WO2007099272A2

WO2007099272A2 - Cosmetic composition comprising a (poly)alkylene glycol ether, an acrylate or methacrylate and acrylate or methacrylate hydroxyester copolymer, and a thickening polymer, and the use thereof as a capillary product

Info

Publication number: WO2007099272A2
Application number: PCT/FR2007/050876
Authority: WO
Inventors: Ludivine Laurent; Cécile Bebot
Original assignee: L'oreal
Priority date: 2006-03-03
Filing date: 2007-03-02
Publication date: 2007-09-07
Also published as: WO2007099272A3

Abstract

The invention relates to a cosmetic composition comprising, in a cosmetically acceptable medium, at least one alkylene glycol or polyalkylene glycol ether, at least one acrylate or methacrylate and acrylate or methacrylate hydroxyester copolymer, and at least one natural or synthetic thickening polymer, the weight ratio between the quantity of acrylate or methacrylate and acrylate or methacrylate hydroxyester copolymers and the quantity of alkylene glycol or polyalkylene glycol ethers being between 0.1 and 15. Said composition is especially used as a hairstyling product.

Description

Cosmetic composition comprising a (poly) alkylene glycol ether, a copolymer of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s), and a thickening polymer, as well as its use as a hair product.

The present invention relates to a cosmetic composition comprising, in a cosmetically acceptable medium, at least one (poly) alkylene glycol ether, at least one copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) and at least one natural or synthetic thickening polymer.

The present invention also relates to a cosmetic hair treatment method using the aforementioned composition, and a use of this cosmetic composition as a hair product, for example as a styling product.

Hair styling products are usually used to build, structure the hairstyle and give it a lasting hold. The corresponding compositions generally comprise one or more film-forming polymers in a cosmetically acceptable medium. These polymers allow the formation of a sheathing film on the hair, thus ensuring the maintenance of the hairstyle.

However, the fixing polymer films thus formed have the disadvantage of being relatively friable, which limits in time the holding of the hairstyle, and causes the formation on the hair of unsightly residues.

To reduce these problems of friability, it is known to incorporate in the styling products based on film-forming polymers a plasticizer. This effectively improves the behavior of the hairstyle over time and limit the formation of residues during the day.

However, despite the addition of such a plasticizer, the non-friability of the polymer films is generally related to the concentration of fixing polymer in the styling product (or degree of fixation): if the concentration of fixing polymer is decreased to reduce the rigidity of the hairstyle, then the polymer film becomes more friable and the hairstyle is less good. There is therefore a need for hair compositions that make it possible to obtain a lasting hold of the hairstyle, whatever the degree of fixation.

The Applicant has now discovered that, surprisingly, the combination of a particular fixing polymer, of the (meth) acrylate (s) / hydroxyester (meth) acrylate (s) type, with an alkylene glycol ether or of polyalkylene glycol and a natural or synthetic thickening polymer, by employing a specific weight ratio between the amount of acrylate (s) or methacrylate (s) copolymer (s) and acrylate (s) or methacrylate hydroxyester (s) ( s) on the one hand and the amount of ether (s) alkylene glycol or polyalkylene glycol, on the other hand, allowed to obtain a hair composition providing improved styling properties. In particular, such an association makes it possible to obtain hair styling products providing a range of flexible to ultra-strong bindings, with an extremely low-friable polymer film, whatever the degree of fixation. It thus becomes possible to formulate long-lasting flexible fastening products.

The present invention makes it possible in particular to prepare hair styling products that provide significantly improved hairstyling durability, including in products with flexible fixation, that is to say with a low concentration of fixing polymer.

Moreover, and quite unexpectedly, the compositions according to the invention have been found to provide a very marked improvement in the cosmetic properties of the hair after disentangling: the hair is much softer and less dry than after the application of a conventional fixing product.

The subject of the present invention is therefore a cosmetic composition comprising, in a cosmetically acceptable medium, at least one alkylene glycol or polyalkylene glycol ether, at least one a copolymer of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s), and at least one natural or synthetic thickening polymer, the weight ratio between the amount of copolymer (s) ( s) acrylate (s) or methacrylate (s) and hydroxyester acrylate (s) or methacrylate (s) on the one hand and the amount of ether (s) alkylene glycol or polyalkylene glycol, on the other hand, being between 0, 1 and 15.

Another subject of the invention consists of a cosmetic hair treatment method using a composition according to the invention as described below.

The subject of the invention is also the use of the composition according to the invention for the cosmetic treatment of the hair, in particular for shaping and / or maintaining the hairstyle.

Other objects, features, aspects and advantages of the invention will emerge even more clearly on reading the following description and example.

In the present disclosure, the term "compound in CY" a compound comprising Y carbon atoms;

According to the invention, the cosmetic composition comprises, in a cosmetically acceptable medium, at least one alkylene glycol or polyalkylene glycol ether, at least one copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) and at least one natural or synthetic thickening polymer. By "cosmetically acceptable medium" is meant a medium compatible with keratin materials and in particular the hair.

Preferably, the cosmetically acceptable medium comprises water and / or at least one cosmetically acceptable solvent chosen from C ₁ -C ₄ lower alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol. -butanol; polyols such as glycol, glycerol, propylene glycol; polyol ethers other than (poly) alkylene glycol ethers; C ₅ -C ₁₀ alkanes; C _{3 -4} ketones such as acetone and methyl ethyl ketone; the alkyl acetates in C ₁ -C ₄ such as methyl acetate, ethyl acetate and butyl acetate; dimethoxyethane, diethoxyethane; and their mixtures.

The composition according to the invention comprises at least one copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), that is to say a copolymer obtained by copolymerization of at least two monomers:

at least one first monomer chosen from acrylic acid, methacrylic acid, C 1 to C 4 alkyl acrylates and methacrylates, and at least one second monomer chosen from C 1 hydroxyalkyl acrylates and methacrylates; at C4.

Preferably, said copolymer is obtained by copolymerization of at least three monomers:

at least one first monomer chosen from acrylic acid and methacrylic acid,

at least one second monomer chosen from C1 to C4 alkyl acrylates and methacrylates, and

at least one third monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates. Preferably, said second monomer comprises at least one C 1 or C 2 alkyl acrylate or methacrylate. In other words, said second monomer can then be methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and mixtures of these compounds. Preferably, said third monomer is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, and mixtures of these compounds.

According to a preferred embodiment, the composition according to the invention comprises a mixture of at least two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) as described above.

It can be a mixture of at least two copolymers with at least two monomers as described above, a mixture of at least two copolymers with at least three monomers as described above, or a mixture of at least one copolymer with at least two monomers and at least one copolymer with at least three monomers as described above.

In a first variant of this preferred embodiment, the composition according to the invention comprises a mixture of two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s). ), each of the copolymers being obtained by copolymerization of at least three monomers as described above, namely: at least one first monomer chosen from acrylic acid and methacrylic acid,

at least one third monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates.

In a second variant of this preferred embodiment, the composition according to the invention comprises a mixture of two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s). ), comprising a first copolymer obtained by copolymerization of at least three monomers as described above: at least a first monomer chosen from acrylic acid and methacrylic acid,

at least one third monomer chosen from C1 to C4 hydroxyalkyl acrylates and methacrylates; and a second copolymer obtained by copolymerization of at least two monomers: at least one first monomer chosen from C1-C4 alkyl acrylates and methacrylates, and at least one second monomer chosen from hydroxyalkyl acrylates and methacrylates; C1 to C4; said second copolymer does not contain monomers consisting of unsaturated carboxylic acids.

When the composition according to the invention comprises a mixture of at least two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), the two copolymers of this The mixture preferably has different glass transition temperatures.

The glass transition temperature (Tg) is measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418-97.

One of the two copolymers preferably has a Tg ranging from 35 ° C. to 250 ° C., more preferably from 40 ° C. to 150 ° C. and even more preferentially from 75 ° C. to 100 ° C. The second copolymer preferably has a Tg ranging from -20 ° C to 35 ° C, more preferably from 0 ° C to 35 ° C and even more preferably from 15 ° C to 30 ° C.

The difference of Tg between the two copolymers is preferably greater than or equal to 10 ° C, more preferably greater than or equal to 20 ° C and even more preferably greater than or equal to 30 ° C.

The copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s) usable (s) in the compositions according to the invention can (can) ) be a block copolymer (s), statistical or alternating. Preferably, it is a random copolymer.

Advantageously, the copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) is an anionic copolymer.

More preferably, it comprises hard sequences and soft sequences, that is to say sequences with two glass transition temperatures (Tg), one of the Tg being between 15 and 35 ° C, preferably between 20 and 30 ° C, the other Tg being between 90 and 1 10 ° C, preferably between 95 and 105 ° C.

Advantageously, the hard sequence comprises at least one monomer chosen from methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and methacrylic acid, and more preferably, the hard sequence comprises all these monomers.

Advantageously, the soft sequence comprises at least one monomer selected from ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, methacrylic acid and more preferably, the soft sequence comprises all these monomers.

Preferably, the molecular weight of this copolymer is between 10,000 g / mol and 200,000 g / mol. Even more preferentially, it is between 20,000 g / mol and 100,000 g / mol. The copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s) can be in a wide variety of forms, for example in the form of solutions or emulsions in water or any other solvent.

They can be synthesized by any known method for preparing a copolymer from its different monomers.

By way of example of copolymers and copolymer mixtures that may be used in the compositions according to the invention, mention may be made, inter alia, of the products sold under the name Acudyne by the company Rohm & Haas, such as, for example, and in a nonlimiting manner, the products proposed under the name ACUDYNE

DHR, ACUDYNE 258, ACUDYNE 180.

The composition according to the invention preferably contains at least 0.01% by weight of copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) , relative to the total weight of the composition. Preferably, it contains from 0.01% to 20% by weight of copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), and even more preferably from 0.1 to 10% by weight, more preferably from 0.5 to 8% by weight, relative to the total weight of the composition. The composition according to the invention also comprises at least one alkylene glycol or polyalkylene glycol ether, that is to say a compound of formula R ₁ - (OR) _n -OR ₂ , with R ₁ denoting a radical alkyl, R denoting an alkylene radical, and R ₂ denoting hydrogen (case of a monoether) or an alkyl radical (case of a diether) and n denoting an integer ranging from 1 to 10,000.

Preferably, R ₁ denotes an alkyl radical comprising from 1 to

8 carbon atoms, R denotes ethylene or propylene, R ₂ denotes hydrogen or an alkyl radical, identical to or different from R ₁ , comprising from 1 to 8 carbon atoms and n denotes an integer ranging from 1 to 10,000.

More preferably, R ₁ denotes an alkyl radical comprising 1 to 4 carbon atoms and R ₂ denotes hydrogen or an alkyl radical, identical to or different from R ₁ , comprising from 1 to 4 carbon atoms.

Preferably, n ranges from 1 to 1000, and more preferably from

1 to 500, even more preferably from 2 to 500, and more preferably from 2 to 250. Even more preferably, the composition according to the invention comprises a mono or di (C 1 -C 8) alkyl ether (s). and propylene glycol or polypropylene glycol having from 2 to 500, and preferably from 2 to 250 propylene glycol units.

More preferably, the composition according to the invention comprises a mono- or a diether of C1-C8 alkyl, preferably C1-C4, and polypropylene glycol having from 2 to 100 propylene glycol units, and more preferably from 2 to 50 propylene glycol units.

The composition according to the invention preferably contains at least 0.01% by weight of ether (s) alkylene glycol or polyalkylene glycol, relative to the total weight of the composition. Preferably, it contains from 0.01 to 15% by weight, more preferably from 0.05 to 10% by weight, and still more preferably from 0.1 to 8% by weight of alkylene glycol ether (s). or polyalkylene glycol, relative to the total weight of the composition. The weight ratio between the amount of copolymer (s) of acrylate (s) or of methacrylate (s) and of acrylate (s) or methacrylate hydroxyester (s) on the one hand and the amount of ether ( s) of alkylene glycol or polyalkylene glycol, on the other hand, is between 0.1 and

15, and preferably between 1 and 10. The composition according to the invention also comprises at least one natural or synthetic thickening polymer. Such a thickening polymer may advantageously be chosen from anionic, amphoteric, zwitterionic, nonionic or cationic, associative or non-associative polymeric thickeners.

Such a thickening polymer may advantageously be chosen from homopolymers of acrylic acid, crosslinked or non-crosslinked, such as, for example, those sold under the name Carbopol by the company Noveon. The composition according to the invention preferably contains at least 0.01% by weight of thickening polymer, relative to the total weight of the composition. Preferably, it contains from 0.1 to 10% by weight of thickening polymer, relative to the total weight of the composition. The compositions according to the invention may also contain at least one non-polymeric thickener such as, for example, an electrolyte or a sugar.

The compositions according to the invention may also contain at least one fatty substance. The fatty substances that can be used in the present invention are chosen in particular from vegetable oils, animal oils, mineral oils, natural or synthetic oils, fatty alcohols, waxes and their mixtures.

As vegetable oil, there may be mentioned sweet almond oil, avocado oil, castor oil, olive oil, liquid jojoba wax, sunflower oil, wheat germ oil, sesame oil, peanut oil, grape seed oil, soybean oil, rapeseed oil, safflower oil, coconut oil , corn oil, hazelnut oil, palm oil, apricot kernel oil, calophyllum oil, evening primrose oil, shea butter, rice bran, corn germ oil, passionflower oil and rye oil.

As animal oil, there may be mentioned perhydrosqualene. As mineral oil, mention may be made of paraffin oil and liquid petroleum jelly.

As synthetic oil, there may be mentioned squalane, poly (α-olefins) such as isododecane or isohexadecane, transesterified vegetable oils and fluorinated oils.

Preferred fatty alcohols include myristyl, cetyl, stearyl, arachidyl, behenyl and erucyl alcohols.

A wax, within the meaning of the present invention, is a lipophilic compound, solid at room temperature (about 25 ° C.), with a reversible solid / liquid state change, having a melting temperature greater than about 40 ° C. and that can go up to 200 ° C, and having in the solid state an anisotropic crystalline organization. Animal and vegetable waxes comprise, as essential components, esters of carboxylic acids and long-chain alcohols. In general, the size of the crystals of the wax is such that the crystals diffract and / or diffuse the light, conferring on the composition which comprises them a more or less opaque cloudy appearance. By bringing the wax to its melting temperature, it is possible to render it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, a recrystallization of the wax in the oils of the mixture, detectable microscopically and macroscopically (opalescence).

As waxes that can be used in the present invention, mention may be made of waxes of animal origin, such as beeswax, spermaceti, lanolin wax and lanolin derivatives; vegetable waxes such as sunflower wax, rice wax, apple wax, Carnauba wax, Candelilla wax, Ouricury wax, Japan wax, cocoa butter wax or cork fiber wax or sugar cane wax; mineral waxes, for example paraffin, petrolatum, lignite or microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene waxes, Fischer-Tropsch waxes, and mixtures thereof. The fatty substances as described above, when they are present in the composition according to the invention, are preferably present in an amount ranging from 0.1 to 30% by weight, preferably from 1 to 20% by weight. and more preferably from 5 to 15% by weight, based on the total weight of the composition.

The composition according to the invention may also comprise at least one surfactant, chosen from cationic surfactants, anionic surfactants, nonionic surfactants other than (poly) alkylene glycol ethers, amphoteric or zwitterionic surfactants.

The composition according to the invention then preferably comprises at least 0.01% by weight of surfactant (s), relative to the total weight of the composition. Preferably, the composition according to the invention contains from 0.01 to 20% by weight of surfactant (s), more preferably from 0.05 to 4% by weight, relative to the total weight of the composition.

By way of example of anionic surfactants that can be used in the compositions according to the present invention, mention may be made in particular (nonlimiting list) of the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, sodium salts and the like). aminoalcohols or alkaline earth (magnesium) salts) of the following compounds: alkylsulfates, alkylethersulfates, alkylamidoethersulfates, alkylarylpolyethersulfates, monoglycerides sulfates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin-sulfonates, paraffin-sulfonates; alkylsulfosuccinates; alkyl ether sulfosuccinates, alkyl amide sulfosuccinates; alkylsulfosuccinamates; alkylsulfoacetates; alkyl ether phosphates, acylsarcosinates; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably comprising from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group.

Among the anionic surfactants that can still be used, mention may also be made of fatty acid salts such as oleic acid salts, ricinoleic, palmitic, stearic; coconut oil or hydrogenated coconut oil acids; acyl lactylates whose acyl radical has 8 to 20 carbon atoms.

It is also possible to use weakly anionic surfactants, such as acid alkyl D galactoside uronic and salts thereof, polyoxyalkylenated (C ₆ - C ₂₄₎ ether carboxylic acids, polyoxyalkylenated (C ₆ -C2 ₄₎ aryl ether carboxylic polyoxyalkylenes, polyoxyalkylenated (C ₆ -C ₂₄ ) alkyl amino carboxylic acids and their salts, in particular those containing from 2 to 50 ethylene oxide groups and mixtures thereof.

Among the anionic surfactants, it is preferred to use, according to the invention, the salts of alkyl sulphates and alkyl ether sulphates and their mixtures.

The cationic surfactants that can be used in the compositions of the present invention comprise, for example, primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated salts, quaternary ammonium salts, and mixtures thereof.

As quaternary ammonium salts, there may be mentioned, for example:

- those corresponding to the following general formula (I):

+

^R 8, ^R 10

X- (I)

R ₉ R ₁₁

in which the radicals R ₈ to R ₁₁ , which may be identical or different, represent a linear or branched aliphatic radical containing from 1 to 30 carbon atoms, or an aromatic radical such as aryl or alkylaryl. The aliphatic radicals may comprise heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens. The aliphatic radicals are for example chosen from alkyl C _{1 -30} alkoxy, C _{1 -30,} polyoxy (C ₂ -C _6), C ₁ -C ₃₀ alkylamide, (C ₁₂ -C 22) alkylamido (C 2 -C ₆ ) alkyl, (C ₁₂ -C 22) alkyl, and C ₁ -C ₃₀ hydroxyalkyl; X is an anion selected from the group of halides, phosphates, acetates, lactates, (C ₂ -C ₆ ) alkyl sulfates, alkyl- or alkylarylsulfonates.

Of the quaternary ammonium salts of formula (I), tetraalkylammonium chlorides, such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl radical has from about 12 to 22, are preferred. carbon atoms, in particular behenyltrimethylammonium, distearyl dimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium chlorides or else palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl (myristylacetate) ammonium chloride sold under the CERAPHYL ^® 70 denomination by the company VAN DYK.

the quaternary ammonium salts of imidazoline, for example those of formula (II) below:

wherein R ₁₂ represents an alkenyl or alkyl radical having

8 to 30 carbon atoms, for example fatty acid derivatives of tallow, R ₁₃ represents a hydrogen atom, a C ₁ -C ₄ alkyl radical or an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, R ₁₄ represents a C ₁ -C ₄ alkyl radical, R ₁₅ represents a hydrogen atom, a C ₁ -C ₄ alkyl radical, X ^" is an anion chosen from the group of halides, phosphates, acetates, lactates and alkyl sulphates. R ₁₂ and R ₁₃ denote a mixture of alkenyl or alkyl radicals containing from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R ₁₄ denotes a methyl radical, R ₁₅ denotes a hydrogen atom, such a product is for example marketed under the name REWOQUAT W 75 by the company REWO;

the quaternary diammonium salts of formula (III):

^R 17 ^R 19

R ₁₆ -N- (CH ₂ ) ₃ -NR ₂₁ 2X- (III)

R 18 R 20

wherein R ₁₆ is an aliphatic radical having about 16 to 30 carbon atoms; R ₁₇ , R ₁₈ , R _1, R ₂₀ and R ₂₁ , which are identical or different, are chosen from a hydrogen atom and an alkyl radical containing from 1 to 4 carbon atoms; and X is an anion selected from the group of halides, acetates, phosphates, nitrates and methylsulfates. Such diammonium quaternary salts include in particular propane dichloride diammonium;

the quaternary ammonium salts containing at least one ester function, such as those of formula (IV) below:

in which :

R22 is selected from alkyl C ₁ -C ₆ hydroxyalkyl or dihydroxyalkyl radicals C ₁ -C ₆ alkyl;

R ₂₃ is chosen from:

O

radical ^R 26 ~ C

linear or branched, saturated or unsaturated C ₁ -C ₂₂ hydrocarbon radicals R ₂₇ ,

- the hydrogen atom, R ₂₅ is selected from:

O

the radical R ₂₈ - C -

the linear or branched, saturated or unsaturated C ₁ -C ₆ hydrocarbon radicals R ₁ , the hydrogen atom,

R24, R2 ₆ and R ₂₈ , which are identical or different, are chosen from linear or branched, saturated or unsaturated C ₇ -C ₂₁ hydrocarbon radicals; r, s and t, identical or different, are integers ranging from 2 to 6; y is an integer from 1 to 10; x and z, which are identical or different, are integers ranging from 0 to 10; X ^" is a simple or complex anion, organic or inorganic, provided that the sum x + y + z is from 1 to 15, that when x is 0, then R ₂₃ denotes R ₂₇ and that when z is 0, then R ₂₅ denotes R29.

The alkyl radicals R ₂₂ may be linear or branched and more particularly linear.

Preferably R ₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical, and more particularly a methyl or ethyl radical.

Advantageously, the sum x + y + z is from 1 to 10. When R ₂₃ is a hydrocarbon radical R ₂₇ , it can be long and have from 12 to 22 carbon atoms, or short and have from 1 to 3 carbon atoms. .

When R ₂₅ is a hydrocarbon radical R ₂₉ , it preferably has 1 to 3 carbon atoms. Advantageously, R ₂₄ , R ₂ and R ₂₈ , which are identical or different, are chosen from linear or branched, saturated or unsaturated C ₁₁ -C ₂₁ hydrocarbon radicals, and more particularly from C ₁₁ -C 18 alkyl and alkenyl radicals. ₂₁ , linear or branched, saturated or unsaturated. Preferably, x and z, identical or different, are 0 or 1.

Advantageously, y is 1. Preferably, r, s and t, which are identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anion is preferably a halide (chloride, bromide or iodide) or an alkyl sulphate more particularly methyl sulphate. However, it is possible to use methanesulphonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as acetate or lactate or any other anion compatible with ammonium with an ester function.

The anion X ^" is even more particularly chloride or methylsulphate, The ammonium salts of formula (IV) are used more particularly in the composition according to the invention in which:

R ₂₂ denotes a methyl or ethyl radical,

- x and y are equal to 1;

z is 0 or 1; r, s and t are equal to 2;

R ₂₃ is chosen from:

O

II

the radical R ₂₆ - C -

methyl, ethyl or C ₁₄ -C ₂₂ hydrocarbon radicals,

- the hydrogen atom; R ₂₅ is chosen from:

O

II

the radical R ₂₈ - C -

- the hydrogen atom;

R ₂₄ , R ₂₆ and R ₂₈ , which are identical or different, are chosen from linear or branched, saturated or unsaturated C ₁₃ -C ₁₇ hydrocarbon radicals, and preferably from alkyl and alkenyl radicals,

C ₁₃ -C ₁₇ , linear or branched, saturated or unsaturated.

Advantageously, the hydrocarbon radicals are linear.

There may be mentioned, for example, the compounds of formula (IV) such as the salts (especially chloride or methylsulfate) of diacyloxyethyl-dimethylammonium, of diacyloxyethyl-hydroxyethyl-methylammonium, of monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxy- ethyl-methylammonium, monoacyloxyethyl-hydroxyethyl-dimethylammonium and mixtures thereof. The acyl radicals preferably have from 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm oil or sunflower oil. When the compound contains more than one acyl radical, the latter may be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine optionally oxyalkylenated on fatty acids or mixtures of fatty acids of plant or animal origin, or by transesterification. of their methyl esters. This esterification is followed by quaternization using an alkylating agent such as an alkyl halide (preferably methyl or ethyl), a dialkyl sulphate (preferably methyl or ethyl), the methyl methanesulfonate, methyl para-toluenesulfonate, glycol or glycerol chlorohydrin.

Such compounds are for example marketed under the names DEHYQUART ^® by the company Henkel, Stepanquat® ^® by the company Stepan, Noxamium ^® by CECA Rewoquat ^® WE 18 by Rewo-Witco.

The composition according to the invention may contain, for example, a mixture of quaternary ammonium mono-, di- and triester salts with a majority by weight of diester salts.

As a mixture of ammonium salts, it is possible to use, for example, the mixture containing 15 to 30% by weight of acyloxyethyl-dihydroxyethyl-methylammonium methylsulfate, 45 to 60% of diacyloxyethyl-hydroxyethyl-methylammonium methylsulfate and 15 to 30% of triacyloxyethylmethylammonium methylsulfate, the acyl radicals having from 14 to 18 carbon atoms and coming from partially hydrogenated palm oil.

It is also possible to use the ammonium salts containing at least one ester function described in US-A-4874554 and US-A-4137180. The nonionic surfactants that can be used in the compositions of the present invention are compounds that are well known per se (see in particular in this connection "Handbook of Surfactants" by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp. 1 16- 178). They are chosen in particular from polyethoxylated, polypropoxylated or polyglycerolated fatty alcohols, polyethoxylated, polypropoxylated or polyglycerolated alpha-diols, polyethoxylated, polypropoxylated or polyglycerolated alkyl (C ₁ -2 ₀ ) phenols or polyethoxylated, polypropoxylated or polyglycerolated fatty acids, chain comprising, for example, from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups ranging in particular from 2 to 50 and the number of glycerol groups ranging in particular from 2 to 30.

It is also possible to mention the condensates of ethylene oxide and of propylene oxide on fatty alcohols; the polyethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, the polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1, 5 to 4, the esters of fatty acids and of ethoxylated sorbitan having from 2 to 30 ethylene oxide units, the fatty acid esters of sucrose, alkylpolyglycosides, vegetable oils, polyethoxylated derivatives _^ N- (C _6- 2 ₄₎ glucamine, oxides amines such as oxides of (C _10-14) amines or oxides of N (acyl C ₁₀ _ ₁₄₎ - aminopropylmorpholine. The amphoteric or zwitterionic surfactants that can be used in the compositions of the present invention comprise, for example, secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms and containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may also be alkyl (C ₈ _ 2o) alkylbetaines, sulphobetaines, (C ₈ 2 ₀₎ amido (C _6- ₈₎ betaines or (C ₈ ₀ _2) amido (alkyl C ₆ _ ₈₎ sulphobetaines. Among the amine derivatives include the products sold under the name Miranol ^®, as described in US patents 2,528,378 and US 2,781,354 and classified in the CTFA dictionary, ^3rd edition, 1982, under the names Amphocarboxy-glycinate and Amphocarboxypropionate of respective structures (1) and (2):

Ra-CONHCH ₂ CH ₂ -N (Rb) (Rc) (CH ₂ COO ^") (1) wherein:

R _a represents an alkyl group derived from an R ₈ -COOH acid present in the hydrolysed coconut oil, a heptyl, nonyl or undecyl group,

Rb represents a beta-hydroxyethyl group, and R ₀ represents a carboxymethyl group; and R _a '-CONHCH ₂ CH ₂ -N (B) (B') (2) wherein: B represents -CH ₂ CH ₂ OX ', B' represents - (CH ₂ ) _Z -Y ', with z = 1 or 2,

X 'represents the group -CH ₂ CH ₂ -COOH or a hydrogen atom,

Y 'represents -COOH or the group -CH ₂ -CHOH-SO ₃ H, R _a ' represents an alkyl group of an R _a '-COOH acid present in coconut oil or in hydrolysed linseed oil, an alkyl group, in particular C ₁₇ and its iso form, an unsaturated C _{17 group} . These compounds are classified in the CTFA dictionary, ^5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate caprylamphodiacetate disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate disodium capryloamphodipropionate, disodium lauroamphodipropionic acid, cocoamphodipropionic acid. Examples include the cocoamphodiacetate sold by Rhodia under the trade name Miranol ^® C2M concentrate.

The compositions according to the invention may also comprise at least one silicone or a silicone derivative, in soluble, dispersed or micro-dispersed form. The silicones or silicone derivatives are preferably present in an amount of less than 10% by weight, preferably ranging from 0.01 to 8%, and still more preferably from 0.1 to 5% by weight relative to the total weight of the composition.

By way of example, mention may be made especially of silicone oils, such as, for example, linear or cyclic polydimethylsiloxanes.

The compositions according to the invention may also contain at least one additional fixing polymer, different from the copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s), to reinforce the holding effect. Such an additional fixing polymer may be of anionic, cationic, nonionic or amphoteric, and preferably anionic, nonionic or amphoteric nature.

The anionic fixing polymers that may be used in the compositions according to the invention are polymers containing groups derived from carboxylic, sulfonic or phosphoric acid and have a number-average molecular mass of between about 500 and 5,000,000.

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

(V) in which n is an integer from 0 to 10, A ₁ denotes a methylene group, optionally linked to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1, via a heteroatom such as oxygen or sulfur, R ₇ denotes a hydrogen atom, a phenyl or benzyl group, R ₈ denotes a hydrogen atom, a lower alkyl or carboxyl group, R 9 denotes a hydrogen atom, a lower alkyl group, a -CH ₂ -COOH group, phenyl or benzyl group. In the abovementioned formula, a lower alkyl group preferably denotes a group having 1 to 4 carbon atoms and in particular the methyl and ethyl groups.

The preferred anionic fixing polymers with carboxylic groups according to the invention are: A) copolymers of acrylic acid and acrylamide; .

B) copolymers of acrylic or methacrylic acid with a monoethylenic monomer chosen from ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted onto a polyalkylene glycol such as polyethylene glycol, and optionally crosslinked. Such polymers are described in particular in French Patent No. 1,222,944 and German Application No. 2,330,956, copolymers of this type comprising in their chain an acrylamide unit optionally N-alkylated and / or hydroxyalkylated such as described in particular in the Luxemburg patent applications Nos ^. 75370 and 75371. Mention may also be made of copolymers of acrylic acid and of C ₁ -C ₄ alkyl methacrylate and terpolymers of vinylpyrrolidone, acrylic acid and alkyl methacrylate. C ₁ -C _20, for example lauryl methacrylate, such as that marketed by the company ISP under the name Acrylidone LM ^® and methacrylic acid terpolymers / ethyl acrylate / butyl acrylate terpolymers such as the product sold under the name Luvimer ^® 100 P by BASF. C) Copolymers derived from crotonic acid, such as those comprising in their chain vinyl acetate or propionate units, and optionally other monomers such as allyl or methallyl esters, vinyl ethers or vinyl esters of a saturated carboxylic acid , linear or branched, long hydrocarbon chain, such as those comprising at least 5 carbon atoms, these polymers may optionally be grafted and crosslinked, or another vinyl ester monomer, allyl or methallylique a carboxylic acid α- or β- cyclic. Such polymers are described, inter alia, in French Patents ^Nos 1 222

944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. A commercial product in this class is the 28-29-30 resin marketed by National Starch.

D) copolymers derived from monounsaturated C ₄ -C ₈ carboxylic acids or anhydrides chosen from:

copolymers comprising (i) one or more maleic, fumaric and itaconic acids or anhydrides and (ii) at least one monomer chosen from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. Such polymers are described in particular in US Patents ^Nos 2,047,398, 2,723,248, January 13 2102, GB Patent No. 839 805. Commercial products include those sold under the Gantrez ^® AN or ES by denominations the ISP company.

copolymers comprising (i) one or more maleic, citraconic and itaconic anhydride units and (ii) one or more monomers chosen from allylic or methallyl esters optionally containing one or more acrylamide, methacrylamide, α-olefin or acrylic or methacrylic ester groups; acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. These polymers are for example described in French Patent Nos ^. 2,350,384 and 2,357,241 of the Applicant.

E) Polyacrylamides having carboxylate groups. The polymers comprising the sulphonic groups are polymers comprising vinylsulphonic, styrene-sulphonic, naphthalenesulphonic or acrylamido-alkylsulphonic units.

These polymers may especially be chosen from:

salts of polyvinylsulphonic acid having a molecular mass of between about 1,000 and 100,000, as well as copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and their esters, as well as acrylamide or its derivatives, vinyl ethers; and vinylpyrrolidone.

- salts of polystyrene sulfonic acid such as the sodium salts are sold under the name Flexan ^® 130 by

National Starch. These compounds are described in patent FR 2 198 719.

polyacrylamidesulfonic acid salts such as those mentioned in US Pat. No. 4,128,631, and more particularly polyacrylamidoethylpropanesulphonic acid.

According to the invention, among the anionic fixing polymers mentioned above, are preferred acrylic acid copolymers such as the acrylic acid terpolymers / ethyl acrylate / N-tert-butylacrylamide sold 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 crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold in particular under the name Resin 28-29-30 by the method NATIONAL STARCH, polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as methylvinylether / anhydride copolymers monoesterified maleic compounds sold, for example, under the name GANTREZ ^® by the company ISP, 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 BASF and vinyl acetate / crotonic acid copolymers and vinyl acetate / crotonic acid copolymers grafted with polyethylene glycol sold under the name ARISTOFLEX ^® A by BASF.

The anionic fixing polymers mentioned above, most particularly preferred are chosen from the methyl vinyl ether / monoesterified maleic anhydride sold under the name Gantrez ^® ES 425 by the company ISP, the acrylic acid terpolymers / ethyl acrylate / N-tert-butylacrylamide sold under the name Ultrahold ^® STRONG by the company BASF, the copolymers of methacrylic acid and of methyl methacrylate sold under the name Eudragit ^® L by the company Rohm Pharma, the vinyl acetate / vinyl tert-butylbenzoate / crotonic acid and the terpolymers crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, the copolymers of methacrylic acid and of ethyl acrylate sold under the name Luvimer ^® MAEX or MAE by BASF, terpolymers vinylpyrrolidone / acrylic acid / methacrylate lauryl sold under the name ACRYLIDONE ^® LM by ISP. The amphoteric fixing polymers that may be used in accordance with the invention may be chosen from polymers comprising units B and C statistically distributed in the polymer chain, where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit derived from an acidic monomer having one or more carboxylic or sulfonic groups, or B and C may denote groups derived from zwitterionic monomers of carboxybetaines or sulfobetaines;

B and C may also designate a cationic polymer chain comprising primary, secondary amine groups, tertiary or quaternary, wherein at least one of the amine groups carries a carboxylic or sulfonic group connected through a hydrocarbon group, or B and C are part of a chain of an ethylene-based polymer. α, β-dicarboxylic acid in which one of the carboxylic 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, which are more particularly preferred, are chosen from the following polymers:

(1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, alpha-chloro acrylic acid, and of a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as more particularly dialkylaminoalkylmethacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US Pat. No. 3,836,537. (2) Polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom by a alkyl group, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as primary, secondary, tertiary and quaternary amine substituted esters of acrylic and methacrylic acids, and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are those compounds whose alkyl groups contain 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 and fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.

Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.

The copolymers whose CTFA name (4th Ed., 1991) is

Octylacrylamide / acrylates / butylaminoethyl-methacrylate copolymer such as the products sold under the name or Lovocryl AMPHOMER® ^® ^® 47 by the company National Starch.

(3) polyamino amides crosslinked and acylated partially or totally derived from poyaminoamides of general formula:

- ^ CO- R ₁ - co-z-3- _(VI)

wherein R ₁₀ represents a divalent group derived from a saturated dicarboxylic acid, an ethylenically double-bonded mono or dicarboxylic aliphatic acid, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or a group derived from the addition of any of said acids with a bis-primary or bis-secondary amine, and Z denotes a group derived from a bis-primary, mono- or bis-secondary polyalkylene polyamine and preferably represents: a) in the proportions of 60 to 100 mol%, the group

where x = 2 and p = 2 or 3, or x = 3 and p = 2 this group derived from diethylene triamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol%, the group (VIIa) above, in which x = 2 and p = 1 and which is derived from ethylenediamine, or the group derived from piperazine:

c) in the proportions of 0 to 20 mol%, the -NH- (CHi) ₆ -NH- group derived from hexamethylenediamine, these polyaminoamides being crosslinked by addition reaction of a bifunctional crosslinking agent chosen from epihalohydrins; , diepoxides, dianhydrides, bis-unsaturated derivatives, by means of 0.025 to 0.35 mole of crosslinking agent per amine group of the polyaminoamide, and acylated by the action of acrylic acid, chloroacetic acid or an alkane -sultone or their salts.

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

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

(4) polymers having zwitterionic units of formula:

in which R ₁₁ denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer of 1 to 3, R ₁₂ and R ₁₃ represent a hydrogen atom, a methyl group, ethyl or propyl, R ₁₄ and R ₁₅ represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R ₁₄ and R ₁₅ does not exceed 10.

Polymers comprising such units may also include units derived from non-zwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.

By way of example, mention may be made of methyl methacrylate / dimethylcarboxymethylammonioethyl methacrylate copolymers.

(5) polymers derived from chitosan having monomeric units corresponding to the following formulas:

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), R ₁₆ represents a group of formula:

R 18 R "Λ, 19

^X 17 C- (O) -C

in which if q = 0, R ₁₇ , R ₁₈ and R _{1, which are} identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or several nitrogen atoms and / or optionally substituted by one or more groups amine, hydroxyl, carboxyl, alkylthio, sulfonic acid, an alkylthio radical whose alkyl group carries an amino residue, at least one of the groups R ₁₇ , R ₁₈ and R 1 being in this case a hydrogen atom; or if q = 1, R ₁₇ , R ₁₈ and R 4 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(6) The polymers corresponding to the general formula (IX) are, for example, described in French Patent 1,400,366:

in which R ₂₀ represents a hydrogen atom, a CH ₃ O, CH ₃ CH ₂ O, phenyl group, R ₂₁ denotes a hydrogen atom or a lower alkyl group such as methyl, ethyl, R ₂₂ denotes a hydrogen atom, hydrogen or a C ₁ -C ₆ lower alkyl group such as methyl, ethyl, R ₂₃ denotes a C ₁ -C ₆ lower alkyl group such as methyl, ethyl or a group corresponding to the formula: -R ₂ 4- N (R ₂₂ ) ₂ , R ₂₄ representing a group -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH (CH ₃ ) -, R ₂₂ having the meanings mentioned above above.

(7) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl-chitosan or N-carboxybutylchitosan.

(8) Amphoteric polymers of the -DXDX type chosen from: a) the 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- (X) where D denotes a group

and X denotes the symbol E or E ', E or E', which may be the same or different, denotes a divalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the unsubstituted or substituted backbone. hydroxyl groups and may further comprise oxygen, nitrogen, sulfur, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide groups, alcohol, ester and / or urethane. b) polymers of formula:

-D-X-D-X- (X ') where D denotes a group

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

(9) (C ₁ -C ₅ ) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N ₅ N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with an N, N-dialkylaminoalkanol. These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam.

Among the amphoteric fixing polymers mentioned above, which are the most particularly preferred according to the invention, mention will be made of those of the family

(3) such as 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 copolymers of methyl methacrylate / dimethyl-carboxyméthylammonio- methyl methacrylate.

The nonionic fixing polymers that can be used according to the present invention are chosen, for example, from: polyalkyloxazolines;

homopolymers of vinyl acetate;

copolymers of vinyl acetate and of acrylic ester;

copolymers of vinyl acetate and of ethylene;

copolymers of vinyl acetate and of maleic ester, for example of dibutyl maleate;

- acrylic ester copolymers such as, for example, copolymers of alkyl methacrylates and alkyl acrylates such as the products sold by the company Rohm & Haas under the names Primal AC-261 K ^® and EUDRAGIT ^® NE 30 D, by BASF under the name 8845, by Hoechst under the name APPRETAN ^® 9212;

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

homopolymers of styrene;

- copolymers of styrene and of alkyl (meth) acrylate such as Mowilith LDM products ^® 691 1 Mowilith ^® DM 61 1 and

MOWILITH ^® LDM 6070 offered by the company HOECHST, RHODOPAS ^® SD 215 and RHODOPAS ^® DS 910 products offered by RHODIA CHIMIE;

copolymers of styrene, of alkyl methacrylate and of alkyl acrylate;

copolymers of styrene and butadiene;

copolymers of styrene, butadiene and vinylpyridine;

copolymers of alkyl acrylate and urethane;

polyamides, homopolymers and copolymers of vinyllactam.

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

According to the present invention, the nonionic setting polymers with vinyllactam motifs can be those described in US Pat. Nos. 3,770,683, 3,929,735, 4,521,504, 5,156,762 and 5,506,315. WO 94/12148, WO 96/06592 and WO 96/10593. They can be in powder form or in the form of solution or suspension.

Homopolymers or copolymers with vinyllactam units comprise units of formula (XI):

- CH ₂ -CH -

NC- ^V (CH ₂ ) _n

° ^(XI) wherein n is independently 3, 4 or 5.

The number-average molecular weight of the polymers with vinyllactam units is generally greater than about 5,000, preferably between about 10,000 and 1,000,000, more preferably between about 10,000 and 100,000. These fixing polymers include polyvinylpyrrolidones such as those marketed under the name Luviskol ^® K30 by BASF; polyvinylcaprolactams such as those sold under the name Luviskol ^® Plus by BASF; poly (vinylpyrrolidone / vinyl acetate) such as those sold under the name PVPVA® S630L ^® by ISP, Luviskol ^® VA 73, VA 64, VA 55, VA 37 and VA 28 by the company BASF; terpolymers and poly (vinylpyrrolidone / vinyl acetate / vinyl propionate) such as, for example, those marketed under the name Luviskol ^® VAP 343 by BASF.

The additional fixing polymers may also be chosen from optionally silicone polyurethanes. As fixing polymers of the polyurethane type, mention may be made of the Luviset Pur and Luviset Si Pur polymers proposed by BASF.

These additional fixing polymers may also be chosen from silicone grafted with a hydrocarbon backbone and silicone or silicone backbone grafts and hydrocarbon grafts such as the products VS 70 and VS 80 proposed by the company 3M. They may also be chosen from polyesters containing sulphonic groups, such as the AQ resins (AQ55, AQ38, and AQ48) proposed by EASTMAN CHEMICAL.

The composition according to the invention may then contain at least 0.01% by weight of additional fixing polymer, relative to the total weight of the composition. More preferably, the composition according to the invention contains from 0.01 to 20% by weight of additional fixing polymer, more preferably from 0.05 to 15% by weight, even more preferably from 0.1 to 10% by weight. , relative to the total weight of the composition. The compositions in accordance with the invention may be packaged in a jar, in a tube, in a pump bottle or in an aerosol device that is usual in cosmetics. The compositions according to the invention may, when they are intended to be packaged in an aerosol-type device, contain at least one propellant, such as a propellant gas.

The propellant can then be chosen for example from dimethyl ether, C ₃ to C ₅ alkanes, halogenated hydrocarbons, and mixtures thereof.

The compositions according to the invention may further contain at least one additive chosen from pearlescent agents; opacifying agents; plasticizers; solar filters; the perfumes ; dyes; conservatives ; pH stabilizers; acids; the basics ; polyols (for example glycols); mineral charges; glitter, and any other additive conventionally used in the cosmetic field.

Those skilled in the art will take care to choose the possible additives and their amounts so that they do not adversely affect the properties of the compositions of the present invention.

These additives are present in the composition according to the invention in an amount ranging from 0 to 50% by weight relative to the total weight of the composition. The compositions according to the invention may be in the form of more or less thickened liquids, gels, creams, pastes or foams.

Preferably, they are in the form of gels.

The composition according to the invention may advantageously be used as a hair product. It may in particular be used as a styling product, for example as a styling gel.

According to a preferred embodiment, it is used as a non-rinsed styling product, that is to say for shaping and / or maintaining the hairstyle not followed by rinsing. The present invention also relates to a cosmetic hair treatment method, for example a hair care method, or a method of shaping and / or holding the hairstyle, which consists in applying to the hair an effective amount of a composition as described above, then to perform a possible rinsing after a possible exposure time.

Preferably, the composition according to the invention is not rinsed. The following example is given by way of illustration of the present invention.

EXAMPLE

In the following example, all amounts are given in percent by weight of active ingredient (MA) based on the total weight of the composition, unless otherwise indicated.

This example illustrates the formulation of a styling gel according to the invention. Such a gel has been prepared from the ingredients indicated in the table below:

(1) marketed under the name ACUDYNE DHR by the company ROHM & HAAS.

(2) marketed under the name CARBOPOL ULTREZ-10 by the company NOVEON.

Results obtained:

The performance of the styling gel composition described above has been evaluated by professionals on panels of models.

This composition provides a very good fixation of the hair, both flexible and durable. In particular, the fixing polymer film is very friable.

In addition, this composition has been found to provide the hair with excellent cosmetic properties. In particular, after disentangling, the hair is not dry, and is particularly soft.

Claims

Cosmetic composition comprising, in a cosmetically acceptable medium, at least one alkylene glycol or polyalkylene glycol ether, at least one copolymer of acrylate (s) or of methacrylate (s) and of acrylate hydroxy ester (s) ) or methacrylate (s), and at least one natural or synthetic thickening polymer, the weight ratio between the amount of copolymer (s) of acrylate (s) or methacrylate (s) and acrylate hydroxyester (s) ) or methacrylate (s) on the one hand and the amount of ether (s) alkylene glycol or polyalkylene glycol, on the other hand, between 0, 1 and 15.

2. Composition according to claim 1, characterized in that the copolymer of acrylate (s) or methacrylate (s) and hydroxyester acrylate (s) or methacrylate (s) is obtained by copolymerization of at least two monomers:

at least one first monomer chosen from acrylic acid, methacrylic acid, C 1 to C 4 alkyl acrylates and methacrylates, and

at least one second monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates.

3. Composition according to the preceding claim, characterized in that said copolymer is obtained by copolymerization of at least three monomers:

at least one first monomer chosen from acrylic acid and methacrylic acid,

4. Composition according to the preceding claim, characterized in that said second monomer comprises at least one C 1 or C 2 alkyl acrylate or methacrylate.

5. Composition according to any one of claims 3 and 4, characterized in that said third monomer is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, and mixtures of these compounds.

6. Composition according to any one of the preceding claims, characterized in that it comprises a mixture of at least two copolymers of acrylate (s) or methacrylate (s) and acrylate hydroxyester (s) or of methacrylate (s).

7. Composition according to the preceding claim, characterized in that it comprises a mixture of two copolymers of acrylate (s) or methacrylate (s) and hydroxyester acrylate (s) or methacrylate (s), each copolymers being obtained by copolymerization of at least three monomers:

at least one first monomer chosen from acrylic acid and methacrylic acid,

8. Composition according to claim 6, characterized in that it comprises a mixture of two copolymers of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s), comprising a first copolymer obtained by copolymerization of at least three monomers: at least one first monomer chosen from acrylic acid and methacrylic acid, at least one second monomer chosen from C1 to C4 alkyl acrylates and methacrylates, and at least one third monomer selected from C1 to C4 hydroxyalkyl acrylates and methacrylates; and a second copolymer obtained by copolymerization of at least two monomers: at least one first monomer chosen from C1 to C4 alkyl acrylates and methacrylates, and at least one second monomer selected from C1 to C4 hydroxyalkyl acrylates and methacrylates; said second copolymer does not contain monomers consisting of unsaturated carboxylic acids.

9. Composition according to any one of claims 6 to

8, characterized in that the two copolymers of the mixture have different glass transition temperatures.

10. Composition according to the preceding claim, characterized in that the difference in glass transition temperature between the two copolymers is greater than or equal to 10 ° C, more preferably greater than or equal to 20 ° C, and even more preferably greater than or equal to at 30 ° C.

1. Composition according to any one of the preceding claims, characterized in that it contains at least 0.01% by weight of copolymer (s) of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s), relative to the total weight of the composition.

12. Composition according to the preceding claim, characterized in that it contains from 0.01 to 20% by weight of copolymer (s) acrylate (s) or methacrylate (s) and hydroxyester acrylate (s) ) or methacrylate (s), more preferably from 0.1 to 10% by weight, more preferably from 0.5 to 8% by weight, relative to the total weight of the composition.

13. Composition according to any one of the preceding claims, characterized in that it comprises at least one alkylene glycol or polyalkylene glycol ether of formula R ₁ - (OR) _n -OR ₂ , with R ₁ denoting a radical alkyl comprising 1 to 8 carbon atoms, R denoting ethylene or propylene, R ₂ denoting hydrogen or an alkyl radical, identical to or different from R ₁ , comprising from 1 to 8 carbon atoms, and n designating a integer from 1 to 10,000.

14. Composition according to the preceding claim, characterized in that R ₁ denotes an alkyl radical comprising from 1 to 4 carbon atoms. carbon and R ₂ denotes hydrogen or an alkyl radical, identical to or different from R ₁ , comprising from 1 to 4 carbon atoms.

15. Composition according to any one of claims 13 and 14, characterized in that n ranges from 1 to 1000.

16. Composition according to the preceding claim, characterized in that n ranges from 1 to 500, and preferably from 2 to 500.

17. Composition according to any one of claims 13 to 16, characterized in that it comprises a mono or diether of alkyl (s) C 1 to C 8 and propylene glycol or polypropylene glycol having from 2 to 500 and preferably from 2 to 250 propylene glycol units.

18. Composition according to the preceding claim, characterized in that it contains a mono or diether of alkyl (s) C1 to C8 and polypropylene glycol having from 2 to 100 propylene glycol units, and more preferably from 2 to 50 propylene glycol units.

19. Composition according to any one of the preceding claims, characterized in that it contains at least 0.01% by weight of ether (s) of alkylene glycol or polyalkylene glycol, relative to the total weight of the composition. .

20. Composition according to the preceding claim, characterized in that it contains from 0.01 to 15% by weight of ether (s) alkylene glycol or polyalkylene glycol, preferably from 0.05 to 10% by weight. weight, more preferably 0, 1 to 8% by weight relative to the total weight of the composition.

21. Composition according to any one of the preceding claims, characterized in that the weight ratio between the amount of copolymer (s) acrylate (s) or methacrylate (s) and acrylate hydroxyester (s) or of methacrylate (s) on the one hand and the amount of ether (s) alkylene glycol or polyalkylene glycol, on the other hand, is between 1 and 10.

22. Composition according to any one of the preceding claims, characterized in that the thickening polymer is chosen from anionic polymeric thickeners, amphoteric, zwitterionic, nonionic or cationic, associative or not.

23. Composition according to the preceding claim, characterized in that the thickening polymer is selected from homopolymers of acrylic acid, crosslinked or uncrosslinked.

24. Composition according to any one of the preceding claims, characterized in that the cosmetically acceptable medium comprises water and / or at least one cosmetically acceptable solvent chosen from C ₁ -C ₄ lower alcohols; polyols; polyol ethers other than (poly) alkylene glycol ethers, C ₅ -C ₁₀ alkanes; C _{3 -4} ketones; C ₁ -C ₄ alkyl acetates; dimethoxyethane, diethoxyethane; and their mixtures.

25. Composition according to any one of the preceding claims, characterized in that it also contains at least one fatty substance, chosen from vegetable oils, animal oils, mineral oils, natural or synthetic oils, fatty alcohols, waxes and their mixtures.

26. Composition according to the preceding claim, characterized in that the fatty substances are present in an amount ranging from 0.1 to 30% by weight, preferably from 1 to 20% by weight, relative to the total weight of the composition.

27. Composition according to any one of the preceding claims, characterized in that it also contains at least one surfactant, selected from cationic surfactants, anionic surfactants, nonionic surfactants other than ethers of (poly) alkylene glycol, amphoteric or zwitterionic surfactants.

28. Composition according to the preceding claim, characterized in that it contains at least 0.01% by weight of surfactant (s), relative to the total weight of the composition.

29. Composition according to the preceding claim, characterized in that it contains from 0.01 to 20% by weight of surfactant (s), preferably from 0.05 to 4% by weight, relative to the total weight of the composition. .

30. Composition according to any one of the preceding claims, characterized in that it further comprises at least a silicone or a silicone derivative, in soluble, dispersed or micro-dispersed form.

31. Composition according to any one of the preceding claims, characterized in that it comprises at least one additional fixing polymer other than the copolymer of acrylate (s) or of methacrylate (s) and of acrylate hydroxyester (s). or of methacrylate (s), of anionic, cationic, nonionic or amphoteric nature.

32. Composition according to the preceding claim, characterized in that it contains at least 0.01% by weight of additional fixing polymer, relative to the total weight of the composition.

33. Composition according to the preceding claim, characterized in that it contains from 0.01 to 20% by weight of additional fixing polymer, preferably from 0.05 to 15% by weight, more preferably 0.1 to 10% by weight. weight relative to the total weight of the composition.

34. Composition according to any one of the preceding claims, characterized in that it contains at least 0.01% by weight of thickening polymer, relative to the total weight of the composition.

35. Composition according to the preceding claim, characterized in that it contains from 0.1 to 10% by weight of thickening polymer, relative to the total weight of the composition.

36. Composition according to any one of the preceding claims, characterized in that it further contains at least one additive chosen from pearlescent agents; opacifying agents; plasticizers; solar filters; the perfumes ; dyes; conservatives ; pH stabilizers; acids; the basics ; polyols; mineral charges; glitter, and any other additive conventionally used in the cosmetic field.

37. Composition according to any one of the preceding claims, characterized in that it is in the form of a more or less thickened liquid, gel, cream, paste or foam.

38. Composition according to the preceding claim, characterized in that it is in gel form.

39. A method of cosmetic treatment of hair, characterized in that it consists in applying to the hair an effective amount of a composition according to any one of the preceding claims, then to perform a possible rinsing after a possible exposure time.

40. Process according to the preceding claim, characterized in that the composition is not rinsed.

41. Use of a composition according to any one of claims 1 to 38 as a hair product.

42. Use of a composition according to any one of claims 1 to 38, for shaping and / or maintaining the hairstyle.