially be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2- amino-2-methyl-1 -propanol salts, 2-amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

Alkali metal or alkaline-earth metal salts, and in particular sodium or magnesium salts, are preferably used.

Among the anionic surfactants mentioned, use is preferably made of (Ce- C2 ₄ )alkyl sulfates, (C6-C2 ₄ )alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, especially in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.

In particular, use is preferably made of (Ci2-C2o)alkyl sulfates, (C12- C2o)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, especially in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds. Better still, it is preferred to use sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.

The amphoteric or zwitterionic surfactant(s), which are preferably (a) non- silicone surfactant(s), which can be used in the present invention may in particular be derivatives of optionally quaternized secondary or tertiary aliphatic amines, in which derivatives the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, the said amine derivatives comprising at least one anionic group, such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may be made in particular of (Cs- C2o)alkylbetaines, sulfobetaines, (C8-C2o)alkylamido(C3-C8)alkylbetaines and (C8-C2o)alkylamido(C6-C8)alkylsulfobetaines. Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that can be used, as defined above, mention may also be made of the compounds of respective structures (A1 ) and (A2):

Ra-C(O)-NH-CH ₂ -CH ₂ -N ⁺ (Rb)(Rc)-CH ₂ C(O)O ^" , M ⁺ , X ^" (A1 ) in which formula (A1 ):

Ra represents a C10-C30 alkyl or alkenyl group derived from an acid Ra-COOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;

Rb represents a β-hydroxyethyl group; and

■ Rc represents a carboxymethyl group;

^■ M ⁺ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine, and

^■ X ^" represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C ₄ )alkyl sulfates, (Ci-

C ₄ )alkyl- or (Ci-C ₄ )alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M ⁺ and X ^" are absent;

Ra'-C(O)-NH-CH ₂ -CH ₂ -N(B)(B') (A2)

in which formula (A2):

■ B represents the group -CH ₂ -CH ₂ -O-X';

^■ B' represents the group -(CH ₂ )zY', with z = 1 or 2;

^■ X' represents the group -CH ₂ -C(O)OH, -CH ₂ -C(O)OZ', -CH ₂ -CH ₂ -C(O)OH or -CH ₂ -CH ₂ -C(O)OZ', or a hydrogen atom;

^■ r represents the group -C(O)OH, -C(O)OZ', -CH ₂ -CH(OH)-SO ₃ H or the group -CH ₂ -CH(OH)-SO ₃ -Z';

^■ Z' represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;

^■ Ra' represents a C10-C30 alkyl or alkenyl group of an acid Ra'-C(O)OH preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially of C17 and its iso form, or an unsaturated C17 group.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol ^® C2M Concentrate. Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of (C8-C2o)alkylbetaines such as cocoylbetaine, (Cs- C2o)alkylamido(C3-C8)alkylbetaines such as cocamidopropylbetaine, and mixtures thereof. More preferentially, the amphoteric or zwitterionic surfactant(s) are chosen from cocamidopropylbetaine and cocoylbetaine.

The cationic surfactant(s) which can be used in the composition according to the invention comprise, for example, salts of optionally polyoxyalkylenated primary, secondary or tertiary fatty amines, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may especially be mentioned include:

- those corresponding to the general formula (A3) below:

in which formula (A3):

■ Rs to Rn , which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one of the groups Rs to Rn comprises from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms; and

■ X ^" represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C ₄ )alkyl sulfates, (Ci- C ₄ )alkyl- or (Ci-C ₄ )alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate.

The aliphatic groups of Rs to Rn may also comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens.

The aliphatic groups of Rs to Rn are chosen, for example, from C1-C30 alkyl, C1-C30 alkoxy, polyoxy(C2-Ce)alkylene, C1-C30 alkylamide, (C12- C22)alkylamido(C2-C6)alkyl, (Ci2-C22)alkylacetate, C1-C30 hydroxyalkyl, X ^" is an anionic counterion chosen from halides, phosphates, acetates, lactates, (Ci- C ₄ )alkyl sulfates, and (Ci-C ₄ )alkyl- or (Ci-C ₄ )alkylarylsulfonates.

Among the quaternary ammonium salts of formula (A3), preference is given firstly to tetraalkylammonium chlorides, for instance dialkyldimethyl- ammonium or alkyltrimethylammonium chlorides in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, or else, secondly, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylamnnoniunn methosulfate, or else, lastly, palmitylamidopropyltrimethylammonium chloride or stearamidopropyl- di methyl (myristyl acetate)ammonium chloride, sold under the name Ceraphyl® 70 by the company Van Dyk;

- quaternary ammonium salts of imidazoline, for instance those of formula (A4) below:

(A4)

in which formula (A4):

^■ Ri2 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example tallow fatty acid derivatives;

^■ Ri3 represents a hydrogen atom, a Ci-C ₄ alkyl radical or an alkenyl or alkyl radical containing from 8 to 30 carbon atoms;

^■ Ri ₄ represents a Ci-C ₄ alkyl group;

^■ Ri ₅ represents a hydrogen atom or a Ci-C ₄ alkyl group;

^■ X ^" represents an organic or inorganic anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (Ci-C ₄ )alkyl sulfates, (Ci- C ₄ )alkyl- or (Ci-C ₄ )alkylarylsulfonates.

Ri2 and R13 preferably denote a mixture of alkyl or alkenyl groups comprising from 12 to 21 carbon atoms, for example tallow fatty acid derivatives, Ri ₄ denotes a methyl group, and R15 denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo;

- di- or triquaternary ammonium salts, in particular of formula (A5) below:

-N- -(CH ₂ -N- 2X ^"

R„ R„

(A5)

in which formula (A5):

^■ R16 denotes an alkyl group comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms;

^■ Ri ₇ is chosen from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group -(CH ₂ )3-N ⁺ (Ri6a)(Ri ₇ a)(Ri8a), X ^" ;

Ri6a, Ri ₇ a, Risa, Ris, R19, R20 and R21 , which may be identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms; and ^■ X ^" , which may be identical or different, represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (Ci-C ₄ )alkyl sulfates, (Ci-C ₄ )alkyl- or (Ci- C ₄ )alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate.

Such compounds are, for example, Finquat CT-P, provided by Finetex

(Quaternium 89), or Finquat CT, provided by Finetex (Quaternium 75);

- quaternary ammonium salts containing one or more ester functions, such as those of formula (A6) below:

in which formula (A6):

^■ R22 is chosen from C1-C6 alkyl and C1-C6 hydroxyalkyl or dihydroxyalkyl groups,

^■ R23 is selected from:

o

- the group ^{R2S c} ,

- linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based groups R ₂₇ ,

- a hydrogen atom,

^■ R25 is selected from:

O

- the group ^R 2 ^~c ,

- the groups R29, which are linear or branched, saturated or unsaturated

C1-C6 hydrocarbon-based radicals;

- a hydrogen atom,

^■ R2 ₄ , R26 and R28, which are identical or different, are selected from linear or branched, saturated or unsaturated C7-C21 hydrocarbon radicals;

■ r, s and t, which may be identical or different, are integers ranging from 2 to 6,

^■ r1 and t1 , which may be identical or different, are equal to 0 or 1 , with r2+r1 =2r and t1 +t2=2t,

^■ y is an integer ranging from 1 to 10,

" x and z, which may be identical or different, are integers ranging from 0 to 10,

^■ X ^" represents an organic or inorganic anionic counterion,

with the proviso that the sum x + y + z is from 1 to 15, that when x is 0, then R ₂ 3 denotes R27 and that when z is 0, then R25 denotes R29. The alkyl groups F½ may be linear or branched, and more particularly linear.

Preferably, F½ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.

Advantageously, the sum x + y + z is from 1 to 10.

When R ₂ 3 is a hydrocarbon-based group R27, it may be long and may have 12 to 22 carbon atoms, or may be short and may have from 1 to 3 carbon atoms.

When R25 is a hydrocarbon-based group R29, it preferably contains 1 to 3 carbon atoms.

Advantageously, R2 ₄ , R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon- based groups, and more particularly from linear or branched, saturated or unsaturated C11-C21 alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, are equal to 0 or 1 . y is advantageously equal to 1 .

Preferably, r, s and t, which may be identical or different, equal 2 or 3, and even more particularly are equal to 2.

The anionic counterion X ^" is preferably a halide, such as chloride, bromide or iodide; a (Ci-C ₄ )alkyl sulfate or a (Ci-C ₄ )alkyl- or (Ci-C ₄ )alkylarylsulfonate. However, it is possible to use methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium containing an ester function.

The anionic counterion X ^" is even more particularly chloride, methyl sulfate or ethyl sulfate.

Use is made more particularly in the composition according to the invention of the ammonium salts of formula (A6) in which:

- R22 denotes a methyl or ethyl group,

- x and y are equal to 1 ,

- z is equal to 0 or 1 ,

- r, s and t are equal to 2,

- R23 is chosen from: the group

methyl, ethyl or C14-C22 hydrocarbon-based groups a hydrogen atom,

- R25 is chosen from: the group

a hydrogen atom, - R2 ₄ , R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.

Advantageously, the hydrocarbon-based radicals are linear.

Among the compounds of formula (A6), examples that may be mentioned include salts, especially the chloride or methyl sulfate, of diacyloxyethyldimethylammonium,

diacyloxyethylhydroxyethylmethylammonium,

monoacyloxyethyldihydroxyethylmethylammonium,

triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably have from 14 to 18 carbon atoms and originate more particularly from a vegetable oil, such as palm oil or sunflower oil. When the compound comprises several acyl groups, the latter can be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolannine, which are optionally oxyalkylenated, with fatty acids or with mixtures of fatty acids of vegetable or animal origin, or by transesterification of their methyl esters. This esterification is followed by a quaternization by means of an alkylating agent, such as an alkyl halide, preferably methyl or ethyl halide, a dialkyl sulfate, preferably dimethyl or diethyl sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or Rewoquat® WE 18 by the company Rewo-Witco.

The composition according to the invention may contain, for example, a mixture of quaternary ammonium salts of monoesters, diesters and triesters with a weight majority of diester salts.

It is also possible to use the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131 .

Preferably, the ammonium salts containing at least one ester function contain two ester functions.

Among the cationic surfactants that may be present in the composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethyl- hydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylamnnoniunn methosulfate, and mixtures thereof.

Preferably, the anionic, cationic or amphoteric surfactant(s) predominantly comprise fatty chains of 8 to 14 carbon atoms.

According to the invention, the term "fatty chain" means, as for the associative polymers, a linear or branched, optionally hydroxylated alkyl or alkenyl chain containing from 8 to 30 and preferably from 10 to 30 carbon atoms.

The surfactants are often mixtures of compounds especially having different fatty-alkyl chains.

The term "predominantly" then means that, for the surfactant under consideration, the weight percentage of compounds having fatty chains ranging from Cs to CM is greater than or equal to 50%.

In other words, the surfactants that may be used in the composition of the invention comprise a mixture of compounds having different fatty chain lengths, this mixture comprising more than 50% of compounds with fatty chains ranging from Cs to Ci ₄ .

The anionic, cationic or amphoteric surfactant(s) of the present invention are present in a concentration of greater than or equal to 2% by weight, preferably in a concentration ranging from 2% to 40%, preferentially from 2% to 25% and even more preferentially ranging from 4% to 10% by weight relative to the total weight of the composition. The composition may be aqueous or anhydrous. It is preferably aqueous.

It then preferably comprises from 5% to 97% water, even more preferentially from 20% to 95% water and better still from 50% to 90% water.

The composition may comprise at least one organic solvent preferably chosen from Ci-C ₄ lower alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol; polyols such as glycerol, propylene glycol and polyethylene glycols; acetone, propylene carbonate, benzyl alcohol, glycol ether derivatives; aminomethylpropanol, and mixtures thereof.

The pH of the compositions used according to the invention is generally between 1 and 13, preferably between 3 and 1 1 and even more preferentially between 6 and 9.

Preferentially, the composition according to the invention may contain active agents conventionally used in the temporary shaping of hair, other than those described previously, and chosen from nonionic surfactants, silicones, non- associative thickeners, cationic associative polymers, direct dyes, in particular cationic or natural dyes or oxidation dyes, organic or mineral pigments, UV- screening agents, fillers, especially nacres, T1O2, resins or clays, fragrances, peptizers, vitamins, amino acids, preserving agents, agents for long-lasting shaping of the hair, especially thiol-based organic reducing agents, non-thiol- based organic reducing agents, alkaline agents, etc.

Needless to say, a person skilled in the art will take care to select the optional additional compounds and/or the amount thereof such that the advantageous properties of the compositions used according to the invention are not, or are not substantially, adversely affected by the envisaged addition.

Preferably, the compositions are in the form of gels. Preferably, the compositions have a viscosity of greater than or equal to 4 Pa.s and better still ranging from 4 Pa.s to 500 Pa.s at a temperature of 25°C and at a shear rate of 1 s ^"1 (measurable, for example, with a Haake RS600 rheometer).

The composition according to the invention may especially be used as a leave-in application on the hair.

A subject of the invention is also a process for treating keratin fibres such as the hair, comprising the application of a cosmetic composition according to the invention.

The invention is illustrated in more detail in the following examples, which are provided by way of illustration and without implied limitation of the invention.

EXAMPLES

The styling gel formulations below according to the invention were prepared. The concentrations are expressed as mass percentages of active materials in the final composition.

Examples 1 to 4:

^(a) Aculyn 88 sold by the company Dow Chemical

^(b) Lupamin 9000 sold by BASF

( ^c) Copolymer 845-Ο sold by the company ISP

^(d) Texapon AOS 225 UP sold by the company Cognis (BASF) ^(e) Oramix L 30 sold by the company SEPPIC

^(f) Plantapon ACG LC sold by the company Cognis (BASF)

Protocol for application of 2.7 g to locks of natural chestnut-brown hair

1 . Ultra Doux camomile shampoo.

2. Rinsing with water, the water temperature being 38°C and the flow rate 4 l/minute, followed by removal of the shampoo by passing the fingers through 15 times under water.

3. Drying of the locks by 2 passes between the fingers.

4. Application of 1 g of the formulation homogeneously along the wet lock. 5. Drying in the open air.

For each of the compositions according to the invention, the gel obtained is homogeneous and thick enough to enable quick and easy application of the composition to the hair. In addition, the product slides well in the hands and on the hair so as to obtain uniform distribution over the entire head of hair.

On application and after drying, significant shaping of the hair and hold of this shape are obtained (presence of hardened locks). Evaluation of the fixing hold:

The hold of the hair is evaluated by successive passes of cold flat tongs through the lock. As more and more passes are performed, the lock becomes less rigid since the polymer film breaks. The more the lock withstands the passes of the cold tongs, the greater the hold of the gel .

It is found that the gels formulated according to the invention allow markedly greater fixing hold than in the case of the same styling gels without surfactant. Evaluation of the rinsing of the gels from the hair:

The locks prepared beforehand according to the above protocol are then rinsed with water according to the following protocol:

1 . Rinsing with water: the water temperature being 38°C and the flow rate 4 l/minute, followed by passing the fingers through 15 times under water.

2. Drying of the locks by 2 passes between the fingers.

3. Drying in the open air.

The locks are then classed according to their degree of cleanliness (removal of the product, smooth feel with no residues) by comparison with an untreated lock and relative to the same gel without surfactant.

It is found each time that the locks treated with a styling gel according to the invention are cleaner after rinsing with water than in the case of the same gel without surfactant. Evaluation of the rinsing of the gels from the hands:

1 g of gel is applied to the hands. The product is spread between the two hands. The hands are then passed under water (water temperature 38°C, flow rate 4 l/minute) and the rinsing time is measured.

It is found each time that the hands are rinsed much more quickly with a styling gel according to the invention. They are cleaner after rinsing with water than in the case of the same gel without surfactant.