WO2014091012A1

WO2014091012A1 - Cosmetic composition in powder form comprising a (meth)acrylic thickening polymer, a fixing polymer and water-insoluble particles

Info

Publication number: WO2014091012A1
Application number: PCT/EP2013/076604
Authority: WO
Inventors: Cécile Bebot; Virginie Masse; Anne-sophie GRAS
Original assignee: L'oreal
Priority date: 2012-12-14
Filing date: 2013-12-13
Publication date: 2014-06-19
Also published as: FR2999423A1; FR2999423B1

Abstract

The present invention relates to a cosmetic composition in powder form, comprising an aqueous phase, water-insoluble particles having a number-average primary size of greater than or equal to 0.2µm, one or more thickening polymers with (meth)acrylic units and one or more fixing polymers different from the thickening polymer or polymers with (meth)acrylic units. It likewise relates to a process for applying this composition with transformation to cream and to the use of this composition for hair treatment, in particular for treating keratin fibres and more particularly for shaping and/or maintaining the shape of the hair.

Description

COSMETIC COMPOSITION IN POWDER FORM COMPRISING A (METH)ACRYLIC THICKENING POLYMER, A FIXING POLYMER AND WATER-INSOLUBLE

PARTICLES The present invention relates to a cosmetic composition in powder form, comprising an aqueous phase, water-insoluble particles, one or more thickening polymers with (meth)acrylic units and one or more fixing polymers, and to the use of such a composition for hair treatment, in particular for treating keratin fibres and more particularly for shaping and/or maintaining the shape of the hair.

In the styling sector, and more particularly among hair products intended for shaping and/or maintaining the hairstyle, the hair compositions are generally composed of a usually alcoholic or aqueous solution and of one or more fixing polymers as a mixture with various cosmetic adjuvants.

These compositions may in particular be in the form of hair gels or mousses that are generally applied to wet hair before blow drying or drying.

The use is known of products which texturize hair fibres in such compositions, in order to endow the hairstyle with body, density and a particular shape. Use is for example made, as texturizing agent, of powders that are incorporated into water or into oil.

The powders permit a very natural effect to be imparted, and permit easy restyling during the day. The resulting compositions, however, sometimes have a rough feel, and occasionally leave residues on the hair.

Documents WO2009/0901 14 and Research Disclosure RD 531004 describe, for example, styling compositions in powder form. The formulation of these compositions, however, is not ideal, and may in particular be excessively fluid. The texture of these compositions, furthermore, was not very cosmetic.

There is therefore a need for a cosmetic composition which has good cosmetic and styling properties and which allows the drawbacks referred to above to be overcome.

The Applicant has found that by combining particular water-insoluble particles, a particular thickening polymer and a fixing polymer it is possible to obtain mixtures which are stable on storage over time and which exhibit good cosmetic and styling properties.

The resulting composition is in powder form and has a soft feel. The texture of the composition, moreover, is advantageous, since the powder turns to cream when spread out in the hands. Application of the resulting composition is facilitated, furthermore, because the powder is not very volatile but is highly melting.

A subject of the present invention is therefore a cosmetic composition in powder form, comprising an aqueous phase, water-insoluble particles having a number- average primary size of greater than or equal to 0.2 μηη, one or more thickening polymers with (meth)acrylic units and one or more fixing polymers different from the thickening polymer or polymers with (meth)acrylic units.

The cosmetic composition is preferably a composition for styling keratin fibres, more particularly human keratin fibres such as the hair.

The invention likewise relates to a cosmetic process for treating keratin fibres, in particular for shaping and/or maintaining the shape of the keratin fibres, that employs the cosmetic composition as defined above. A subject of the invention is also the use of a composition as defined previously for hair treatment, in particular for treating keratin fibres and more particularly for shaping and/or maintaining the shape of the hair.

Other subjects, features, aspects and advantages of the invention will emerge even more clearly from reading the description and examples which follow.

In the text hereinbelow, the term "at least one" is equivalent to the term "one or more".

WATER-INSOLUBLE PARTICLES

The composition according to the invention comprises water-insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη.

For the purposes of the present invention, the term "water-insoluble compound" refers to a compound whose solubility in water at 25°C and at atmospheric pressure is less than 0.1 % and better still less than 0.001 %.

The particle or particles advantageously exhibit a number-average primary size of from 0.2 to 500 μηη, preferably from 0.5 to 300 μηη and more preferentially from 1 to

200 μηι, especially from 1 to 100 μηι.

For the purposes of the present invention, the term "primary particle size" is intended to mean the maximum dimension that it is possible to measure between two diametrically opposed points of an individual particle.

The size of the particles may be determined by transmission electron microscopy or by measuring the specific surface area by the BET method or using a laser particle sizer.

Preferably, the particles of the invention are not coloured pigments.

The particles used in the cosmetic composition may have various shapes, for example sphere-shaped, flakes, needles or platelets, and preferably they are substantially spherical.

The particle(s) may be filled, hollow or porous.

When the particles are hollow, they comprise at least one continuous envelope (or a surface layer) and at least one cavity. The envelope of the particles is preferably flexible to lend itself to mechanical deformation.

For the purposes of the present invention, the term "porous particles" means particles having a structure comprising pores that are variable in size and number. The porosity associated with the size of the particles may be characterized quantitatively by measuring the specific surface area via the BET method.

Preferably, the porous particles have a specific surface area of greater than or equal to 1 m²/g, preferably greater than or equal to 2 m²/g and even more preferentially greater than or equal to 4 m²/g.

The specific surface area is determined according to the BET (Brunauer-Emmett- Teller) method as described in the "Journal of the American Chemical Society", vol. 60, page 309, February 1938, and corresponds to international standard ISO 5794/1 (appendix D). The specific surface area determined by the BET method corresponds to the total specific surface area, including the micropores, of the organic particles under consideration.

The composition comprises particles of one or more, preferably polymeric, organic compounds and/or particles of one or more inorganic compounds. The organic or inorganic particle or particles may be optionally surface-treated by a hydrophobic treatment agent.

Thus, the organic particles may be made hydrophobic by coating or chemical grafting with products such as:

silanes such as triethoxycaprylylsilanes,

silicones, for instance methicones or dimethicones,

amino acids or N-acylamino acids or salts thereof,

metal soaps such as aluminium dimyristate or the aluminium salt of hydrogenated tallow glutamate,

- fluoro derivatives, for instance perfluoroalkyl phosphates, perfluoroalkyl silanes, polyhexafluoropropylene oxides or polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups,

lecithin or isopropyl triisostearyl titanate,

fatty acids such as stearic acid.

The term "alkyl" mentioned in the compounds mentioned above may especially denote a linear, branched or cyclic alkyl group comprising from 1 to 30 carbon atoms and especially from 5 to 16 carbon atoms.

The N-acylamino acids may comprise an acyl group comprising from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group.

The salts of these compounds may be the aluminium, magnesium, calcium, zirconium, zinc, sodium or potassium salts.

The amino acid may be, for example, lysine, glutamic acid or alanine. The particles of one or more polymeric organic compounds may consist of crosslinked or non-crosslinked polymers.

These polymers are preferably in the vitreous state, i.e. they have a glass transition temperature that is significantly higher than room temperature or the working temperature (for example human body temperature).

When the particles of one or more organic compounds are hollow, they comprise at least one continuous envelope (or a surface layer) and at least one cavity. The envelope of the particles is preferably flexible to lend itself to mechanical deformation.

It generally comprises at least one polymer, a homopolymer or copolymer, formed from ethylenically unsaturated monomers.

The monomers used may in particular be acrylic or methacrylic acid esters, such as methyl acrylate and methyl methacrylate, vinylidene chloride, acrylonitrile or styrene and derivatives thereof.

The particles of one or more organic compounds used in the cosmetic composition according to the invention may be chosen from polyamide powders, acrylic polymer powders, especially crosslinked sodium polyacrylate powder or polymethyl methacrylate powder, acrylic copolymer powders, especially powders of polymethyl methacrylate/ethylene glycol dimethacrylate, of polyallyl methacrylate/ethylene glycol dimethacrylate, of an ethylene glycol dimethacrylate/lauryl methacrylate copolymer, of polyacrylate/alkylacrylate, polystyrene powders, polyethylene powders, especially polyethylene/acrylic acid powders, and silicone resin microbeads.

As non-limiting illustrations, organic particles according to the invention that may be mentioned more particularly include: - polyamide (Nylon®) powders, for example those sold under the names Orgasol® 4000 and Orgasol® 2002 UD NAT COS 204 by the company Atochem,

- acrylic polymer powders, especially of crosslinked sodium polyacrylate, for instance those sold under the name ASAP 2000 by the company Chemoal or Hysorb M7055 by the company BASF, polymethyl methacrylate powders, for instance those sold under the name Covabead® LH85 or Covabead® PMMA by the company Sensient or those sold under the name Micropearl® MHB, Micropearl® M 100 or Micropearl® M 310 sold by the company Matsumoto,

- acrylic copolymer powders, especially of polymethyl methacrylate/ethylene glycol dimethacrylate, for instance those sold under the name Dow Corning 5640

Microsponge® Skin Oil Adsorber by the company Dow Corning, or those sold under the name Ganzpearl® GMP-0800 by the company AICA Kogyo, of polyallyl methacrylate/ethylene glycol dimethacrylate, for instance those sold under the name Polypore® L200 or Polypore® E200 sold by the company Amcol, of ethylene glycol dimethacrylate/lauryl methacrylate copolymer, for instance those sold under the name Polytrap® 6603 by the company Dow Corning, or of polyacrylate/ethylhexyl acrylate, for instance those sold under the name Techpolymer® ACX 806C by the company Sekisui,

- polystyrene powders, such as those sold under the name Polysphere 3000 SP by the company Presperese,

- polystyrene/divinylbenzene powders, for instance those sold under the name Techpolymer® SBX8 by the company Sekisui,

- styrene/acrylate copolymer powders, for instance those sold under the name Sunspheres Powder by the company Rohm & Haas,

- polyethylene powders, especially of polyethylene/acrylic acid sold under the name Flobeads® by the company Sumitomo, or polyethylene beads sold under the name Micropoly 220 L by the company Micro Powders,

- silicone resin microbeads, such as those sold under the name Tospearl® by the company Toshiba Silicone, in particular Tospearl® 240A and Tospearl® 120A,

- expanded terpolymer microspheres of vinylidene chloride, acrylonitrile and methyl methacrylate, sold under the brand name Expancel by the company Nobel Casco and in particular under the references 551 DE 12, 551 DE 20, 551 DE 50, 461 DE 50, 642 WE 50 and 551 DE 80.

Preferably, the organic particles used in the composition in accordance with the invention are chosen from polyamide powders, crosslinked sodium polyacrylate powders, polyethylene powders and polymethyl methacrylate powders.

As indicated above, the organic particle or particles may be optionally surface- treated with a hydrophobic treatment agent.

By way of example, mention may be made of the polymethyl methacrylate microspheres coated with isopropyl triisostearyl titanate of size 2-15 μηη sold by Kobo under the reference BPA-515.

The particles of one or more inorganic compounds used in the cosmetic composition according to the invention may be chosen from metal particles, oxides, inorganic salts, carbides, nitrides, sulfides and hydroxides.

The term "metal particles" means particles formed by metals chosen from alkaline-earth metals, transition metals, rare-earth metals and alloys of these metals. Preferably, the metals used are in particular boron, aluminium, copper, cadmium, selenium, silver, gold, indium, iron, platinum, nickel, molybdenum, silicon, titanium, tungsten, antimony, palladium, zinc and tin, and alloys of these metals. Among these metals, very particular preference is given to aluminium, gold, silver, platinum, cadmium, selenium and alloys of these metals.

The particles of one or more inorganic compounds may also be oxides. Mention may be made of oxides of the elements in columns 1 to 14 of the Periodic Table of the Elements. In particular, mention may be made especially of titanium oxide, zinc oxide, cerium oxide, zirconium oxide, aluminium oxide and bismuth oxychloride. Among these compounds, zinc oxide is most particularly preferred.

The particles of one or more inorganic compounds may be inorganic salts. Mention may be made especially of barium sulfate, calcium carbonate, calcium sulfate, calcium phosphate and magnesium hydrogen carbonate. Among these compounds, calcium carbonate is preferred.

The particles of one or more inorganic compounds may be carbides, nitrides, borides, sulfides and hydroxides. Mention may be made in particular of aluminium hydroxide.

The particles of one or more inorganic compounds belonging to the classes described above may also include clays, silicates, alumina, aluminium hydroxide, silica, kaolin and hydroxyapatite.

In particular, the silicas that can be used may be natural and untreated. Mention may thus be made of the silicas sold under the names Sillitin N85, Sillitin N87, Sillitin N82, Sillitin V85 and Sillitin V88 by the company Hoffmann Mineral, or Sunsil 130 by the company Sunjin Chemical, MSS-500-3 H by the company Kobo, Sunsphere H 51 by the company AGC Si-Tech, and the hollow particles of ellipsoidal amorphous silica sold by Kobo under the reference Silica Shells.

They may be fumed silicas.

The fumed silicas may be obtained by high-temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas which have a substantial number of silanol groups on their surface. The surface of said silica may be modified chemically by chemical reaction, giving rise to a decrease in the number of silanol groups. Silanol groups can in particular be replaced by hydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups may more particularly be:

(a) trimethylsiloxyl groups, which are obtained in particular by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are known as "Silica silylate" according to the CTFA (6th Edition, 1995) ;

(b) dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "Silica dimethyl silylate" according to the CTFA (6th edition, 1995).

In particular, among the hydrophobic silicas, mention may be made of silica aerogels.

Aerogels are ultralight porous materials which were first produced by Kristler in

1932.

They are generally synthesized by a sol-gel process in a liquid medium and then dried by extraction with a supercritical fluid. The supercritical fluid most commonly used is supercritical C0₂. This type of drying makes it possible to avoid the contraction of the pores and of the material.

Other types of drying also make it possible to obtain porous materials starting from gel, namely (i) drying by freeze drying, which consists in solidifying the gel at low temperature and in then subliming the solvent, and (ii) drying by evaporation. The materials thus obtained are referred to respectively as cryogels and xerogels. The sol- gel process and the various types of drying are described in detail in Brinker CJ., and Scherer G.W., Sol-Gel Science: New York: Academic Press, 1990.

A "hydrophobic silica" is any silica whose surface is treated with silylating agents, for example with halogenated silanes such as alkylchlorosilanes, siloxanes, more particularly dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, so as to functionalize the OH groups with silyl groups Si-Rn, for example trimethylsilyl groups.

The hydrophobic aerogel particles which can be used in the present invention preferably have advantageously a specific surface area per unit mass (SM) of from 500 to 1500 m²/g, preferably from 600 to 1200 m²/g and more preferably from 600 to 800 m²/g and/or have an oil absorption capacity as measured at the wet point of from 5 to 18 ml/g of particles, preferably from 6 to 15 ml/g and more preferably from 8 to 12 ml/g.

The absorption capacity measured at the wet point, denoted Wp, corresponds to the amount of oil which needs to be added to 100 g of particles in order to obtain a homogeneous paste.

It is measured according to the wet point method or method of determining oil uptake by powder in accordance with the principle described in standard NF T 30-022. It corresponds to the amount of oil adsorbed on the available surface of the powder and/or absorbed by the powder, by measurement of the wet point, described below: a quantity m = 2 g of powder is placed on a glass plate and then the oil (isononyl isononanoate) is added dropwise. Following addition of 4 to 5 drops of oil to the powder, mixing is carried out with a spatula, and addition of the oil is continued until conglomerates of oil and powder are formed. From this point on, the oil is added one drop at a time, and the mixture is then triturated with the spatula. Addition of oil is halted when a smooth and firm paste is obtained. This paste must be able to be spread over the glass plate without cracks or the formation of lumps. The volume Vs (expressed in ml) of oil used is then noted.

The oil uptake corresponds to the ratio Vs/m.

The hydrophobic silica aerogel particles used according to the present invention are preferably silylated silica aerogel particles (INCI name: Silica silylate).

The preparation of hydrophobic silica aerogel particles surface-modified by silylation is further described in document US 7,470,725.

Use will be made in particular of hydrophobic silica aerogel particles surface- modified with trimethylsilyl groups.

The hydrophobic aerogel particles that may be used in the present invention advantageously have a size, expressed as the mean diameter (D[0.5]), of less than 1500 μηη and preferably of from 1 to 30 μηη, more preferably from 5 to 25 μηη, very preferably from 5 to 20 μηη and even more preferably from 5 to 15 μηη.

The specific surface area per unit of mass can be determined by the nitrogen adsorption method, known as the BET (Brunauer-Emmett-Teller) method, described in the Journal of the American Chemical Society, Vol. 60, page 309, February 1938 and corresponding to International standard ISO 5794/1 (Annex D). The BET specific surface area corresponds to the total specific surface area of the particles under consideration.

The sizes of the aerogel particles according to the invention may be measured by static light scattering using a commercial MasterSizer 2000 particle size analyser from Malvern. The data are processed on the basis of the Mie scattering theory. This theory, which is exact for isotropic particles, makes it possible to determine, in the case of non- spherical particles, an "effective" particle diameter. This theory is described in particular in the publication by Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

According to one advantageous embodiment, the hydrophobic aerogel particles used in the present invention have a specific surface area per unit mass (SM) of from 600 to 800 m²/g and a size expressed as the volume mean diameter (D[0.5]) of from 5 to 20 μηη, more preferably from 5 to 15 μηη.

According to one preferred embodiment, use will be made more particularly of

VM-2270, whose particles have a mean size of from 5 to 15 microns and a specific surface area per unit mass of from 600 to 800 m²/g.

The hydrophobic aerogel particles used in the present invention may advantageously have a tapped density p of from 0.04 g/cm³ to 0.10 g/cm³, preferably from 0.05 g/cm³ to 0.08 g/cm³.

In the context of the present invention, this density can be assessed according to the following protocol, referred to as the tapped density protocol:

40 g of powder are poured into a graduated measuring cylinder and then the measuring cylinder is placed on a Stav 2003 device from Stampf Volumeter. The measuring cylinder is subsequently subjected to a series of 2500 tapping actions (this operation is repeated until the difference in volume between 2 consecutive tests is less than 2%); and then the final volume Vf of tapped powder is measured directly on the measuring cylinder.

The tapped density is determined by the ratio: mass (m)/Vf, in this instance 40/Vf (Vf being expressed in cm³ and m in g).

According to one embodiment, the hydrophobic aerogel particles used in the present invention have a specific surface area per unit volume, SV, of from 5 to 60 m²/cm³, preferably from 10 to 50 m²/cm³ and more preferably from 15 to 40 m²/cm³.

The specific surface area per unit of volume is given by the relationship:

SV = SM^*p

were p is the tapped density expressed in g/cm³ and SM is the specific surface area per unit of mass, expressed in m²/g, both as defined earlier on above.

According to one preferred embodiment, the hydrophobic aerogel particles according to the invention have a specific surface area per unit of mass (SM) ranging from 500 to 1500 m²/g, preferably from 600 to 1200 m²/g and better still from 600 to 800 m²/g, and a size, expressed as the mean diameter (D[0.5]), ranging from 1 to 30 μηη and/or an oil absorption capacity, measured at the wet point, ranging from 5 to 18 ml/g of particles, preferably from 6 to 15 ml/g and better still from 8 to 12 ml/g.

Hydrophobic silica aerogels that may be used in the invention include, for example, the aerogel sold under the name VM-2260 (INCI name: Silica silylate) by the company Dow Corning, which has particles with a mean size of approximately 1000 microns and a specific surface area per unit mass of from 600 to 800 m²/g. Mention may also be made of the aerogels sold by Cabot under the references Aerogel TLD 201 , Aerogel OGD 201 and Aerogel TLD 203, Enova Aerogel MT 1 100 and Enova Aerogel MT 1200.

Use will be made more particularly of the aerogel sold under the name VM 2270 (INCI name Silica silylate) by the company Dow Corning, in which the particles have a mean size of from 5 to 15 microns and a specific surface area per unit mass of from 600 to 800 m²/g.

The inorganic particles according to the invention may also be particles of aluminium hydroxide and more particularly particles of aluminium hydroxide that are coated with triethoxycaprylylsilane, such as those available from the company Sensient under the name Alumina ES EM.

The inorganic particles according to the invention may also be clay particles. Clays are products that are already well known per se, which are described, for example, in the publication Mineralogie des argiles [Mineralogy of Clays], S. Caillere, S. Henin, M. Rautureau, 2nd Edition 1982, Masson, the teaching of which is included herein by way of reference.

Clays are silicates containing a cation that may be chosen from calcium, magnesium, aluminium, sodium, potassium and lithium cations, and mixtures thereof.

Examples of such products that may be mentioned include clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites and saponites, and also of the family of vermiculites, stevensite and chlorites.

The clays may be of natural or synthetic origin. Preferably, clays that are cosmetically compatible and acceptable with keratin fibres such as the hair are used.

The clay can be chosen from montmorillonite, bentonite, hectorite, attapulgite, sepiolite and mixtures thereof. Preferably, the clay is a bentonite or a hectorite.

The clays may be chosen from organophilic clays.

Organophilic clays are clays modified with a chemical compound chosen from quaternary amines, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkyl aryl sulfonates and amine oxides, and mixtures thereof.

Preferably, the organophilic clays according to the invention are clays modified with a chemical compound chosen from quaternary amines.

Organophilic clays that may be mentioned include quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Elementis, Tixogel VP by United Catalyst, and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites such as those sold under the names Bentone 27V by Elementis, Tixogel LG by United Catalyst, and Claytone AF and Claytone APA by Southern Clay; and quaternium-18/benzalkonium bentonites such as those sold under the names Claytone HT and Claytone PS by Southern Clay.

The organophilic clay is particularly chosen from modified hectorites such as the hectorite modified by C10-C12 fatty acid ammonium chloride, in particular distearyldimethylammonium chloride and stearylbenzyldimethylammonium chloride.

The water-insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη are preferably hydrophobic. The water-insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη are preferably chosen from particles of one or more inorganic compounds, more preferably from inorganic hydroxides, silicates and silica.

The water-insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη are preferably hydrophobized, i.e. treated with a hydrophobic treatment agent.

The composition according to the invention may preferably comprise from 1 % to 40% by weight, preferably from 5% to 30% and more preferentially from 10% to 20% by weight of water-insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη, relative to the total weight of the said composition.

THICKENER

The composition according to the present invention further comprises one or more thickening polymers with (meth)acrylic units.

The term "(meth)acrylic" within the meaning of the present application is understood to mean "acrylic or methacrylic".

A polymer with (meth)acrylic units is understood in the sense of the present invention to be a polymer resulting from the polymerization of one or more monomers including one or more monomers of structure (A):

where R₃ denotes a hydrogen atom or a linear or branched un Ci-C₄ alkyl radical, R₄ denotes a hydrogen atom, a linear or branched C C₄ alkyl radical, a radical NR₅R₆, a linear or branched Ci-C₃₀ alkoxy radical optionally substituted by one or more hydroxyl radicals or by a quaternary ammonium radical,

R₅ and R₆ denote a hydrogen atom or an optionally oxyalkylenated Ci-C₃₀ alkyl radical, it being possible for the alkyl radical to contain a sulfonic group.

Preferably R₃ denotes a hydrogen atom or a methyl radical.

For the purposes of the present invention, the term "thickening polymer" means a polymer capable, by its presence, of increasing the viscosity of the medium by at least 50 centipoise at 25°C and at a shear rate of 1 s^' Preferably, the thickening polymer has, at 1 % in water or a 50/50 water/alcohol mixture by weight at 25°C, a viscosity of greater than 100 centipoise at a shear rate of 1 s^' These viscosities may especially be measured with viscometers or rheometers with cone-plate geometry.

The thickening polymers with (meth)acrylic units are chosen in particular from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and (CrC₆)alkyl acrylate,

(d) nonionic homopolymers and copolymers containing ethylenically unsaturated monomers of ester and/or amide type; (e) ammonium acrylate homopolymers or copolymers of ammonium acrylate and of acrylamide;

(f) homopolymers and copolymers of (meth)acrylamido(Ci-C₄)alkyl sulfonic acids,

(g) crosslinked methacryloyl(Ci-C₄)alkyl tri(Ci-C₄)alkylammonium homopolymers and copolymers.

(a) The term "associative thickener" refers according to the invention to an amphiphilic thickener comprising both hydrophilic units and hydrophobic units, more particularly comprising at least one C₈-C₃₀ fatty chain and at least one hydrophilic unit.

Acrylic associative thickeners which can be used according to the invention include the acrylic associative polymers chosen from:

(i) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit;

(ii) anionic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit;

(iii) cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit;

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

the fatty chains containing from 10 to 30 carbon atoms.

(i) The acrylic nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit are preferably selected from:

(1 ) copolymers of Ci-C₆ alkyl acrylates or methacrylates and of amphiphilic monomers containing at least one fatty chain (for example, oxyethylenated (C₈-

C₂2)alkyl acrylates) such as, for example, the oxyethylenated methyl methacrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208.

(2) copolymers of hydrophilic acrylates or methacrylates and of hydrophobic monomers containing at least one fatty chain (for example (C₈-C₂2)alkyl

(meth)acrylates) such as, for example, polyethylene glycol methacrylate/lauryl methacrylate copolymer.

(ii) Acrylic anionic amphiphilic polymers may be chosen from those containing at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit of unsaturated carboxylic acid (Ci₀-C₃o)alkyl ester type. They are preferably chosen from those in which the hydrophilic unit of olefinic unsaturated carboxylic acid type corresponds to the monomer of formula (I) below:

H„C= C— C— OH

Ί " (I)

R¹ O

in which formula R¹ denotes H or CH₃ or C₂H₅, i.e. acrylic acid, methacrylic acid or ethacrylic acid units, and in which the hydrophobic unit of unsaturated carboxylic acid (Cio-C₃o)alkyl ester type corresponds to the monomer of formula (II) below:

H„C= C— C— OR²

R O in which formula R¹ denotes H or CH₃ or C₂H₅ (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH₃ (methacrylate units), and R² denotes a C10-C30 and preferably C12-C22 alkyl radical.

Unsaturated carboxylic acid (Ci₀-C₃₀) alkyl esters in accordance with the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

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

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

(i) acrylic acid and one or more esters of formula (III) below:

H₂C= C- C- OR² (I, ,) * ⁰

in which R¹ denotes H or CH₃, and R² denotes an alkyl radical having from 12 to

22 carbon atoms, and a crosslinking agent, such as, for example, those composed of 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of Ci₀-C₃₀ 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 Ci₀-C₃₀ 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 that formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacrylate.

CH₂ = C^

Said crosslinker is a monomer containing a group with at least one other polymerizable group in which the unsaturated bonds are not conjugated with one another. Mention may be made in particular of polyallyl ethers such as, in particular, polyallyl sucrose and polyallyl pentaerythritol.

Among said polymers above, the ones most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1 , Pemulen TR2, Carbopol 1382, and more preferentially still Pemulen TR1 , and the product sold by the company S.E.P.C. under the name Coatex SX.

Anionic amphiphilic polymers with fatty chains further include the methacrylic acid/methyl acrylate/ethoxylated alcohol dimethyl-meta-isopropenylbenzyl isocyanate copolymer sold under the name Viscophobe DB 1000 by the company Amerchol.

Other fatty-chain anionic amphiphilic polymers that may be mentioned include those comprising at least one acrylic monomer containing sulfonic group(s), in free or partially or totally neutralized form and comprising at least one hydrophobic portion.

The hydrophobic portion present in the polymers of the invention preferably contains from 8 to 22 carbon atoms, more preferentially still from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.

Preferentially, the sulfonic polymers in accordance with the invention are partially or totally neutralized with an inorganic base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.

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

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

When they are crosslinked, the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol di(meth)acrylate or tetraethylene glycol di(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, and also allyl esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.

Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate

(TMPTA) will be used more particularly. The degree of crosslinking will generally range from 0.01 mol% to 10 mol% and more particularly from 0.2 mol% to 2 mol% relative to the polymer.

The acrylic monomers containing sulfonic group(s) are chosen especially from (meth)acrylamido(C1 -C22)alkylsulfonic acids and N-(C1 -C22)alkyl(meth)acryl amido(C1 -C22)alkylsulfonic acids, for instance undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.

More preferentially, use will be made of (meth)acrylamido(C1 -C22)alkylsulfonic acids such as, for example, acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2- methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2- acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid,

2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and also their partially or totally neutralized forms.

2-Acrylamido-2-methylpropanesulfonic acid (AMPS®), and also partially or totally neutralized forms thereof, will more particularly be used.

The amphiphilic polymers in accordance with the invention may in particular be chosen from statistical amphiphilic AMPS® polymers modified by reaction with a C₆-C₂2 mono-n-alkylamine or a di-n-alkylamine, of the kind described in patent application WO00/31 154, the polymers described in that application form part of the content of the present description. These polymers may also contain other ethylenically unsaturated hydrophilic monomers, chosen for example from (meth)acrylic acids, their β-substituted alkyl derivatives or their esters obtained with monoalcohols or with monoalkylene or polyalkylene glycols, or (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.

The polymers of the invention may be chosen from amphiphilic copolymers of AMPS® and at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic moiety having from 8 to 50 carbon atoms and more preferentially from 8 to 22 carbon atoms and more preferentially still from 8 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

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

These copolymers are described especially in patent application EP-A-750 899, 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 nonionic 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 nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behaviour - 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 particular copolymers are chosen preferably from the acrylates or acrylamides of the formula (IV) below:

in which R-i and R₃, which are identical or different, denote a hydrogen atom or a linear or branched CrC₆ alkyl radical (preferably methyl); Y denotes O or NH; R₂ denotes a hydrophobic hydrocarbon radical containing at least from 8 to 50 carbon atoms and more preferentially from 8 to 22 carbon atoms and more preferentially still from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.

The radical R₂ is chosen preferably from C₆-Ci₈ alkyl radicals which are linear (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (Ci₂) or adamantane (Ci₀)); C₆-Ci₈ perfluoroalkyl radicals (for example the group of formula -(CH₂)2-(CF₂)9-(CF₃); the cholesteryl radical (C₂₇) or a cholesterol ester residue such as the cholesteryl oxyhexanoate group; and polycyclic aromatic groups such as naphthalene or pyrene. Among these radicals, the ones that are more particularly preferred are linear alkyl radicals and more particularly the n- dodecyl radical. According to one particularly preferred form of the invention, the monomer of formula (IV) comprises at least one alkylene oxide unit (x > 1 ) and preferably a polyoxyalkylenated chain. The polyoxyalkylenated chain, preferentially, is composed of ethylene oxide units and/or propylene oxide units and more particularly is composed of ethylene oxide units. The number of oxyalkylene units generally ranges from 3 to 100, more preferentially from 3 to 50 and more preferentially still from 7 to 25.

Among these polymers, mention may be made of:

- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers comprising from 15% to 60% by weight of AMPS® units and from 40% to 85% by weight of (C₈-Ci₆)alkyl(meth)acrylamide units or of (C₈-Ci₆)alkyl(meth)acrylate units relative to the polymer, such as those described in patent application EP A750 899 ;

- terpolymers comprising 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS® units and from 5 to 80 mol% of n-(C₆-Ci₈)alkylacrylamide units, such as those described in patent US 5089578.

Mention may also be made of the copolymers of fully neutralized AMPS® and dodecyl methacrylate, and also of non-crosslinked and crosslinked copolymers of AMPS® and n-dodecylmethacrylamide, such as those described in the abovementioned Morishima articles.

Mention will be made more particularly of the copolymers composed of 2- acrylamido-2-methylpropanesulfonic acid (AMPS®) units, of formula (V) below:

(V)

CH,

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

and of units of formula (VI) below:

in which x denotes an integer from 3 to 100, preferably from 5 to 80 and more preferentially from 7 to 25; Ri has the same meaning as that indicated above in the formula (I), and R₄ denotes a linear or branched C₆-C₂2 and more preferentially C10-C22 alkyl.

Particularly preferred polymers are those for which x = 25, Ri denotes methyl and R₄ represents n-dodecyl; they are described in the Morishima articles mentioned above. The polymers for which X⁺ denotes sodium or ammonium are more particularly preferred.

(iii) The cationic amphiphilic polymers used in the present invention are preferably selected from polyacrylates containing amine side groups.

The polyacrylates containing quaternized or non-quaternized amine side groups contain, for example, hydrophobic groups of the type of steareth-20 (polyoxyethylenated (20) stearyl alcohol) or (Ci₀-C₃o)alkyl PEG-20 itaconate.

Examples of polyacrylates containing amino side chains that may be mentioned are the polymers 8781 -124B or 9492-103 or Structure Plus from the company National Starch.

(iv) As amphoteric amphiphilic polymers containing at least one fatty chain, mention may be made of copolymers of methacrylamidopropyltrimethylammonium chloride/acrylic acid/C10-C30 alkyl methacrylate, the alkyl radical preferably being a stearyl radical.

(b) The crosslinked acrylic acid homopolymers include those crosslinked with an alcohol allyl ether from the sugar series, such as, for example, the products sold under the names Carbopols 980, 981 , 954, 2984 and 5984 by the company Goodrich, or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA, Cosmedia SP^® or crosslinked sodium polyacrylate containing 90% solids and 10% water, Cosmedia SPL^® or sodium polyacrylate in inverse emulsion, containing approximately 60% of active solids, an oil (hydrogenated polydecene) and a surfactant (PPG-5 Laureth-5), both sold by the company Cognis, and partially neutralized, crosslinked sodium polyacrylates in the form of an inverse emulsion comprising at least one polar oil, for example that polyacrylate sold under the name Luvigel^® EM, sold by the company BASF.

(c) The crosslinked copolymers of (meth)acrylic acid and Ci-C₆ alkyl acrylate include the product sold under the name Viscoatex 538C by the company Coatex, which is a crosslinked copolymer of methacrylic acid and ethyl acrylate in aqueous dispersion with an active substance content of 38%, or the product sold under the name Aculyn 33 by the company Rohm & Haas, which is a crosslinked copolymer of acrylic acid and ethyl acrylate in aqueous dispersion, containing 28% of active substance. Mention may be made more particularly 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 the company Noveon.

(d) The nonionic homopolymers or copolymers containing ethylenically unsaturated monomers of ester and/or amide type include the products sold under the following names: Cyanamer P250 by the company Cytec (polyacrylamide); PMMA MBX-8C by the company US Cosmetics (methyl methacrylate/ethylene glycol dimethacrylate copolymer); Acryloid B66 by the company Rohm & Haas (butyl methacrylate/methyl methacrylate copolymer); BPA 500 by the company Kobo (polymethyl methacrylate).

(e) Mention may be made, among ammonium acrylate homopolymers, of the product sold under the name Microsap PAS 5193 by the company Hoechst.

Mention may be made, among the copolymers of ammonium acrylate and of acrylamide, of the product sold under the name Bozepol C Nouveau or the product PAS 5193 sold by the company Hoechst (they are described and prepared in documents FR-2 416 723, US-2 798 053 and US-2 923 692). (f) Poly(meth)acrylamido-(Ci-C4)alkylsulfonic acids.

According to the present invention, the poly(meth)acrylamido-(Ci-C₄)alkylsulfonic acid or acids are preferably crosslinked.

Even more particularly, they are partially or totally neutralized.

These are water-soluble or water-swellable polymers.

Among these polymers, mention may especially be made of:

- polyacrylamidomethanesulfonic acid,

- polyacrylamidoethanesulfonic acid,

- polyacrylamidopropanesulfonic acid,

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

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

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

Polymers of this type and especially crosslinked and partially or totally neutralized poly(2-acrylamido-2-methylpropanesulfonic acid)s are known, described and prepared in patent application DE-196 25 810.

They are generally characterized by the fact that they comprise, randomly distributed:

a) from 90% to 99.9% by weight of units of formula (VII) below:

(VI I)

CH„

O NH (^— CH₂SO₃ ^" x⁺

CH₃

in which X⁺ denotes a cation or a mixture of cations, including H⁺,

b) from 0.01 % to 10% by weight of at least one crosslinking unit containing at least two olefinic double bonds,

the weight proportions being defined relative 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, one cation equivalent of that of an alkaline-earth metal, or the ammonium ion.

The crosslinked and neutralized poly-(2-acrylamido-2-methylpropanesulfonic acid) preferably comprises from 98% to 99.5% by weight of units of formula (I) and from 0.5% to 2% by weight of crosslinking units.

The crosslinking units containing at least two olefinic double bonds are selected, for example, from dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane or other polyfunctional alcohol allyl or vinyl ethers, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane diallyl ether, methylenebisacrylamide or divinylbenzene.

The crosslinking units having at least two olefinic double bonds are even more particularly chosen from those conforming to the general formula (VIII) below:

in which R-i denotes a hydrogen atom or a C1-C4 alkyl and more particularly methyl (trimethylolpropane triacrylate). The crosslinked and partially or totally neutralized poly(2-acrylamido-2- methylpropanesulfonic acids) are generally known under the names "Ammonium polyacrylamido-2-methylpropanesulfonate" or "Ammonium polyacryldimethyltauramide" (INCI name).

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

(g) Crosslinked polymers of methacryloyloxy(Ci-C4)alkyltri(Ci-C4)alkylammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized by methyl chloride, the homo- or copolymerization being followed by crosslinking with an olefinically unsaturated compound, more particularly methylenebisacrylamide.

It is possible more particularly to use a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride (20/80 by weight) copolymer in the form of a dispersion containing 50% by weight of the said copolymer in inorganic oil. This dispersion is sold under the name Salcare® SC 92 by the company Ciba. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba;

Preferably, the (meth)acrylic thickening polymer(s) according to the invention is (are) anionic.

The thickening polymers with (meth)acrylic units are more particularly chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and (CrC₆)alkyl acrylate.

With further preference, the thickening polymers with (meth)acrylic units are more particularly chosen from crosslinked acrylic acid homopolymers.

The thickening polymers with (meth)acrylic units are preferably aqueous- thickening polymers. The composition according to the present invention advantageously comprises from 0.05% to 20%, preferably from 0.1 % to 10%, more preferably from 0.3% to 5% and even more preferably from 0.5% to 3% by weight of one or more (meth)acrylic thickening polymers, relative to the total weight of the composition.

The weight ratio of water-insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη to thickening polymer or polymers with (meth)acrylic units preferably ranges from 1 to 100, preferably from 2 to 50, more preferably from 5 to 20.

FIXING POLYMER

As indicated previously, the compositions comprise at least one fixing polymer different from the thickening polymers used according to the invention. A fixing polymer in the sense of the present invention is any polymer that allows the hair to be shaped or the hair to be held in a given shape.

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 aqueous medium or insoluble in this same medium and may in that case be used in the form of dispersions of solid or liquid particles of polymer (latex or pseudo-latex). The anionic fixing polymers generally used are polymers containing groups derived from carboxylic, sulfonic or phosphoric acid, and have a number-average molecular mass of between approximately 500 and 5 000 000.

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 No. 1 222 944 and German patent application No. 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 Nos. 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-ie f-butylacrylamide terpolymers such as Ultrahold Strong sold by the company BASF. Mention may also be made of copolymers of acrylic acid and of Ci-C₄ alkyl methacrylate and terpolymers of vinylpyrrolidone, of acrylic acid and of C1-C2₀ alkyl methacrylate, 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 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. Polymers of these kinds are described in references including French patents Nos. 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 National Starch;

D) copolymers of monounsaturated C₄-C₈ 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 chosen from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidated. Polymers of these kinds are described more particularly in US patents Nos. 2047398, 2723248, 21021 13 and in GB patent No. 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 chosen from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, oc-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 Nos. 2 350 384 and 2 357 241 by the Applicant.

E) Polyacrylamides containing carboxylate groups.

F) Homopolymers and copolymers comprising sulfonic groups, such as the polymers containing vinylsulfonic, styrenesulfonic, naphthalenesulfonic or acrylamidoalkylsulfonic units. These polymers may in particular be chosen 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 esters thereof, and also acrylamide or derivatives thereof, 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 National Starch. 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 L 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 National Starch, 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 polymers that can be used according to the present invention are preferably chosen 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 approximately 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 CH₃ 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;

R₄, R₅ and R₆, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical;

Ri and R₂, 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 ) also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (CrC₄) 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 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,

- the copolymer 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/vinylcaprolactam/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 pyrrolidonecarboxylate.

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 pyrrolidonecarboxylate 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 described 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 under the name Celquat L 200 and Celquat H 100 by the company National Starch. The amphoteric fixing polymers that may be used in accordance with the invention may be selected from polymers comprising units B and C distributed randomly in the polymeric chain, where B denotes a unit deriving from a monomer containing at least one basic nitrogen atom, and C denotes a unit deriving from an acidic monomer containing one or more carboxylic or sulfonic groups, or else B and C may denote groups deriving from zwitterionic carboxybetaine or sulfobetaine monomers;

B and C may 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 of a polymer with an α,β-dicarboxylic ethylene unit, in which one of the carboxyl groups has been reacted with a polyamine containing 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 containing 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, ochloroacrylic 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, dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US patent No. 3 836 537;

(2) polymers comprising units derived from:

a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with 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-ie f- butylacrylamide, N-ie f-octylacrylamide, N-octylacrylamide, N-decylacrylamide, N- dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids and also from monoalkyl esters, having 1 to 4 carbon atoms, of the maleic or fumaric acids or anhydrides.

The preferred basic comonomers are aminoethyl, butylaminoethyl, Ν,Ν'- dimethylaminoethyl and N-tert-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 National Starch, are particularly used.

(3) Crosslinked and acylated polyaminoamides partially or totally derived from polyaminoamides of general formula:

CO— R_in— CO (IX) in which R₁₀ represents a divalent group derived from a saturated dicarboxylic acid, from an aliphatic mono- or dicarboxylic acid with an ethylenic double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms with these acids, or from a group deriving from the addition of any of said acids with a bis-primary or bis- secondary amine, and Z denotes a group deriving from a bis-primary or mono- or bis- secondary polyalkylene-polyamine, and preferably represents:

a) in proportions of from 60 mol% to 100 mol%, the group

N + (CH₂)_X - N - (X)

H H

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

this group deriving from diethylenetriamine, from triethylenetetraamine 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-(CH₂)6-NH- group being derived from hexamethylenediamine,

these polyaminoamides being crosslinked by addition reaction of a difunctional crosslinking agent chosen 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:

in which R-n denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, Ri2 and Ri₃ represent a hydrogen atom or a methyl, ethyl or propyl group, Ri₄ and R-I5 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R₁₄ and Ri₅ does not exceed 10.

The polymers comprising such units may also comprise units derived from non- zwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or from alkyl acrylates or methacrylates, from 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 under the name Diaformer Z301 by the company 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), R₁₆ represents a group of formula:

R 19

R 17 -<⁰>-?

in which, if q = 0, R17, Ri₈ 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, Ri₈ and R19 being, in this case, a hydrogen atom;

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

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

in which R₂₀ represents a hydrogen atom or a CH₃0, CH₃CH₂0 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-C₆ lower alkyl group such as methyl or ethyl, R23 denotes a lower Ci-C₆ alkyl group such as methyl or ethyl, or a group corresponding to the following formula: -R24-N(R₂2)2, R24 representing a -CH₂-CH₂-, -CH2-CH2-CH2- or - CH₂-CH(CH₃)- 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- (XIII)

where D denotes a group

/ \

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- (XIV)

where D denotes a group

/ \

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 alkyi 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) (CrC₅)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 National Starch 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 chosen, 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, such as for example, copolymers of alkyi acrylates and alkyi methacrylates, such as the products proposed 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, and by the company Hoechst under the name Appretan^® N9212;

- copolymers of acrylonitrile and a nonionic monomer, chosen, for example, from butadiene and alkyi (meth)acrylates; mention may be made of the products provided under the name CJ 0601 B by the company Rohm & Haas;

- styrene homopolymers;

- styrene copolymers, for instance copolymers of styrene and of an alkyi (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 alkyi methacrylate and of alkyi acrylate; copolymers of styrene and of butadiene; or copolymers of styrene, of butadiene and of vinylpyridine;

- polyamides;

- vinyllactam homopolymers such as vinylpyrrolidone homopolymers, in particular sold under the name PVP K90 by the company ISP, and such as 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.

The alkyl groups of the abovementioned nonionic polymers 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 constituted 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.

Polymers of these kinds are, for example, the copolymers obtainable by radical polymerization from the mixture of monomers formed by:

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 of formula:

CH₂ -CH₃

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 which may be mentioned is the Luviflex^® Silk product 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 to which the present invention is particularly directed are those described in patent applications 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 also in patent applications EP 0 656 021 and WO 94/03510 from the company BASF, and EP 0 619 1 1 1 from the company National Starch.

Polyurethanes particularly suitable in the present invention include the products sold under the names Luviset Pur^® and Luviset^® Si Pur by the company BASF. In one embodiment, the fixing polymer or polymers used in the composition according to the invention is or are fixing polymers comprising at least one vinyllactam unit. The fixing polymer or polymers used in the composition according to the invention preferably is or are nonionic fixing polymers, more particularly nonionic fixing polymers chosen from vinyllactam homopolymers, such as vinylpyrrolidone homopolymers, polyvinylcaprolactam, and vinyllactam copolymers, such as a poly(vinylpyrrolidone/vinyllactam) copolymer, poly(vinylpyrrolidone/vinyl acetate) copolymers, and poly(vinylpyrrolidone/vinyl acetate/vinyl propionate) terpolymers.

More preferentially, the nonionic fixing polymer or polymers used in the composition according to the invention is or are chosen from vinylpyrrolidone homopolymers and poly(vinylpyrrolidone/vinyl acetate) copolymers.

The amount of fixing polymer or polymers used in the compositions according to the present invention is from 0.01 % to 20%, preferably from 0.1 % to 10% by weight, relative to the total weight of the composition. The composition according to the invention comprises an aqueous phase.

Preferably, the water content is from 10% to 98%, preferably from 20% to 96%, more preferably from 50% to 96% by weight, more preferably still from 70% to 96% by weight, relative to the total weight of the composition. The composition may further comprise one or more organic solvents, more particularly water-soluble organic solvents, such as Ci-C₇ alcohols; mention may in particular be made of Ci-C₇ aliphatic monoalcohols or C₆-C₇ aromatic monoalcohols, of polyols such as glycerol and of C₃-C₇ polyol ethers.

The composition of the invention may further comprise at least one typical cosmetic ingredient, in particular chosen from propellants; oils; solid fats and in particular C₈-C₄o esters, C₈-C₄₀ acids; C₈-C₄₀ alcohols, sunscreens; moisturizing agents; anti-dandruff agents; antioxidants; chelating agents; pearlizing and opacifying agents; plastifying agents or coalescents; fillers; silicones; polymeric or non-polymeric thickeners or gellants, other than the (meth)acrylic thickening polymers already mentioned; emulsifiers; polymers, especially conditioning polymers; perfumes; alkalifying agents such as aqueous sodium hydroxide solution, or acidifying agents; silanes; and crosslinking agents. The composition can, of course, comprise several cosmetic ingredients appearing in the above list.

Depending on their nature and the purpose of the composition, the normal cosmetic ingredients can be present in normal amounts which can be easily determined by those skilled in the art and which can be, for each ingredient, between 0.01 % and 80% by weight. Those skilled in the art will take care to choose the ingredients included in the composition and the amounts thereof so that they do not harm the properties of the compositions of the present invention.

The composition according to the invention initially takes the form of a powder.

When it is spread, the powder turns into a texture with a liquid component, such as a cream, a gel, a serum or a paste, preferably in the form of cream. The cosmetic composition according to the invention may advantageously be used for the cosmetic treatment of hair. More particularly, the composition may be employed for the styling of hair, for example for shaping and/or maintaining the shape of the hairstyle.

The present invention likewise relates to a process for cosmetic treatment of the hair, for example a process for shaping and/or maintaining the shape of the hairstyle, which involves applying to the hair an effective amount of a composition according to the invention as described above, then in carrying out an optional rinse after an optional leave-on time.

Preferably, the composition according to the invention is not rinsed off.

The process of the invention may be performed at room temperature (25°C) or using heat at a temperature ranging from 40°C to 250°C using any heating device: hood, hairdryer, tongs. The invention is illustrated in more detail in the following examples, which are provided by way of illustration and without limitation of the invention.

EXAMPLES

Styling compositions were produced from the ingredients indicated, as a weight percentage of product in unmodified form, in the tables below:

AS = Active Substances

Cosmedia SP sold by the company BASF

Alumina AS-EM sold by the company Sensient

Luviskol VA 64 W sold by the company BASF

(¹⁾ Cosmedia SP sold by the company BASF

⁽²⁾ Alumina AS-EM sold by the company Sensient

⁽⁴⁾ PVP K90 sold by the company ISP

⁽⁵⁾ Aerogel VM2270 sold by the company Dow Corning The resulting compositions are in powder form.

The compositions may be packaged in a shaker-type plastic tube. The compositions are delivered either to the hands, to be worked subsequently in the palms of the hands and applied to the hair, or directly to the hair, to be subsequently worked directly onto the hair. In both cases, the powder turns to a cream.

Application of the composition to the hair is very easy, owing to the low volatility and highly melting nature of the powder.

The composition provides the hair with hold and also with a soft, smooth, glossy character.

Claims

1 Cosmetic composition in powder form, comprising an aqueous phase, water- insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη, one or more thickening polymers with (meth)acrylic units and one or more fixing polymers different from the thickening polymer or polymers with (meth)acrylic units. 2 Composition according to Claim 1 , wherein the water-insoluble particles have a number-average primary size of from 0.2 to 500 μηη, preferably from 0.5 to 300 μηη and more preferentially from 1 to 200 μηη, especially from 1 to 100 μηη.

3 Composition according to either of the preceding claims, wherein the water-insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη are chosen from particles of one or more polymeric organic compounds and/or particles of one or more inorganic compounds, preferably from particles of one or more inorganic compounds. 4 Composition according to any one of the preceding claims, wherein the water- insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη are chosen from metal particles, oxides, inorganic salts, carbides, nitrides, sulfides and hydroxides, in particular from clays, silicates, alumina, silica, kaolin and hydroxyapatite, preferably from inorganic hydroxides, silicates and silica.

5 Composition according to any one of the preceding claims, wherein the water- insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη are hydrophobized. 6 Composition according to any one of the preceding claims, wherein the water- insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη are present in the composition in concentrations of from 1 % to 40% by weight, preferably from 5% to 30% and more preferentially from 10% to 20% by weight, relative to the total weight of the composition.

7 Composition according to any one of the preceding claims, wherein the thickening polymer or polymers with (meth)acrylic units are chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and (CrC₆)alkyl acrylate,

(d) nonionic homopolymers and copolymers containing ethylenically unsaturated monomers of ester and/or amide type;

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

(f) homopolymers and copolymers of (meth)acrylamido(C1 -C4)alkyl sulfonic acids,

(g) crosslinked methacryloyl(C1 -C4)alkyl tri(C1 -C4)alkylammonium homopolymers and copolymers. 8 Composition according to any one of the preceding claims, wherein the thickening polymer or polymers with (meth)acrylic units are chosen from:

(a) acrylic associative thickeners;

(b) crosslinked acrylic acid homopolymers;

(c) crosslinked copolymers of (meth)acrylic acid and (CrC₆)alkyl acrylate, preferably from crosslinked acrylic acid homopolymers.

9 Composition according to any one of the preceding claims, wherein the thickening polymer or polymers with (meth)acrylic units represent from 0.05% to 20%, preferably from 0.1 % to 10%, more preferably from 0.3% to 5% and even more preferably from 0.5% to 3% by weight, relative to the total weight of the composition.

10 Composition according to any one of the preceding claims, wherein the weight ratio of water-insoluble particles having a number-average primary size of greater than or equal to 0.2 μηη to thickening polymer with (meth)acrylic units ranges from 1 to 100, preferably from 2 to 50, more preferably from 5 to 20.

1 1 Cosmetic composition according to any one of the preceding claims, wherein the fixing polymer or polymers are chosen from anionic, nonionic, amphoteric or cationic, preferably nonionic, fixing polymers.

12 Cosmetic composition according to any one of the preceding claims, wherein the fixing polymer or polymers comprise at least one vinyllactam unit. 13 Composition according to any one of the preceding claims, characterized in that the fixing polymer or polymers are present in proportions of at least 0.001 % by weight, preferably of from 0.05% to 10% by weight, more preferentially from 0.05% to 8% by weight, especially from 0.1 % to 7% by weight, relative to the total weight of the composition.

14 Composition according to any one of the preceding claims, characterized in that water is present in the composition in an amount of from 10% to 98%, preferably from 20% to 96%, more preferably from 50% to 96% by weight, more preferably still from 70% to 96% by weight, relative to the total weight of the composition.

15 Cosmetic process for treating keratin fibres, in particular human keratin fibres such as the hair, characterized in that it consists in applying to the said fibres an effective amount of a composition as defined according to any one of Claims 1 to 14. 16 Process according to Claim 15, characterized in that the powder becomes a cream when it is spread out in the hand or on the fibres.

17 Use of a composition according to any one of Claims 1 to 14 for hair treatment, in particular for treating keratin fibres and more particularly for shaping and/or maintaining the shape of the hair.