Cosmetic composition comprising at least one acrylic and/or methacrylic thickening polymer, at least one fixing polymer and at least one anti-seborrhoeic agent

The invention relates to a cosmetic composition for keratinous fibres comprising (i) one or more thickening polymers comprising acrylic and/or methacrylic units, (ii) one or more fixing po lymers other than the polymers (i), and (iii) one or more anti-seborrhoeic agents . The invention also relates to the use of this composition for styling the hair. The invention also relates to the use of this composition for removing excess sebum on the scalp and/or hair.

Finally, the invention relates to a method for the cosmetic treatment of keratinous fibres, preferably the hair, comprising the application o f this composition to the keratinous fibres .

In the field of styling, in particular among hair products intended for the shaping and/or form retention of the hairstyle, the hair compositions are generally composed of a solution, generally alcoholic or aqueous, and o f one or more fixing polymers, as a mixture with various cosmetic adjuvants.

These compositions can be provided in the form o f hair gels or foams which are generally applied to wet hair, before carrying out a blow drying or a drying.

In particular, hair gels are composed in particular o f one or more thickening polymers or gelling agents in combination with one or more fixing po lymers, which generally have the role o f forming a film at the surface of the keratinous fibres to be fixed.

These styling gels are o ften perceived, on the part of consumers, as rendering the hair greasy.

This greasy aspect of the hair, which is a nuisance with regard to the feel, may also prove to be a nuisance from an aesthetic viewpoint. Thus, there exists a need to have available novel styling gel compositions which, while contributing an appropriate and lasting styling, do not leave a greasy appearance on the hair and scalp .

Conventional grease-control agents cannot be easily incorporated in aqueous media to result in stable compositions with acceptable cosmetic properties.

The Applicant Company has now discovered, surprisingly, that the combination o f a specific thickening polymer comprising acrylic and/or methacrylic units, of a fixing polymer and of an anti- seborrhoeic agent makes it possible to respond to the abovementioned problems in a particularly effective and satisfactory manner.

A subj ect-matter of the invention is thus a cosmetic composition for keratinous fibres comprising (i) one or more thickening polymers comprising acrylic and/or methacrylic units, (ii) one or more fixing po lymers other than the polymers (i), and (iii) one or more anti-seborrhoeic agents .

The composition according to the invention has excellent properties of use . In particular, it is easily and uniformly distributed over the hair.

The composition according to the invention also makes it possible to fix the hair in an effective and lasting fashion, thus resulting in particularly satisfactory shaping and/or form retention o f the hairstyle.

The treated hair is supple and not very sticky.

The composition does not leave large amounts of residues after removing with washing or by a mechanical effect.

In addition, the composition according to the invention has very good anti-seborrhoeic properties. This is because it makes it possible to remove excess sebum on the scalp and/or hair. The hair thus does not have a greasy appearance.

A further subj ect-matter of the invention is the use o f this composition for styling the hair.

Another subject-matter of the invention is the use o f this composition for removing excess sebum on the scalp and/or hair. Finally, a subj ect-matter of the invention is a method for the cosmetic treatment o f keratinous fibres, preferably the hair, comprising the application of this composition to the keratinous fibres.

Other subj ect-matters, characteristics, aspects and advantages of the invention will become even more clearly apparent on reading the description and the examp le which fo llow.

In that which fo llows and unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "of between" and "ranging from ... to

Moreover, the expression " at least one" used in the present description is equivalent to the expression "one or more" .

The composition according to the invention comprises one or more thickening polymers comprising acrylic and/or methacrylic units .

The term "po lymer comprising acrylic and/or methacrylic units" is understood to mean, within the meaning o f the present invention, a po lymer resulting from the polymerization o f one or more monomers including one or more monomers of structure (I) :

Ri denoting a hydrogen atom or a linear or branched C ₁ -C ₄ alkyl radical,

R ₂ denoting a hydrogen atom, a linear or branched C ₁ -C ₄ alkyl radical, an NR ₃ R ₄ radical or a linear or branched C ₁ - C30 alkoxy radical, optionally substituted by one or more hydroxyl radicals or by a quaternary ammonium radical,

R ₃ and R ₄ denoting a hydrogen atom or an optionally oxyalkylenated C ₁ - C30 alkyl radical, it being possible for the alkyl radical to comprise a sulfonic group .

Preferably, Ri denotes a hydrogen atom or a methyl radical.

The term "thickening po lymer" is understood to mean, within the meaning of the present invention, a polymer capable, by its presence, of increasing the viscosity o f the medium by at least 50 centipoises at 25°C and at a shear rate of 1 s ^{" 1} . Preferably, the solution obtained by dissolving the thickening polymer at 1 % by weight in water or in a 50/50 by weight water/alcohol mixture exhibits a viscosity at 25 ° C and at a shear rate of 1 s ^{" 1} which is greater than 100 centipoises . These viscosities can be measured using in particular viscometers or rheometers having cone-plate geometry.

The thickening polymers comprising acrylic and/or methacrylic units can be chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (C i - C ₆ )alkyl acrylate;

(d) non-ionic homopolymers and copolymers comprising ethylenically unsaturated monomers of ester and/or amide type;

(e) ammonium acrylate homopolymers or copolymers o f ammonium acrylate and of acrylamide;

(f) (meth)acrylamido(C i -C ₄ )alkylsulfonic acid homopolymers and copolymers;

(g) crosslinked methacryloyloxy(C i -C ₄ )alkyltri(C i - C ₄ )alkylammonium homopolymers and copolymers .

The thickening polymers comprising acrylic and/or methacrylic units can preferably be chosen from acrylic associative thickeners.

The term "associative thickener" is understood to mean, according to the invention, an amphiphilic thickener comprising both hydrophilic units and hydrophobic units, in particular comprising at least one C 8 - C 30 fatty chain and at least one hydrophilic unit.

Mention may be made, as acrylic associative thickeners which can be used in the composition according to the invention, of acrylic associative po lymers chosen from:

(i) non-ionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit;

(ii) anionic amphiphilic po lymers comprising at least one hydrophilic unit and at least one unit having a fatty chain; (iii) cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one unit having a fatty chain;

(iv) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one unit having a fatty chain;

the fatty chains having from 10 to 30 carbon atoms.

The non-ionic amphiphilic polymers can preferably be chosen from:

(1) copolymers of Ci-C ₆ alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain (for example oxyethylenated (C ₈ -C ₂₂ )alkyl acrylates), such as, for example, the oxyethylenated methyl methacrylate/stearyl acrylate copolymer sold by Goldschmidt under the name Antil 208;

(2) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain (for example (C ₈ -C ₂₂ )alkyl (meth)acrylates), such as, for example, polyethylene glycol methacrylate/lauryl methacrylate copolymer.

The anionic amphiphilic polymers can be chosen from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and at least one hydrophobic unit of unsaturated carboxylic acid (Cio-C3o)alkyl ester type. They are preferably chosen from those for which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of following formula (II):

H ₂ C= in which formula R ₃ denotes H or CH ₃ or C ₂ H ₅ , that is to say acrylic acid, methacrylic acid or ethacrylic acid units, and for which the hydrophobic unit of unsaturated carboxylic acid (Cio-C ₃ o)alkyl ester type corresponds to the monomer of following formula (III): in which formula R ₄ denotes H or CH ₃ or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH ₃ (methacrylate units), R ₅ denoting a Cio-C ₃ o and preferably C12-C22 alkyl radical.

(Cio-C ₃ o)alkyl esters of unsaturated carboxylic acids in accordance with the invention comprise, 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 amphiphilic polymers of this type are, for example, described and prepared according to Patents US-3 915 921 and US-4 509949.

The anionic amphiphilic polymers which can be used in the context of the present invention can more particularly denote polymers formed from a mixture of monomers comprising:

(i) acrylic acid and one or more esters of following formula (IV):

H ₂ C=C C— OR ₇

in which R ₆ denotes H or CH ₃ , R ₇ denoting an alkyl radical having from 12 to 22 carbon atoms, and a crosslinking agent, such as, for example, those constituted of from 95% to 60%> by weight of acrylic acid (hydrophilic unit), 4% to 40%> by weight of Cio-C ₃ o alkyl acrylate (hydrophobic unit) and 0%> to 6%> by weight of crosslinking polymerizable monomer, or 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of Cio-C ₃ o alkyl acrylate (hydrophobic unit) and 0. 1 % to 0.6% by weight of crosslinking polymerizable monomer,

(ii) essentially acrylic acid and lauryl methacrylate, such as the product formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacrylate.

The said crosslinking agent is a monomer comprising a

^{C H} 2 ^{= C} \

group with at least one other polymerizable group , the unsaturated bonds of which are non-conjugated with respect to one another. Mention may in particular be made o f po lyallyl ethers, such as, in particular, po lyallyl sucrose and polyallyl pentaerythrito l.

Among the said po lymers above, preference is very particularly given, according to the present invention, to the products sold by Goodrich under the trade names Pemulen TR1 , Pemulen TR2 and Carbopol 1382 , and more preferably still Pemulen TR 1 , and to the product sold by S .E .P .C . under the name Coatex SX.

Mention may also be made, as anionic amphiphilic polymers having fatty chains, o f the copolymer of methacrylic acid, methyl acrylate and dimethyl-meta-isopropenylbenzyl isocyanate of ethoxylated alcohol so ld under the name Viscophobe DB 1000 by Amercho l.

Mention may be made, as other anionic amphiphilic polymers having fatty chains, of those comprising at least one acrylic monomer having sulfonic group(s), in free or partially or completely neutralized form, and comprising at least one hydrophobic portion.

The hydrophobic portion present in the polymers of the invention preferably comprises from 8 to 22 carbon atoms, more preferably still from 8 to 1 8 carbon atoms and more particularly from 12 to 1 8 carbon atoms.

Preferably, the sulfonic polymers in accordance with the invention are partially or completely neutralized by an inorganic base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base, such as mono-, di- or triethano lamine, an aminomethylpropanedio l, N-methylglucamine, basic amino acids, such as arginine and lysine, and mixtures o f these compounds.

The sulfonic amphiphilic polymers in accordance with the invention generally have a number-average mo lecular weight ranging from 1000 to 20 000 000 g/mo l, preferably ranging from 20 000 to 5 000 000 g/mo l and more preferably still ranging from 100 000 to 1 500 000 g/mo l.

The sulfonic amphiphilic polymers according to the invention may or may not be crosslinked. Crosslinked amphiphilic polymers are preferably chosen.

When they are crosslinked, the crosslinking agents can be chosen from po lyo lefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by radical polymerization. Mention may be made, for examp le, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glyco l divinyl ether, hydroquinone diallyl ether, ethylene glyco l di(meth)acrylate or tetraethylene glycol di(meth)acrylate, trimethylo lpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylo lpropane diallyl ether, allyl (meth)acrylate, allyl ethers o f alcoho ls o f the sugar series, or other allyl or vinyl ethers o f polyfunctional alcoho ls, and also allyl esters o f phosphoric and/or vinylpho sphonic acid derivatives, or mixtures o f these compounds.

Methylenebisacrylamide, allyl methacrylate or trimethylo lpropane triacrylate (TMPTA) will more particularly be used. The degree of crosslinking will generally vary from 0.0 1 mol% to 1 0 mo l% and more particularly from 0.2 mo l% to 2 mo l%, with respect to the polymer.

The acrylic monomers having sulfonic group(s) are chosen in particular from (meth)acrylamido(C i -C ₂₂ )alkylsulfonic acids and N- (C i -C ₂₂ )alkyl(meth)acrylamido(C i -C ₂₂ )alkylsulfonic acids, such as undecylacrylamidomethanesulfonic acid, and also their partially or completely neutralized forms. More preferably, use will be made of (meth)acrylamido(C i - C22)alkylsulfonic acids, such as, for example, acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4- trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3 -heptanesulfonic acid, and also their partially or completely neutralized forms .

More particularly, use will be made of 2-acrylamido-2- methylpropanesulfonic acid (AMPS®), and also its partially or completely neutralized forms.

The amphiphilic polymers in accordance with the invention can in particular be chosen from random amphiphilic AMPS® polymers modified by reaction with an n-mono(C6 - C22)alkylamine or a di[n-(C ₆ - C22)alkyl] amine, such as those described in Patent Application WO 00/3 1 1 54; the polymers described in this patent application form part of the content of the present description. These polymers can also comprise other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcoho ls or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

The po lymers o f the invention can be cho sen from amphiphilic copolymers of AMPS® and of at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic portion having from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 8 to 1 8 carbon atoms and more particularly from 12 to 1 8 carbon atoms .

These same copolymers can additionally comprise one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcoho ls or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

These copolymers are described in particular in Patent Application EP-A-750 899, in Patent US 5 089 578 and in the following Yotaro Morishima publications:

"Self-assembling amphiphilic polyelectrolytes and their nanostructures", Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;

"Micelle formation of random copolymers of sodium 2- (acrylamido)-2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering", Macromolecules, 2000, Vol. 33, No. 10, 3694-3704;

"Solution properties of micelle networks formed by non-ionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior", Langmuir, 2000, Vol. 16, No. 12, 5324-5332;

- "Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido)-2-methylpropanesulfonate and associative macromonomers", Polym. Preprint, Div. Polym. Chem., 1999, 40(2), 220-221.

The ethylenically unsaturated hydrophobic monomers of these specific copolymers are preferably chosen from the acrylates or acrylamides of following formula (V):

in which Rs and Rio, which are identical or different, denote a hydrogen atom or a linear or branched Ci-C ₆ alkyl radical (preferably methyl); Y denotes O or NH; R ₉ denotes a hydrophobic hydrocarbon radical comprising at least from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 6 to 1 8 carbon atoms and more particularly from 12 to 1 8 carbon atoms; and x denotes a number of mo les o f alkylene oxide and varies from 0 to 100.

The R9 radical is preferably chosen from linear C ₆ -C i ₈ (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl or n-dodecyl) alkyl radicals or branched or cyclic (for example cyclododecane (C _{1 2} ) or adamantane (C _{1 0} )) alkyl radicals; C ₆ -C i ₈ perfluoroalkyl radicals (for example the group of formula -(CH ₂ ) 2-(CF ₂ ) 9-CF ₃ ) ; the cholesteryl (C ₂₇ ) radical or a cholesterol ester residue, such as the cholesteryl oxyhexanoate group; or polycyclic aromatic groups, such as naphthalene or pyrene. Preference is more particularly given, among these radicals, to linear alkyl radicals and more particularly to the n- dodecyl radical.

According to a particularly preferred form of the invention, the monomer of formula (V) comprises at least one alkylene oxide unit (x > 1 ) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain preferably consists of ethylene oxide units and/or of propylene oxide units and more particularly still consists o f ethylene oxide units .

The number o f oxyalkylene units generally varies from 3 to 1 00, more preferably from 3 to 50 and more preferably still from 7 to 25.

Mention may be made, among these po lymers, of:

- copolymers which are or are not crosslinked and which are or are not neutralized, comprising from 15 % to 60% by weight o f AMPS® units and from 40% to 85 % by weight of (C ₈ - C i ₆ )alkyl(meth)acrylamide units or of C ₈ -C i ₆ )alkyl (meth)acrylate units, with respect to the polymer, such as those described in Application EP-A-750 899;

- terpolymers comprising from 10 mo l% to 90 mo l% o f acrylamide units, from 0. 1 mo l% to 1 0 mo l% of AMPS® units and from 5 mo l% to 80 mo l% of n-(C ₆ -C i ₈ )alkylacrylamide units, such as those described in Patent US-5 089 578. Mention may also be made o f copolymers o f completely neutralized AMPS® and of dodecyl methacrylate, and also non- crosslinked and crosslinked copolymers of AMPS® and of n- dodecylmethacrylamide, such as those described in the abovementioned papers by Morishima.

Mention will more particularly be made of the copo lymers constituted of 2-acrylamido-2-methylpropanesulfonic acid (AMPS®) units o f fo llowing formula (VI) :

in which X is a proton, an alkali metal cation, an alkaline earth metal cation or the ammonium ion,

and of units o f fo llowing formula (VII) :

in which x denotes an integer varying from 3 to 100, preferab ly from 5 to 80 and more preferably from 7 to 25 , Rn has the same meaning as that indicated above for Rs in the formula (V) and R12 denotes a linear or branched C 6 - C22 and more preferably C 10 - C22 alkyl.

The polymers which are particularly preferred are those for which x = 25 , Rn denotes methyl and R 12 represents n-dodecyl; they are described in the abovementioned papers by Morishima. The polymers for which X denotes sodium or ammonium are more particularly preferred.

As explained above, the acrylic associative thickeners which can be used in the composition according to the invention can be chosen from cationic amphiphilic polymers and amphoteric amphiphilic polymers.

The cationic amphiphilic polymers which can be used in the composition according to the present invention are preferably chosen from polyacrylates having aminated side groups.

The polyacrylates having quaternized or non-quaternized aminated side groups possess, for example, hydrophobic groups of the steareth-20 (polyoxyethylenated (20) stearyl alcohol) or (Cio-C3o)alkyl PEG-20 itaconate type.

Mention may be made, as examples of polyacrylates having aminated side chains, of the polymers 8781-124B or 9492-103 or Structure Plus from National Starch.

Mention may be made, as amphoteric amphiphilic polymers, of methacrylamidopropyltrimethylammonium chloride/acrylic acid/Cio- C30 alkyl methacrylate copolymers, the alkyl radical preferably being a stearyl radical.

As explained above, the thickening polymers comprising acrylic and/or methacrylic units can also be chosen from:

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (Ci- C ₆ )alkyl acrylate;

(d) non-ionic homopolymers and copolymers comprising ethylenically unsaturated monomers of ester and/or amide type;

(e) ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide;

(f) (meth)acrylamido(Ci-C ₄ )alkylsulfonic acid homopolymers and copolymers;

(g) crosslinked methacryloyloxy(Ci-C ₄ )alkyltri(Ci- C ₄ )alkylammonium homopolymers and copolymers. Mention may be made, among crosslinked acrylic acid homopolymers, of those crosslinked by an allyl ether of an alcohol of the sugar series, such as, for example, the products sold under the names Carbopol 980, 981, 954, 2984 and 5984 by Goodrich or the products sold under the names Synthalen M and Synthalen K by 3 VSA, Cosmedia SP® or crosslinked sodium polyacrylate comprising 90% of dry matter and 10%> of water, Cosmedia SPL® or sodium polyacrylate as inverse emulsion comprising approximately 60% of dry active matter, an oil (hydrogenated polydecene) and a surfactant (PPG- 5 Laureth-5), both sold by Cognis, or partially neutralized crosslinked sodium polyacrylates occurring in the form of an inverse emulsion comprising at least one polar oil, for example that sold under the name Luvigel® EM by BASF.

Mention may be made, among crosslinked copolymers of (meth)acrylic acid and of Ci-C ₆ alkyl acrylate, of the product sold under the name Viscoatex 538C by Coatex, which is a crosslinked copolymer of methacrylic acid and of ethyl acrylate as an aqueous dispersion comprising 38%> of active material, or the product sold under the name Aculyn 33 by Rohm & Haas, which is a crosslinked copolymer of acrylic acid and of ethyl acrylate as an aqueous dispersion comprising 28% of active material. Mention may more particularly be made of the crosslinked methacrylic acid/ethyl acrylate copolymer in the form of an aqueous 30% dispersion manufactured and sold under the name Carbopol Aqua SF-1 by Noveon.

Mention may be made, among non-ionic homopolymers or copolymers comprising ethylenically unsaturated monomers of ester and/or amide type, of the products sold under the names of: Cyanamer P250 by Cytec (polyacrylamide); PMMA MBX-8C by US Cosmetics (methyl methacrylate/ethylene glycol dimethacrylate copolymer); Acryloid B66 by Rohm & Haas (butyl methacrylate/methyl methacrylate copolymer); or BPA 500 by Kobo (polymethyl methacrylate). Mention may be made, among ammonium acrylate homopolymers, of the product sold under the name Microsap PAS 5 1 93 by Hoechst.

Mention may be made, among copolymers of ammonium acrylate and of acrylamide, of the product sold under the name Bozepol C Nouveau or the product PAS 5 193 sold by Hoechst (they are described and prepared in the documents FR-2 4 16 723 , US-2 798 053 and US-2 923 692) .

Preference is preferably given, among (meth)acrylamido(C i - C4)alkylsulfonic acid homopolymers and copolymers, to the use o f crosslinked polymers .

More particularly still, they are partially or completely neutralized.

These are water-so luble or water-swellable polymers.

Mention may in particular be made, among these po lymers, o f:

- polyacrylamidomethanesulfonic acid,

- polyacrylamidoethanesulfonic acid,

- polyacrylamidopropanesulfonic acid,

- poly(2-acrylamido-2-methylpropanesulfonic acid),

- poly(2-methacrylamido-2-methylpropanesulfonic acid),

- poly(2-acrylamido-n-butanesulfonic acid) .

Polymers of this type and in particular crosslinked and partially or completely neutralized poly(2-acrylamido-2- methylpropanesulfonic acids) are known, described and prepared in Patent Application DE- 196 25 8 10.

They are generally characterized in that they comprise, randomly distributed:

i) from 90% to 99.9% by weight of units of fo llowing formula

(VIII) : (VIII) in which X denotes a cation or a mixture of cations, including ii) from 0.01 % to 10% by weight of at least one crosslinking unit having at least two olefinic double bonds,

the proportions by weight being defined with respect to the total weight of the polymer.

X ⁺ represents a cation or a mixture of cations chosen in particular from a proton, an alkali metal cation, a cation equivalent to that of an alkaline earth metal, or the ammonium ion.

Preferably, the crosslinked and neutralized poly(2-acrylamido - 2-methylpropanesulfonic acid) comprises from 98%> to 99.5 % by weight of units of formula (VIII) and from 0.5 % to 2% by weight of crosslinking units.

The crosslinking units having at least two olefinic double bonds are chosen, for example, from dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane or other polyfunctional alcoho l allyl or vinyl ethers, tetraethylene glycol diacrylate, triallylamine, trimethylo lpropane diallyl ether, methylenebisacrylamide or divinylbenzene.

The crosslinking units having at least two olefinic double bonds are more particularly still chosen from those corresponding to the fo llowing general formula (IX) :

in which R1 3 denotes a hydrogen atom or a C ₁ -C ₄ alkyl and more particularly methyl (trimethylolpropane triacrylate) .

The crosslinked and partially or completely neutralized poly(2- acrylamido-2-methylpropanesulfonic acids) are generally known under the names "Ammonium polyacrylamido-2-methylpropanesulfonate" or "Ammonium polyacryldimethyltauramide" (INCI name) .

A product which is particularly preferred according to the invention is that sold by Clariant under the trade name Hostacerin AMPS®; this is a crosslinked poly(2-acrylamido-2- methylpropanesulfonic acid) partially neutralized with aqueous ammonia.

Mention may be made, among crosslinked methacryloyloxy(C i - C ₄ )alkyltri(C i -C ₄ )alkylammonium homopolymers and copolymers, of crosslinked polymers of methacryloyloxy(C i -C ₄ )alkyltri(C i - C4)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized by methyl chloride or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized by methyl chloride, the homo- or copolymerization being fo llowed by crosslinking by an olefinically unsaturated compound, in particular methylenebisacrylamide.

Use may more particularly be made of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride (20/80 by weight) copolymer in the form of a dispersion comprising 50% by weight of the said copolymer in mineral oil. This dispersion is so ld under the name of Salcare® SC 92 by Ciba. Use may also be made of a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names of Salcare® SC 95 and Salcare® SC 96 by Ciba.

Preferably, the thickening polymers having acrylic and/or methacrylic units are thickening polymers for an aqueous phase.

Preferably, the thickening polymer or polymers having acrylic and/or methacrylic units according to the invention are anionic.

These polymers are more particularly chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and of (Ci-

C ₆ )alkyl acrylate.

More preferably, the thickening polymers having acrylic and/or methacrylic units are more particularly chosen from crosslinked acrylic acid homopolymers.

The thickening polymers comprising acrylic and/or methacrylic units which can be used in the composition according to the invention preferably represent from 0.05% to 10% by weight, more preferably from 0.1% to 3% by weight and in particular from 0.3% to 2% by weight, with respect to the total weight of the composition.

As indicated above, the composition according to the invention also comprises one or more fixing polymers.

The term "fixing polymer" is understood to mean, within the meaning of the present invention, any polymer which makes it possible to confer a form on the hair and/or to retain the hair in a given form.

The fixing polymers may be soluble in the medium of the composition 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).

The fixing polymers which can be used in the composition according to the invention can be chosen from anionic, cationic, amphoteric and non-ionic fixing polymers.

The anionic fixing polymers which can be used in the compositions according to the invention can be polymers comprising groups derived from carboxylic acid, sulfonic acid or phosphoric acid and have a number-average mo lecular weight of between approximately 500 and 5 000 000.

The anionic fixing polymers comprising carboxylic groups which are preferred according to the invention are :

A) Copolymers o f acrylic acid and of acrylamide sold in the form o f their sodium salts under the names Reten 421 , 423 or 425 by Hercules or the sodium salts of polyhydroxycarboxylic acids.

B) Copolymers of acrylic or methacrylic acid with a monoethylenic monomer, such as ethylene, styrene, vinyl esters or acrylic or methacrylic acid esters, optionally grafted to a polyalkylene glyco l, such as po lyethylene glycol, and optionally crosslinked. Such polymers are described in particular in French Patent 1 222 944 and German Application 2 330 956, the copolymers of this type comprising an optionally N-alkylated and/or N-hydroxyalkylated acrylamide unit in their chain, as are described in particular in Luxembourgian Patent Applications 75370 and 75371 , or provided under the Quadramer name by American Cyanamid. Mention may also be made of acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers, such as Ultrahold Strong, sold by BASF . Mention may also be made o f copolymers of acrylic acid and of C 1 - C4 alkyl methacrylate and terpolymers of vinylpyrrolidone, of acrylic acid and of C 1 - C20 alkyl methacrylate, for example lauryl methacrylate, such as that sold by 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 BASF .

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 Amercho l.

C) Crotonic acid copolymers, such as those comprising, in their chain, vinyl acetate or propionate units and optionally other monomers, such as allyl or methallyl esters, vinyl ethers or vinyl esters of a linear or branched saturated carboxylic acid having a long hydrocarbon chain, such as those comprising at least 5 carbon atoms, it optionally being possible for these polymers to be grafted or crosslinked, or also another monomer which is a vinyl, allyl or methallyl ester 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 78 1 , 1 564 1 10 and 2 439 798. Commercial products coming within this category are the resins 28-29-30 , 26- 13 - 14 and 28- 13 - 10 so ld by National Starch.

D) Copolymers o f monounsaturated C 4 - C 8 carboxylic acids or anhydrides chosen from:

- copo lymers comprising (i) one or more maleic, fumaric or 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 functional groups o f 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 1 3 , and GB Patent 839 805 . Commercial products are in particular those sold under the names Gantrez® AN or ES by ISP;

- copolymers comprising (i) one or more maleic, citraconic or itaconic anhydride units and (ii) one or more monomers chosen from allyl or methallyl esters, optionally comprising one or more acrylamide, methacrylamide, a-olefin, acrylic or methacrylic ester, acrylic or methacrylic acid or vinylpyrrolidone groups in their chain, the anhydride functional groups o f these copolymers optionally being monoesterified or monoamidated.

These po lymers are, for example, described in French Patents 2 350 384 and 2 357 241 by the Applicant Company.

E) Polyacrylamides comprising carboxylate groups .

F) Homopolymers and copolymers comprising sulfonic groups, such as po lymers comprising vinylsulfonic, styrenesulfonic, naphthalenesulfonic or acrylamidoalkylsulfonic units. These polymers can in particular be chosen from:

- salts o f polyvinylsulfonic acid having a molecular weight o f between approximately 1000 and 100 000, as well as copolymers with an unsaturated comonomer, such as acrylic or methacrylic acids and their esters, as well as acrylamide or its derivatives, vinyl ethers and vinylpyrro lidone;

- salts of polystyrenesulfonic acid, such as the sodium salts so ld, for example, under the names Flexan® 500 and Flexan® 130 by National Starch. These compounds are described in Patent FR 2 198 71 9;

salts o f polyacrylamidesulfonic acids, such as those mentioned in Patent US 4 128 63 1 and more particularly the polyacrylamidoethylpropanesulfonic acid sold under the name Cosmedia Polymer HSP 1 1 80 by Henkel.

G) Mention may be made, as other anionic fixing po lymer which can be used in the composition according to the invention, o f branched block anionic polymers .

Such polymers are described in particular in French Patent Application FR 2 8 14 675. Mention may be made o f the products sold under the name Fixate G- 100 L (INCI name : AMP-Acrylates/Allyl methacrylate copolymer) or Fixate Superhold Polymer (INCI name : Polyacrylate-2 Crosspolymer) by Lubrizo l.

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 in particular under the name Ultrahold® Strong by 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 in particular under the name Resin 28-29-30 by National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives or acrylic acid and its esters, such as the methyl vinyl ether/monoesterified maleic anhydride copolymers sold, for example, under the name Gantrez® by ISP, the copolymers of methacrylic acid and o f methyl methacrylate sold under the name Eudragit® L by Ro hm Pharma, the copolymers of methacrylic acid and of ethyl acrylate sold under the name Luvimer® MAEX or MAE by BASF, the vinyl acetate/crotonic acid copolymers sold under the name Luviset CA 66 by BASF, the vinyl acetate/crotonic acid copolymers grafted by polyethylene glycol sold under the name Aristoflex® A by BASF, and the po lymers so ld under the name Fixate G- 100 L (INCI name : AMP- Acrylates/Allyl methacrylate copolymer) or Fixate Superhold Polymer (INCI name : Polyacrylate-2 Crosspolymer) by Lubrizo l.

Preferably, the anionic fixing po lymer or polymers according to the invention are chosen from branched block anionic polymers .

The cationic fixing po lymers which can be used in the composition according to the present invention are preferably chosen from po lymers comprising primary, secondary, tertiary and/or quaternary amine groups forming part of the po lymer chain or directly connected to the latter, and having a molecular weight of between 500 and approximately 5 000 000 and preferably between 1000 and 3 000 000.

Mention may more particularly be made, among these polymers, of the fo llowing cationic po lymers :

( 1 ) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of fo llowing formulae :

—

X

(A) (B) (C)

in which:

P i 6 denotes a hydrogen atom or a CH ₃ radical; A is a linear or branched alkyl group comprising from 1 to 6 carbon atoms or a hydroxyalkyl group comprising from 1 to 4 carbon atoms;

Ri 7 , Ri 8 and R19 , which are identical or different, represent an alkyl group having from 1 to 1 8 carbon atoms or a benzyl radical;

Ri 4 and R1 5 , which are 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 ) additionally comprise one or more units deriving from comonomers which can be chosen from the family o f the acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower ( C 1 - C 4 ) alkyl groups, groups derived from acrylic or methacrylic acids or their esters, vinyllactams, such as vinylpyrrolidone or vinylcaprolactam, or vinyl esters .

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

copolymers of acrylamide and of dimethylaminoethyl methacrylate which is quaternized with dimethyl sulfate or with a dimethyl halide, such as that sold under the name Hercoflo c® by Hercules,

copolymers of acrylamide and o f methacryloyloxyethyltrimethylammonium chloride, described, for example, in Patent Application EP-A-080 976 and sold under the name Bina Quat P 1 00 by Ciba-Geigy,

copolymer of acrylamide and o f methacryloyloxyethyltrimethylammonium methosulfate, such as that so ld under the name Reten by Hercules,

- vinylpyrro lidone/dialkylaminoalkyl acrylate or methacrylate copolymers, which may or may not be quaternized, such as the products sold under the Gafquat® name by 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 ,

- polymers comprising a fatty chain and comprising a vinylpyrro lidone unit, such as the products sold under the names Styleze W20 and Styleze W 10 by ISP,

dimethylamino ethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 7 13 by ISP, and

quaternized vinylpyrro lidone/dimethylaminopropylmethacrylamide copolymers, such as the product sold under the name Gafquat® HS 100 by ISP .

(2) Non-cellulo sic cationic po lysaccharides, preferably comprising quaternary ammonium, such as those described in United States Patents 3 589 578 and 4 03 1 307, such as guar gums comprising trialkylammonium cationic groups. Such products are sold in particular under the trade names of Jaguar C 13 S , Jaguar C 15 and Jaguar C 17 by Meyhall.

(3) Quaternary copolymers of vinylpyrrolidone and of vinylimidazole.

(4) Chitosans or their salts ; the salts which can be used are in particular chitosan acetate, lactate, glutamate, gluconate or pyrrolidonecarboxylate.

Mention may be made, among these compounds, of the chitosan having a degree of deacetylation o f 90.5 % by weight sold under the name Kytan Brut Standard by Aber Technologies or the chitosan pyrrolidonecarboxylate sold under the name Kytamer® PC by

Amercho l.

(5) Cationic cellulo se derivatives, such as copolymers o f cellulo se or of cellulo se derivatives grafted with a water-so luble monomer comprising a quaternary ammonium and described in particular in Patent US 4 13 1 576, such as hydroxyalkylcellulo ses, for example hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses, grafted in particular with a methacryloyloxyethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.

The marketed products corresponding to this definition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by National Starch.

The amphoteric fixing po lymers which can be used in accordance with the invention can be chosen from polymers comprising (B) and (C) units randomly distributed in the polymer chain, where (B) denotes a unit deriving from a monomer comprising at least one basic nitrogen atom and (C) denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulfonic groups or else (B) and (C) can denote groups deriving from zwitterionic carboxybetaine or sulfobetaine 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 else (B) and (C) form part of a chain o f a po lymer comprising an α,β-dicarboxyethylene unit, one o f the carboxylic groups of which has been reacted with a polyamine comprising one or more primary or secondary amine groups .

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

( 1 ) Copolymers comprising acidic vinyl units and comprising basic vinyl units, such as those resulting from the copolymerization o f a monomer derived from a vinyl compound carrying a carboxylic group, such as more particularly acrylic acid, methacrylic acid, maleic acid or a-chloroacrylic acid, and o f a basic monomer derived from a substituted vinyl compound comprising at least one basic atom, such as more particularly dialkylaminoalkyl methacrylate and acrylate or dialkylaminoalkylmethacrylamide and -acrylamide . Such compounds are described in United States Patent 3 836 537.

(2) Polymers comprising units deriving : a) from at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom by an alkyl group, b) from at least one acidic comonomer comprising one or more reactive carboxylic groups, and

c) from at least one basic comonomer, such as esters comprising primary, secondary, tertiary and quaternary amine substituents o f acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

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

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

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

Use is made in particular o f the copolymers for which the CTFA name (4 ^th Ed. , 1 991 ) is

Octylacrylamide/acrylates/butylamino ethyl methacrylate copolymer, such as the products sold under the name Amphomer® or Lovocryl® 47 by National Starch.

(3) Partially or completely acylated and crosslinked polyamino amides deriving from polyaminoamides of general formula:

+CO— R ₀ — CO

(XIII) in which R ₂ o represents a divalent group derived from a saturated dicarboxylic acid, from an aliphatic mono- or dicarboxylic acid comprising an ethylenic double bond, from an ester of a lower alkano l having from 1 to 6 carbon atoms of these acids, or from a group deriving from the addition o f any one o f the said acids with a bisprimary or bissecondary amine, and Z denotes a group deriving from a bisprimary, mono- or bissecondary polyalkylenepolyamine and preferably represents :

a) in the proportions o f from 60 mo l% to 1 00 mo l%, the group

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

this group deriving from diethylenetriamine, triethylenetetramine or dipropylenetriamine;

b) in the proportions of from 0 mo l% to 40 mo l%, the group (XIV) above in which x = 2 and p = 1 and which derives from ethylenediamine, or the group deriving from piperazine : c) in the proportions of from 0 mo l% to 20 mo l%, the group - NH-(CH ₂ ) ₆ -NH- deriving from hexamethylenediamine,

these polyaminoamides being crosslinked by addition reaction of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides or bisunsaturated derivatives, by means o f from 0.025 to 0.35 mo l o f crosslinking agent per amine group of the polyamino amide, and acylated by reaction with acrylic acid, chloroacetic acid or an alkane sultone or their salts. The saturated carboxylic acids are preferably chosen from acids having from 6 to 10 carbon atoms, such as adipic acid, 2,2,4- trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid or acids comprising an ethylenic double bond, such as, for example, acrylic acid, methacrylic acid or itaconic acid.

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

(4) Polymers comprising zwitterionic units of formula:

in which R ₂ i denotes a polymerizable unsaturated group , such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3 , R ₂₂ and R ₂₃ represent a hydrogen atom or a methyl, ethyl or propyl group, and R ₂₄ and R ₂₅ represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R ₂₄ and R ₂₅ does not exceed 10.

The po lymers 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.

Mention may be made, by way o f example, o f methyl met hacry late/methyl dimethylcarboxymethylammonio ethyl methacrylate copolymers, such as the product sold under the name Diaformer Z301 by Sandoz .

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

(XVI) (XVII) (XVIII) the unit (XVI) being present in proportions of between 0% and 30% , the unit (XVII) in proportions o f between 5 % and 50%> and the unit (XVIII) in proportions o f between 30%> and 90%> , it b eing understood that, in this unit (XVIII) , R ₂₆ represents a group of formula :

in which, if q = 0 , R ₂₇ , R ₂₈ and R ₂ g , which are identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue, optionally interrupted by one or more nitrogen atoms and/or optionally sub stituted by one or more amine , hydroxyl, carboxyl, alkylthio or sulfonic groups, or an alkylthio residue in which the alkyl group carries an amino residue , at least one of the R ₂₇ , R ₂ s and R ₂ g groups being, in this case, a hydrogen atom;

or, if q = 1 , R ₂₇ , R ₂₈ and R ₂ g each represent a hydrogen atom, and also the salts formed by these compounds with bases or acids .

(6) Polymers with the units corresponding to the general formula (XIX) are, for example , described in French Patent 1 400 366 : in which R ₃₀ represents a hydrogen atom or a CH ₃ 0, CH ₃ CH ₂ 0 or phenyl group, R ₃ i denotes a hydrogen atom or a lower alkyl group, such as methyl or ethyl, R ₃₂ denotes a hydrogen atom or a lower C i -C ₆ alkyl group, such as methyl or ethyl, and R ₃₃ denotes a lower C i -C ₆ alkyl group, such as methyl or ethyl, or a group corresponding to the formula: -R ₃₄ -N(R ₃₂ ) ₂ , R ₃₄ representing a -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH(CH ₃ )- group and R ₃₂ having the meanings mentioned above.

(7) Polymers derived from the N-carboxyalkylation o f chitosan, such as N-(carboxymethyl)chitosan or N-(carboxybutyl)chitosan, which are so ld under the "Evalsan" name by Jan Dekker.

(8) Amphoteric po lymers o f the -D-X-D-X- type chosen from: a) polymers obtained by reaction o f chloroacetic acid or sodium chloroacetate with compounds comprising at least one unit o f formula:

-D-X-D-X-D- (XX) ere D denotes a group

/ \

N N

\ / and X denotes the symbo l E or E' , E or E' , which are identica l or different, denoting a divalent group which is a straight- or branched-chain alkylene group comprising up to 7 carbon atoms in the main chain which is unsub stituted or substituted by hydro xyl groups and which can additionally comprise oxygen, nitrogen and sulfur atoms or from 1 to 3 aromatic and/or heterocyclic rings ; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thio ether, sulfo xide, sulfone, sulfonium, alkylamine or alkenylamine group s or hydro xyl, benzylamine, amine oxide , quaternary ammonium, amide, imide , alcohol, ester and/or urethane groups ,

b) po lymers o f formula :

-D-X-D-X- (XXI) where D denotes a

/ \

N N

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

(9) (C ₁ -C ₅ )alkyl vinyl ether/maleic anhydride copo lymers partially modified by semiamidation with an N,N- dialkylamino alkylamine, such as Ν,Ν-dimethylaminopropylamine, or by semiesterification with an Ν,Ν-dialkylaminoalkanol. These copolymers can also comprise other vinyl comonomers, such as vinylcapro lactam.

Mention will be made, among the amphoteric fixing po lymers mentioned above which are the most particularly preferred according to the invention, o f those of family (3), such as the copolymers for which the CTFA name is Octylacrylamide/acrylates/butylamino ethyl methacrylate copolymer, such as the products sold under the name

Amphomer®, Amphomer® LV 71 or Lovocryl® 47 by National Starch, and those of family (4), such as the methyl methacrylate/methyl dimethylcarboxymethylammonio ethyl methacrylate copolymers, sold, for example, under the name Diaformer Z301 by Sandoz.

The non-ionic fixing po lymers which can be used in the composition according to the present invention are chosen, for example, from:

- polyalkyloxazo lines;

- vinyl acetate homopolymers;

- vinyl acetate copolymers, such as, for example, copolymers o f vinyl acetate and of acrylic ester, copolymers of vinyl acetate and o f ethylene, or copolymers of vinyl acetate and of maleic ester, for example o f dibutyl maleate;

- acrylic ester homopolymers and copolymers, such as, for example, copolymers of alkyl acrylates and of alkyl methacrylates, such as the products provided by Rohm & Haas under the names Primal® AC-261 K and Eudragit® NE 30 D, by BASF under the name 8845 or by Hoechst under the name Appretan® N92 12;

- copolymers o f acrylonitrile and of a non-ionic monomer chosen, for example, from butadiene and alkyl (meth)acrylates;

mention may be made of the products provided under the name CJ 0601 B by Rohm & Haas;

- styrene homopolymers;

- styrene copolymers, such as, for example, copolymers of styrene and of alkyl (meth)acrylate, such as the products Mowilith® LDM 691 1 , Mowilith® DM 61 1 and Mowilith® LDM 6070 provided by Hoechst or the products Rhodopas® SD 215 and Rhodopas® DS 9 10 provided by Rhone-Poulenc; copolymers of styrene, of alkyl methacrylate and of alkyl acrylate; copolymers o f styrene and o f butadiene; or copolymers of styrene, of butadiene and o f vinylpyridine;

- polyamides;

vinyllactam homopolymers, such as vinylpyrrolidone homopolymers, sold in particular under the name PVP K90 by ISP, and such as the po lyvinylcaprolactam so ld under the name Luviskol® Plus by BASF; and

- 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 so ld under the names PVPVA® S630L by ISP and Luviskol® VA 73 , VA 64, VA 55 , VA 37 and VA 28 by BASF, and po ly(vinylpyrro lidone/vinyl acetate/vinyl propionate) terpolymers, such as, for example, that sold under the name Luviskol® VAP 343 by BASF .

The alkyl groups of the non-ionic po lymers mentioned above preferably have from 1 to 6 carbon atoms.

Use may also be made, according to the invention, o f fixing polymers o f grafted silicone type comprising a po lysiloxane portion and a portion composed 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 po lymers 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 po lymers can be amphoteric, anionic or non-ionic and they are preferably anionic or non-ionic, and more preferably anionic.

Such polymers are, for example, copolymers capable of being obtained by radical polymerization starting from the monomer mixture formed o f:

a) from 50% to 90% by weight of tert-butyl acrylate, b) from 0% to 40% by weight of acrylic acid, c) from 5 % to 40% by weight of a silicone macromer formula:

CH ₂ = -CH ₃ where v is a number ranging from 5 to 700 , the percentages by weight being calculated with respect to the total weight of the monomers.

Other examples of grafted silicone polymers are in particular polydimethylsiloxanes (PDMSs) to which mixed polymer units o f the poly(meth)acrylic acid type and o f 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.

Mention may be made, as other type of silicone fixing po lymer, of the product Luviflex® Silk sold by BASF .

Use may also be made, as fixing polymers, of functionalized or non-functionalized and silicone or non-silicone cationic, non-ionic, anionic or amphoteric po lyurethanes, or their mixtures.

The po lyurethanes particularly targeted by the present invention are those described in Patent Applications EP 0 75 1 1 62, EP 0 637 600, EP 0 648 485 and FR 2 743 297, of which the Applicant Company is the proprietor, and also in Patent Applications EP 0 656 021 and WO 94/035 10 o f BASF and EP 0 619 1 1 1 of National Starch.

Mention may be made, as po lyurethanes particularly highly suitable in the present invention, o f the products sold under the names Luviset PUR® and Luviset® Si PUR by BASF .

Preferably, the fixing polymers of the compositions of the invention are non-ionic or anionic. In a first preferred alternative form, the fixing polymers of the compositions o f the invention are non-ionic and are preferably chosen from homopolymers and copolymers of vinyllactams, in particular o f vinylpyrro lidone.

In a second preferred alternative form, the fixing po lymers o f the compositions o f the invention are anionic and are preferably chosen from branched block anionic po lymers, such as Fixate G- 100 L (INCI name : AMP-Acrylates/Allyl methacrylate copolymer) or Fixate Superhold Polymer (INCI name : Polyacrylate-2 Crosspolymer) from Lubrizo l.

The fixing po lymer or polymers which can be used in the composition according to the invention preferably represent from 0. 1 % to 20% by weight, more preferably from 0.5 %> to 1 0%> by weight and better still from 1 % to 7% by weight, with respect to the total weight of the composition.

Preferably, the ratio by weight of the total amount of fixing polymers (ii) to the total amount of thickening polymers (i) varies from 1 to 10, preferably from 1 .5 to 9 and more preferably from 2 to 8.

The composition according to the invention also comprises one or more anti-seborrhoeic agents .

The term "anti-seborrhoeic agent" is understood to mean a compound capable o f regulating the activity o f the sebaceous glands and/or of removing the excess sebum on the hair and/or scalp .

Mention may in particular be made, as anti-seborrhoeic agent which can be used in the composition according to the invention, o f retinoic acid, benzoyl peroxide, sulfur, vitamin B6 (or pyridoxine), selenium chloride or sea fennel; mixtures of extract of cinnamon, o f tea and of octanoylglycine, such as Sepicontrol A5 TEA® from Seppic; mixtures of cinnamon, of sarcosine and of octanoylglycine, so ld in particular by Seppic under the trade name Sepicontrol A5®; zinc salts, such as zinc gluconate, zinc pyrrolidonecarboxylate (or zinc pidolate), zinc lactate, zinc aspartate, zinc carboxylate, zinc salicylate or zinc cysteate; copper derivatives and in particular copper pidolate, such as Cuivridone® from So labia; extracts of plants of the species Arnica montana, Cinchona succirubra, Eugenia caryophyllata , Humulus lupulus, Hypericum perforatum, Mentha piperita, Rosmarinus officinalis, Salvia oficinalis and Thymus vulgaris, all so ld, for example, by Maruzen; meadowsweet {Spiraea ulmaria) extracts, such as that so ld under the name Sebonormine® by Silab; Laminaria saccharina algal extracts, such as that sold under the name Phlorogine® by Biotechmarine; mixtures of extracts of roots of great burnet (Sanguisorba officinalis! Poterium officinale), of rhizomes o f ginger {Zingiber officinalis) and of bark of cinnamon {Cinnamomum cassia), such as that sold under the name Sebustop® by Solabia; linseed extracts, such as that sold under the name Linumine® by Lucas Meyer; Phellodendron extracts, such as those sold under the name Phellodendron extract BG by Maruzen or Oubaku liquid B by Ichimaru Pharcos; mixtures of argan oil, of Serenoa serrulata (saw palmetto) extract and of sesame seed extract, such as that sold under the name Regu SEB® by Pentapharm; mixtures of extracts of willowherb, o f Terminalia chebula, of nasturtium and of bioavailable zinc (microalgae), such as that sold under the name Seborilys® by Green Tech; extracts of Pygeum afrianum, such as that sold under the name Pygeum afrianum sterolic lipid extract by Euromed; extracts of Serenoa serrulata, such as those sold under the name Viapure Sabal by Actives International or those sold by Euromed; mixtures of extracts of plantain, of Berberis aquifolium and of sodium salicylate, such as that sold under the name Seboclear® by Rahn; clove extract, such as that sold under the name Clove extract powder by Maruzen; argan oil, such as that sold under the name Lipofructyl® by Laboratoires Serobio logiques; milk protein filtrates, such as that sold under the name Normaseb® by Sederma; Laminaria algal extracts, such as that so ld under the name Laminarghane® by Biotechmarine; Laminaria digitata algal o ligosaccharides, such as that sold under the name Phycosaccharide AC by Codif; sugar cane extracts, such as that sold under the name Po licosano l® by Sabinsa; sulfonated shale oil, such as that sold under the name Ichtyo l Pale® by Ichthyo l; meadowsweet {Spiraea ulmaria) extracts, such as that sold under the name Cytobio l® Ulmaire by Libio l; sebacic acid, sold in particular in the form o f a sodium polyacrylate gel under the name Sebosoft® by Sederma; glucomannans extracted from konj ac corm and modified with alkylsulfonate chains, such as that sold under the name Biopol Beta by Arch Chemical; Sophora angustifolia extracts, such as those sold under the name Sophora powder or Sophora extract by Bio land; extracts of Cinchona succirubra bark, such as that so ld under the name Red Bark HS by Alban Muller; Quillaja saponaria extracts, such as that sold under the name Panama Wood HS by Alban Muller; lipoamino acids, in particular derived from glycine, such as glycine grafted to an undecylenic chain or to an octanoyl chain (capryloyl glycine), such as those sold under the names Lipacide UG OR and Lipacide C8G by Seppic; the mixture of o leano lic acid and o f nordihydroguaiaretic acid, such as that sold in the form of a gel under the name AC . Net by Sederma; phthalimidoperoxyhexanoic acid; tri(C i ₂ -C i ₃ )alkyl citrate, sold under the name Cosmacol® ECI by Saso l; tri(C i ₄ -C i s)alkyl citrate, sold under the name Cosmacol® ECL by Saso l; 10-hydroxydecanoic acid and in particular mixtures o f 1 0- hydroxydecanoic acid, of sebacic acid and of 1 , 10-decanedio l, such as that sold under the name Acnacidol® BG by Vincience; yeast protein hydro lysates, such as Asebio l LS from Co gnis (mixture with vitamins) ; and their mixtures.

The anti-seborrhoeic agent or agents can also be chosen from absorbent powders .

The absorbent powders which can be used in the composition according to the invention are preferably inorganic or organic powders .

More specifically, the sebum-absorbing powder or powders can be chosen from:

- starches,

- inso luble silicates, in particular calcium silicates, perlites or zeo lites,

- polylactic acids,

- silicas, - polyamide (Nylon®) powders,

- powders of acrylic polymers, in particular of polymethyl methacrylate, of po ly(methyl methacrylate/ethylene glyco l dimethacrylate), of poly(allyl methacrylate/ethylene glyco l dimethacrylate) or of ethylene glycol dimethacrylate/lauryl methacrylate copolymer;

- powders of silicone elastomer, obtained in particular by polymerization of organopolysiloxane having at least two hydrogen atoms each bonded to a silicon atom and o f an organopolysiloxane comprising at least two ethylenically unsaturated groups (in particular two vinyl groups) in the presence of a platinum catalyst; and

- their mixtures.

The absorbent powders can be in the form coated with a hydrophobic treatment agent.

The hydrophobic treatment agent can be chosen from fatty acids, such as stearic acid; metal soaps, such as aluminium dimyristate or the aluminium salt o f hydrogenated tallow glutamate; amino acids; N-acylamino acids or their salts ; lecithin, isopropyl-triisostearyl titanate, and their mixtures .

The N-acylamino acids can comprise an acyl group having from

8 to 22 carbon atoms, such as, for example, a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group . The salts of these compounds can be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid can, for example, be lysine, glutamic acid or alanine.

The term " alkyl" mentioned in the compounds cited above denotes in particular an alkyl group having from 1 to 30 carbon atoms and preferably having from 5 to 16 carbon atoms.

The starches which can be used in the present invention are, for example, maize starch, potato starch, tapioca starch, rice starch, wheat starch and cassava starch.

The starches may or may not be modified.

A modified starch is a starch which has been modified by processes known to a person skilled in the art, such as, for examp le, esterification, etherification, oxidation, acid hydrolysis, crosslinking or enzymatic conversion.

Non-limiting examp les o f modified starch comprise aluminium starch octenylsuccinate, sodium starch octenylsuccinate, calcium starch octenylsuccinate, distarch phosphate, hydroxyethyl starch phosphate, hydroxypropyl starch phosphate, sodium carboxymethyl starch and sodium starch glycolate.

Preferably, the calcium silicates used as sebum-absorbing powder exhibit a sebum uptake of greater than 200 ml/ 100 g, better still between 400 ml/ 100 g and 600 ml/ 100 g and more preferably o f approximately 475 ml/ 100 g.

The specific surface area (BET) preferably ranges from approximately 150 m ² /g to 600 m ² /g, better still from 300 m ² /g to 600 m ² /g and more preferably still from 3 10 m ² /g to 350 m ² /g.

The size of the silicate particles is preferably less than 20 micrometres.

These inso luble calcium silicates are generally prepared by reaction of reactive silica with an alkaline earth metal reagent, preferably an alkaline earth metal oxide or hydroxide, and a source of aluminium, such as sodium aluminate or alumina. As the final properties of the silicate depend on the reactivity o f the silica, the preferred source of silica is the reaction product of a so luble silicate, such as sodium silicate, and of a mineral acid, such as sulfuric acid. Suitable amorphous synthetic alkaline earth metal silicates are manufactured by JM Huber Corporation and are sold under the Hubersorb® names. Methods for preparing these silicas are disclosed in greater detail in Patent US 4 557 91 6. Other suitable silicates are available from JM Huber Corporation, such as the sodium alumino silicate sold under the Zeo lexg brand name and the sodium magnesium aluminosilicate sold under the Hydrex® brand name.

The perlites which can be used in the composition according to the present invention are generally inso luble alumino silicates o f vo lcanic origin which have the composition:

70.0-75.0% by weight of silica Si0 ₂ ; 12.0-15.0% by weight of aluminium oxide A1 ₂ 0 ₃ ;

3.0-5.0% of sodium oxide Na ₂ 0;

3.0-5.0%) of potassium oxide K ₂ 0;

0.5-2%) of iron oxide Fe ₂ 0 ₃ ;

0.2-0.7%) of magnesium oxide MgO;

0.5-1.5%) of calcium oxide CaO;

0.05-0.15% of titanium oxide Ti0 ₂ .

Mention may preferably be made, as perlite which can be used in the composition according to the invention, of Perlite 5μ.

Mention may in particular be made, as examples of zeolites, of insoluble sodium or potassium aluminosilicate compounds, such as the product provided by Zeochem under the Xmol name.

The polylactic acids which can be used in the present invention are in particular Accurel EP600 from Akzo Nobel or the product provided under the name Lactic Acid Polymer 9105 by Dajac Labs.

Mention may be made, as silica powder, of:

- the porous silica microspheres sold under the name Silica Beads SB-700 by Miyoshi or the name Sunsphere® H51 or Sunsphere® H33 by Asahi Glass;

- the polydimethylsiloxane-coated amorphous silica microspheres sold under the name SA Sunsphere® H33 or SA Sunsphere® H53 by Asahi Glass.

Mention may be made, as Nylon powder, of the Nylon powder sold under the name Orgasol® 4000 by Atochem.

Mention may be made, as powder of acrylic polymers, of:

- the polymethyl methacrylate powders sold under the name Covabead® LH85 by Wackherr;

- the poly(methyl methacrylate/ethylene glycol dimethacrylate) powders sold under the name Dow Corning 5640 Microsponge® Skin Oil Adsorber by Dow Corning and the name Ganzpearl® GMP-0820 by Ganz Chemical;

- the poly(allyl methacrylate/ethylene glycol dimethacrylate) powders sold under the name Poly-Pore® L200 or Poly-Pore® E200 by Amcol Health and Beauty Solutions Inc.; these powders have in particular a sebum uptake of greater than or equal to 1 ml/g, better still ranging from 1 ml/g to 20 ml/g;

the ethylene glycol dimethacrylate/lauryl methacrylate copolymer powders sold under the name Po lytrap® 6603 by Dow Corning.

Mention may be made, as silicone elastomer powder, of the powders sold under the names Trefil® Powder E-505 C and Trefil® Powder E-506C by Dow Corning.

Preferably, the anti-seborrhoeic agent or agents used in the composition according to the invention are chosen from lipoamino acids, in particular capryloyl glycine, insoluble silicates, in particular perlites, and a combination o f both these types of compound.

In a preferred embodiment of the invention, the said anti- seborrhoeic agent or agents comprise a combination o f one or more absorbent powders as defined above and of one or more lipoamino acids, and preferably the said anti-seborrhoeic agent or agents comprise a combination o f one or more absorbent powders chosen from perlite, kaolin or silica and of one or more lipoamino acids .

In a particularly preferred embodiment, the said anti- seborrhoeic agent or agents comprise a combination of perlite and o f one or more lipoamino acids, preferably a combination o f capryloyl glycine and of perlite.

The anti-seborrhoeic agent or agents which can be used in the composition according to the invention preferably represent from 0. 1 % to 1 0% by weight, more preferably from 0.2% to 5 % by weight and in particular from 0.3 % to 2% by weight, with respect to the total weight of the composition.

The composition according to the invention can additionally comprise one or more additives other than the obligatory compounds already described.

Mention may be made, as additive which can be used in accordance with the invention, without imp lied limitation, o f polymers, other than the thickening polymers and fixing polymers described above, chosen from anionic, cationic, non-ionic and amphoteric polymers and their mixtures, cationic, anionic, amphoteric or zwitterionic and non-ionic surfactants, fatty substances, sunscreens, inorganic or organic pigments, sequestering agents, peptizing agents, in particular 40 or 60 EO oxyethylenated hydrogenated castor oil, ethoxylated or non-ethoxylated fatty alcohols, plasticizing agents, so lubilizing agents, acidifying or basifying agents, inorganic or organic thickening agents, in particular polymeric thickening agents other than those mentioned above, opacifying agents, antioxidants, agents for combating hair lo ss, hydroxy acids, pearlescent agents, dyes, fragrances and preservatives.

Of course, a person skilled in the art will take care to choose this or these optional additional compounds so that the advantageous properties intrinsically attached to the composition according to the invention are not, or not substantially, detrimentally affected by the envisaged addition or additions.

The above additives can generally be present in an amount, for each o f them, o f between 0% and 20% by weight, with respect to the total weight of the composition.

Particularly preferably, the composition according to the invention also comprises water, which advantageously represents from 40% to 99%, preferably from 50% to 95 % and better still from 55 % to 80%) by weight, with respect to the total weight of the composition.

The composition can additionally comprise one or more water- so luble organic so lvents (so lubility o f greater than or equal to 5 % by weight in water at 25 °C and at atmospheric pressure) .

Mention may be made, as water-so luble organic so lvent, for example, of linear or branched and preferably saturated monoalcohols or dio ls comprising from 2 to 1 0 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanedio l) , neopentyl glyco l, 3 -methyl- 1 ,5 -pentanedio l, butylene glycol, dipropylene glycol or propylene glycol; aromatic alcoho ls, such as phenylethyl alcoho l; po lyo ls comprising more than two hydroxyl functional groups, such as glycerol; polyo l ethers, such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers, such as, for example, propylene glyco l monomethyl ether; and also diethylene glycol alkyl ethers, in particular C ₁ - C4 alkyl ethers, such as, for examp le, diethylene glyco l monoethyl ether or monobutyl ether, alone or as a mixture.

The water-so luble organic solvents, when they are present, generally represent from 1 % to 40% by weight and preferably from 5 % to 35 % by weight, with respect to the total weight of the composition.

Preferably, the composition according to the invention is provided in the gel form.

In a preferred alternative form, the viscosity o f the compositions of the invention is greater than or equal to 1 poise, better still greater than or equal to 2 poises and even better still greater than or equal to 5 poises at 25 °C and at a shear rate of 1 s ^{" 1} . This viscosity can be determined with a rheometer having cone-plate geometry.

Another subject-matter of the invention is a composition as defined above for combating the excess sebum of the hair and/or of the scalp .

The fo llowing example is given purely by way of illustration o f the present invention.

EXAMPLE :

The fo llowing composition was prepared from the ingredients shown in the table below (in which the contents are shown as grams o f active material) :

Composition:

( 1 ) Polymer so ld under the name Carbopo l 980.

(2) Polymer so ld under the name Fixate Superho ld by Lubrizo l.

(3) Compound sold under the name Lipacide C 8G by Seppic.

(4) Compound sold under the name Perlite 5 μ .

The composition according to the invention was evaluated by 10 users, aged from 20 to 40 years, stating to have greasy hair and/or scalps.

The users recorded that the composition exhibits a pleasant appearance and application. Furthermore, it is easily distributed over the who le o f the scalp .

The users recorded a good shape retention throughout the day of the hairstyle shaped by means o f the composition according to the invention, whether on wet hair or on dry hair.

All the users perceive, in a very marked way, a lasting grease- control effect which persists all day. They record that the sheen o f their hair is natural and that their hair is supple and not very sticky.