WO2010076490A2

WO2010076490A2 - Cosmetic composition containing a polyamine having diazirine groups, and use thereof for photo-grafting a non-saccharide polymer other than polyamine polymers

Info

Publication number: WO2010076490A2
Application number: PCT/FR2009/052550
Authority: WO
Inventors: Gabin Vic
Original assignee: L' Oreal
Priority date: 2008-12-15
Filing date: 2009-12-15
Publication date: 2010-07-08
Also published as: FR2939657B1; WO2010076490A3; FR2939657A1

Abstract

The invention relates to a cosmetic composition containing, in a cosmetically acceptable medium: a) at least one photo-activated compound obtained from a polyamine polymer, containing at least two -NH- and/or -N- amino units to which at least two photo-activated diazirine groups are covalently bonded; and b) one or more non-saccharide polymers other than the a) compounds.

Description

Cosmetic composition comprising a polyamine having diazirine groups and use for photo-grafting of a non-saccharide polymer other than polyamine polymers

The invention relates to a cosmetic composition comprising a photoactivatable compound derived from a polyamine polymer on which are covalently bound at least two photoactivatable diazirine groups, and one or more non-saccharide polymers different from the polyamine polymers mentioned above. above. The invention also relates to the use of this composition for fixing said at least one non-saccharide polymer on keratin materials.

The products used to fix cosmetic agents, in particular polymers, on keratin materials generally have the disadvantage of being eliminated very quickly during washing or during other treatments.

To overcome this disadvantage, it is generally sought to graft the surface polymers on keratin materials.

The grafting of surface polymers on keratin materials makes it possible to obtain hair styling effects that are durable, soft or glossy depending on the nature of the polymer, without degrading the hair fiber.

The grafting of surface polymers on keratin materials is particularly difficult to achieve. Indeed, it must be done under mild conditions applicable in cosmetics, so as not to degrade the hair fiber.

Document FR 2 839 446 discloses a photoactivatable cosmetic composition comprising a diazirine and a cosmetic active covalently bonded to form a diazirine-active compound. This photoactivatable composition is used to fix cosmetic active agents on keratin materials, using the diazirine compound which provides the bond between the cosmetic agent and the keratin materials.

FR 2 831 534 discloses a photoactivatable compound comprising a carrier molecule on which at least two photoactivatable functional groups are covalently bound. By means of the photoactivatable compound described in this document, the covalent grafting on the keratin material of the cosmetic active agents present in the medium is provided.

Document WO 2006/018729 discloses polyamine polymers bearing photoactivatable diazirine groups that can be photo-grafted onto the surface of a substrate, for cosmetic use. Documents EP 1 321 125, EP 1 458 335 and EP 1 458 336 disclose cosmetic compositions, in particular capillary compositions, comprising at least one polymer with a non-silicone skeleton, comprising non-photoactivatable reactive chemical functions that can be chemically grafted. on the hair so as to form a rigid sheathing, soft or tacky on the hair. In the same way, document FR 2 833 487 discloses cosmetic compositions comprising at least two polymers having complementary non-photoactivatable chemical functions capable of reacting with one another after application to the hair in order to form a permanent cladding on the hair. The polymers used in said compositions are very specific polymers, and the results obtained are not yet completely satisfactory.

There is therefore a need for a cosmetic composition which makes it possible to fix surface polymers on the keratin material, whatever the nature of these polymers, in a simple, safe and durable manner, without degrading the keratin material, this fixation being able to to be located.

The subject of the invention is therefore a cosmetic composition comprising, in a cosmetically acceptable medium, a) one or more photoactivatable compounds obtained from polyamine polymers containing at least two amino units -NH- and / or ^~ N- s _U covalently bound at least two photoactivatable diazirine groups, and b) one or more non-saccharide polymers different from the compounds a).

The polyamine polymer (s) that can be used to obtain the photoactivatable compound (s) of the composition according to the invention may be linear, branched, hyperbranched or dendrimeric. Hyperbranched polymers are molecular constructs having a branched structure, usually around a heart. Their structure is generally devoid of symmetry: the basic units or monomers used for the construction of hyperbranched polymer may be of different types and their distribution is irregular. The branches of the polymer may be of different natures and lengths. The number of basic units, or monomers, may be different depending on the different branches. While being asymmetric, hyperbranched polymers may have: an extremely branched structure, around a heart; successive layers or generations of ramifications; a layer of terminal chains.

The hyperbranched polymers are generally derived from the polycondensation of one or more ABx monomers, A and B being reactive groups capable of reacting together, where x is an integer greater than or equal to 2, but other methods of preparation can be envisaged. The hyperbranched polymers are characterized by their degree of polymerization DP = 1 -b, where b is the percentage of non-terminal functional groups of B which have not reacted with an A group. The condensation being non-systematic, contrary to the synthesis. dendrimers, the degree of polymerization is less than 100%. In the usual way, by the known synthetic methods, DP is between 15 and 90%.

It is also possible to react a terminal group T on the hyperbranched polymer to obtain a particular functionality at the end of chains. Several hyperbranched polymers can be associated with each other, by a covalent bond or another type of bond, through their terminal groups. Such polymers, called bridged polymers, come within the definition of hyperbranched polymers according to the present invention. Dendrimers are highly branched polymers and oligomers with a well-defined chemical structure, and are said to be "perfect" hyperbranched polymers.

Generally, the dendrimers comprise a core, a predetermined number of generations of branches, or spindles, and terminal groups. Generations of spindles consist of structural units, which are identical for the same generation of spindles and which may be identical or different for different generations of spindles. Generations of spindles extend radially in a geometric progression from the heart. The end groups of a nth generation dendrimer are the terminal functional groups of the Nth generation or terminal generation spindles.

The definition of dendrimers given above includes molecules with symmetrical branches. It also includes non-symmetric branching molecules, such as, for example, dendrimers whose spindles are lysine groups, in which the branching of a spindle generation on the former is done on the amines α and ε of lysine, which leads to a difference in the length of the spindles of the different branches.

Star-filled polymers, or "dense star polymers," starburst polymers, rod-shaped dendrimers, or "rod-shaped dendrimers," are included in the present definition of dendrimers. The molecules denoted arborais and molecules in cascade also fall within the definition of the dendrimers according to the present invention.

Several dendrimers can be associated with each other by a covalent bond or other type of bond through their terminal groups to give entities known as "bridged dendrimers", "dendrimer aggregates" or "bridged dendrimer". ". Such entities are included in the definition of the dendrimers according to the present invention.

Dendrimers may be in the form of a set of molecules of the same generation, called monodisperse sets; they can also be in the form of sets of different generations, called polydisperses. The definition of the dendrimers according to the present invention includes monodisperse as well as polydisperse sets of dendrimers.

The polyamine polymer (s) that may be used to form the photoactivatable compound (s) of the composition according to the invention may be chosen from:

the polyalkyleneimines, preferably the poly (C ₂ -C ₅ alkyleneimines), polymers grafted with a (C ₂ -C ₅ ) alkyleneimine, preferably polymers grafted with ethyleneimine, better polyamidoamines, crosslinked or not, grafted with ethyleneimine,

copolymers based on aminoalkyl (C ₁ -C ₄ ) (meth) acrylate, preferably based on aminoethyl (meth) acrylate,

polyallylamines,

polycondensates of at least one compound chosen from piperazine, 1- (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, 1-alkyl (dC ₂₅ ) piperazine, 1, 4-di (C ₁ -C 5 alkyl) piperazine, 1 - (2-hydroxy (C ₂ -C 25) alkyl) piperazine, imidazole, C ₁ -C ₅ alkylimidazole, or mixtures thereof, with at least one compound selected from C ₆ -C ₂₂ alkylene dihalide, epihalohydrin and / or C ₈ -C ₂₂ bisepoxide,

the polymers containing in their structure at least 2 successive units of the same basic amino acid, the expression at least 2 units includes in particular at least 2, 3, 4, 5, 6, 7, 8, 9 and 10 units, polyamidoamines,

dendrimers containing primary amines in the terminal position.

Among the polyalkyleneimines that may be used in the composition according to the invention, mention may be made of polyethyleneimines and polypropyleneimines.

The polyethyleneimines (PEI) that can be used according to the invention generally have the following formula: - (CH ₂ -CH ₂ -NH) _n - where n is the average number of ethyleneimine units, n being between 5 and 10,000.

Homopolymers of ethyleneimine can be connected. In particular, PEI-7 (n = 7), PEI-15 (n = 15), PEI-30 (n = 30),

PEI-45 (n = 45), PEI-275 (n = 275), PEI-700 (n = 700), PEI-1000 (n = 1000), PEI-1400 (n = 1400), PEI-1500 (n = 1500), PEI-1750 (n = 1750), and PEI-2500 (n = 2500).

The polyethyleneimines are especially described in the documents: "KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY", 3rd edition, vol.20, 1982, p.214-216, and "Polyethyleneimine Prospective Application" HN Feigenbaum, Cosmetics & Toiletries, 108, 1993 , p.73.

The polyamine polymers that can be used to form the one or more photoactivatable compounds of the composition according to the invention can also be chosen from polymers grafted with a (C ₂ -C ₅ ) alkyleneimine, preferably polymers grafted with ethyleneimine, better polyamidoamines, crosslinked or not, grafted with ethyleneimine.

The polyamidoamines can be prepared from polyalkylene polyamines chosen from those having from 3 to 10 carbon atoms, for example diethylene triamine, triethylene tetramine, dipropylene triamine, tripropylene tetramine and di-hexa methylene. triamine, amino-propylethylene di-amine, bis-aminopropylethylene di-amine, and mixtures thereof, and from a monocarboxylic aliphatic acid.

As explained above, the polyamine polymer (s) may also be chosen from polycondensates of at least one compound selected from a) piperazine, 1 - (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, 1 - alkyl (CrC ₂ 5) piperazine, 1, 4-di (alkyl (C-ι-C ₂ 5)) piperazine, 1 - (2-hydroxy (alkyl (C ₂ - C ₂ 5) )) piperazine, imidazole, C 1 -C ₂₅ alkylimidazole, or mixtures thereof, with at least one compound selected from b) C ₆ -C ₂₂ alkylene dihalide, epihalohydrin and / or C ₈ -C bisepoxide ₂₂ . Advantageously, the constituent (s) of group a) and the constituent (s) of group b) are present in a molar ratio of between 1: 0.8 and 1: 1, 1.

A preferred polycondensate is, for example, polycondensate of piperazine and imidazole with epihalohydrin.

Such polycondensates that can be used in the composition according to the invention are described in particular in US Pat. No. 6,025,322.

The polyamine polymer (s) that may be used to form the photoactivatable compound (s) of the composition according to the invention may also be chosen from polymers containing in their structure at least 2 successive units of one and the same basic amino acid. The at least one basic amino acid is preferably chosen from ornithine, asparagine, glutamine, lysine and arginine.

Said polyamine polymers containing at least 2 successive units of the same basic amino acid that can be used in the composition according to the invention generally contain 2 to 10,000 basic amino acid units. Preferably, the polyamine polymer used to form the photoactivatable compound (s) is different from ovalbumin, albumin, keratin and collagen.

The polyamine polymer (s) constituting the photoactivatable compound (s) of the composition according to the invention may also be chosen from dendrimers containing terminal primary amines. By dendrimers containing terminal primary amines is meant polymeric compounds consisting of a core and generation of base units, monomers or spindles, on which a terminal group T bearing a primary amine function has been grafted. .

These include for example polyamidoamines dendrimers, such as those sold under the trade name STARBU RST ^® PAMAM by the company

DENDRITECH (ethylene diamine copolymers sequences and methyl acrylate), or those sold under the commercial reference ASTROMOLS ^® (DAB) by DSM. Preferably, the polyamines used to obtain the photoactivatable compounds of the invention are polyethyleneimines, polylysines and polyalkylamines.

In a particularly preferred manner, the polyamine polymer (s) forming the photoactivatable compound (s) of the composition according to the invention are chosen from: polyethyleneimines (PEI), polyallylamines and poly L-lysine.

As explained above, at least two photoactivatable diazirine groups are covalently bound to said polyamine polymer.

By photoactivatable diazirine groups is meant diazirine groups capable of generating reactive species (carbenes, nitrenes, radical species, for example) by simple exposure to radiation of one or more wavelengths of between 200 and 450 nm, preferably 300 and 450 nm and even more preferably 300 and 380 nm. This exposure can be achieved by means of solar simulators, UV lamps or by simple action of solar radiation. These reactive species have the property of being able to be inserted non-selectively in numerous chemical bonds such as C-H, N-H, O-H and C-C bonds.

C = C, S-H, S≡C, keratinous material.

Preferably, the diazirine groups covalently bonded to the polyamine polymer are obtained by grafting onto the polyamine polymer a diazirine of formula:

wherein Ri is selected from the group consisting of a hydrogen atom, an alkyl radical Ci-Ci ₀ linear or branched, an alkenyl C ₂ to Ci ₀ linear or branched alkynyl, _C2 to C10 linear or branched, CF ₃ , CCI ₃ , CBr ₃ , NR ' ₃ +, SR' ₂ +, SH ₂₊ , NH ₃ +, NO ₂ , SO ₂ R ', C≡N, COOH, F, Cl, Br, I , OR, COOR ', SO ₃ H, COR ¹ , SH, SR', OH, where R 'is a linear or branched C ₁ -C ₁₀ alkyl radical,

Z is a single covalent bond or a spacer group which is a linear, branched or cyclic carbon chain, saturated or unsaturated, in C ₁ -C ₁ 00, preferably C ₁ -C ₅₀ , which chain may be interrupted by heteroatoms such as as sulfur, oxygen, nitrogen, silicon or phosphorus and may also comprise one or more substituents such as hydroxyl groups, amines, thiols, carbamates, ethers, acids, esters, amides, cyano, ureido,

Y represents a function selected from the group formed by alcohols, amines, thiols, thiosulfates, carboxylic acids and its derivatives such as anhydrides, acid chlorides, esters, acetals and hemi-acetals, aminals and hemi-amines, ketones, aldehydes, alpha-hydroxyketones, epoxidized alpha-haloketones, lactones, thiolactones, azalactones, isocyanates, thiocyanates, imines, imides (succinimides, glutimides), imidoesters, aziridines, imidates, oxazine and oxazoline, oxazinium and oxazolinium, halogens (fluorine, chlorine, iodine, bromine), chlorotriazines, chloropyrimidines, chloroquinoxalines, chlorobenzotriazoles, sulfonyl halides (X = F, Cl, I or Br); SO ₂ X, siloxanes, silanols, silanes, pyridyldithio, N-hydroxysuccinimide esters, activated or unactivated vinyls, including acrylonitriles, acrylic and methacrylic esters, crotonic acids and esters, cinnamic acids and esters, styrenes, butadienes, vinyl ethers, vinyl ketone, maleic esters, maleimides, vinyl sulfones, hydrazines, phenyl glyoxals, epoxies, Ar represents an aromatic ring selected from the group consisting of:

in which R ₂ , R 3, R ₄ and R ₅ represent, independently of one another, radicals chosen from the group formed by a hydrogen atom, a linear or branched C ₁ -C ₁₀ alkyl radical, an alkenyl C ₂ to C ₁ 0 straight or branched alkynyl, C ₂ to C ₁ 0 straight or branched, CF _3, CCI _3, CBr _3, NR _'3 +, SR' ₂ +, SH ₂ +, NH ₃ +, NO ₂ , SO ₂ R ', ON, COOH, F, Cl, Br, I ₁ OR, COOR', SO ₃ H, COR ', SH, SR', OH, where R 'is an alkyl radical to C ₁ 0 straight or branched.

A particularly preferred diazirine for forming diazirine groups on the polyamine polymer is 3- (4-Oxiranylphenyl) -3-trifluoromethyl-3H-diazirine of the following formula:

A process for synthesizing the compound (2) is described in the application WO 2006/0191 16. Another particularly preferred diazirine for forming diazirine groups on the polyamine polymer is the compound of the following formula:

(5) The compound of formula (5) can be obtained by a method such as that described in Nassal M., J. Am. Chem. Soc., 1984, 106, 7540-7545.

A process for the synthesis of polyamines carrying diazirine groups obtained from compounds (2) or (5) is described in application WO 2006/0191 16.

The chemical reactions that are used to synthesize the photoactivatable compound present in the composition according to the invention depend on the Y groups and the complementary groups on the polyamine polymer, all the conventional chemical reactions that can be used. In a similar way, it is possible to protect the groups that one does not wish to see react. All conventional reactions of protection and de-protection of reactive functions can be used.

According to a first preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (10) comprising a unit of formula (3) and a unit of formula (A), and having a mean molecular mass of weight between 2,000 and 100,000:

Generally, the molar ratio of the unit of formula (3) to the unit of formula (A) is from 1: 50 to 1: 2.

According to a second preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (1 1) comprising a unit of formula (4), a unit of formula (B) and a unit of formula (B). '), and having a weight average molecular weight of between 2,000 and 150,000:

Generally, the molar ratio of the unit of formula (4) and units of formula (B) and (B ') is between 1: 50 and 1: 2.

According to a third preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (12) comprising a unit of formula (6), a unit of formula (C) and a unit of formula (C) , and having a weight average molecular weight of between 2,000 and 150,000:

Generally, the molar ratio of the unit of formula (6) and the unit of formula (C) and (C) is between 1: 50 and 1: 2.

According to a fourth preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (13) comprising a unit of formula (7) and a unit of formula (A), and having an average molecular weight of weight between 2,000 and 100,000:

Generally, the molar ratio of the unit of formula (7) to the unit of formula (A) is from 1: 50 to 1: 2.

According to a fifth preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (14) comprising a unit of formula (8), a unit of formula (B) and a unit of formula (B ') ), and having a weight average molecular weight of between 2,000 and 150,000:

Generally, the molar ratio of the unit of formula (8) and units of formulas (B) and (B ') is between 1: 50 and 1: 2.

According to a sixth preferred embodiment of the invention, the photoactivatable compound is a photoactivatable compound (15) comprising a unit of formula (9), a unit of formula (C) and a unit of formula (C) , and having a weight average molecular weight of between 2,000 and 150,000:

Generally, the molar ratio of the unit of formula (9) and units of formulas (C) and (C) is between 1: 50 and 1: 2.

Generally, the photoactivatable compound (s) represent (s) between 0.01% and 90% by weight of the total weight of the composition.

The photoactivatable compounds (10), (1 1) and (12) can be obtained by reacting the compound of formula (2) described above with a polyamine. If polyethyleneimine (PA) is used, the photoactivatable compound (10) is obtained. If polyallylamine hydrochloride (PB) is used, the photoactivatable compound (11) is obtained. If poly L-lysine hydrobromide (PC) is used, the photoactivatable compound (12) is obtained.

Polyethylene imine (PA), polyallylamine hydrochloride (PB), and poly L-lysine hydrobromide (PC) are commercial products available commercially. These products have at least one of the following repeating units.

Polyethylene imine

Polyallylamine hydrochloride

Poly L-lysine hydrobromide

The reaction between the compound of formula (2) and a polyamine can be carried out as follows. Generally, the epoxy groups, under heating, undergo a ring opening and generate 2-amino hydroxyl derivatives by a nucleophilic substitution reaction due to amines.

The photoactivatable compounds (10), (1 1) and (12) are produced by reacting each polyamine (PA), (PB) and (PC) and the compound of formula (2) in a solvent which is a mixture 1: 1 dimethylformaldehyde and water overnight at about 50 ⁰ C in the dark. In the case where the polyamine compounds (PB) and (PC) are used, it is preferable to carry out the reaction in the presence of bases so as to neutralize the hydrochloride or the hydrobromide. Once the reaction is complete, the desired photoactivatable compound can be prepared by distilling off the solvent, dissolving the compound produced once more in water, and separating by exclusion / diffusion chromatography. Elution of the photoactivatable compound can be confirmed by measuring the absorption of light at 254 nm and 360 nm.

The photoactivatable compounds (13), (14) and (15) can be obtained by reacting the compound of formula (5) with a polyamine. Generally, halogenated alkyl compounds and amines readily bind under heating in the presence of bases by a nucleophilic substitution reaction. For example, the photoactivatable compound (13) is produced by reacting the compound of formula (5) with polyamine (PA) in a solvent which is a 1: 1 mixture of dimethylformaldehyde and water overnight in the presence of bases, at a temperature of approximately 50 ⁰ C in the dark. The preparation can be made after distilling off the solvent, dissolving these compounds again in water, and separating them by exclusion / diffusion chromatography. Photoactivatable compounds (14) and (15) can also be obtained in a similar manner using polyamines (PB) or (PC) in place of polyamine (PA).

In the reaction scheme described below for the photoactivatable compound (13), a substituted phenyl group is attached to all amino groups, but in general in the polyamine compounds certain amino groups of the polyamine (PA) exist as free amino groups, i.e. as amino groups without attached substituted phenyl group.

The diazirine groups of the photoactivatable compound (s) present in the composition according to the invention make it possible to graft the photoactivatable compound (s) onto the keratin materials. Under the effect of irradiation at a wavelength of between 200 and 450 nm, or under the effect of exposure to natural light, the diazirine groups react with the compounds constituting the keratin materials.

According to a first embodiment of the invention, by means of the one or more photoactivatable compounds present in the cosmetic composition according to the invention, the covalent grafting on the keratinous material of the non-saccharide polymer or polymers different from the polyamine polymers present is ensured. in the composition. The grafting of the photoactivatable compound on the non-saccharide polymer or polymers different from the polyamine polymers on the one hand and on the keratin material on the other hand can be done in a single step, but it is also possible, if this procedure is desired. , prior to grafting the photoactivatable compound onto the non-saccharide polymer or polymers different from the polyamine polymers, then grafting this combination onto the keratin materials or else grafting the photoactivatable compound onto the keratin materials and then grafting this combination onto the non-saccharide polymers different from polyamine polymers.

According to a second embodiment of the invention, the diazirine groups of the photoactivatable compound or compounds present in the composition according to the invention are graft on both the non-saccharide polymer (s) different from the polyamine polymers, and on the surface of the hair.

As explained above, the cosmetic composition according to the invention comprises at least one non-saccharide polymer other than the photoactivatable compounds of the invention. For the purposes of the present invention, the term "non-saccharide polymer" means any polymer that does not comprise a monosaccharide unit. This polymer may be a silicone or non-silicone polymer, as defined below.

Preferably, these non-saccharide polymers other than the photoactivatable compounds of the invention are soluble in the medium. Among the non-saccharide polymers other than the photoactivatable compounds of the invention, mention may be made of substantive conditioning polymers, fixing polymers, thickening polymers and hydrophobic film-forming polymers.

By non-silicone polymer is meant in the sense of the present invention a polymer not containing -Si-O-Si- sequence. As non-silicone polymer used according to the invention, there may be mentioned those described in EP 1 647 260.

These polymers are those used in cosmetics, natural or synthetic, and in particular those obtained by radical polymerization or by polycondensation or by ring opening. They can be anionic, cationic, nonionic or amphoteric.

The non-silicone polymer has a main chain comprising carbon and hydrogen atoms, which can be interrupted by one or more heteroatoms such as O, N, P and S, and which may comprise one or more end-of-chain or lateral functions.

The non-silicone polymer generally comprises at least five repeating units linked by different or different covalent bonds. It can be a homopolymer or random, block, block or alternating copolymer.

As natural polymers, proteins such as albumin, ovalbumin, keratin, collagen can be used.

The natural polymers may be chemically modified, it will thus be possible to introduce into the main chain of this natural polymer at least one group selected from hydroxyalkyl, carboxyalkyl, amino, thio, and aldehyde and epoxy functions.

The non-silicone polymer used in the present invention can be dendritic, linear, branched, sequenced, comb-shaped or star-shaped.

By dendritic polymers or dendrimers is meant the polymers as described by D.A. Tomalia et al., Angewandlte Chemie, Int. Engl. Ed., Vol. 29, No. 2, p 138-

175. These dendrimers are molecular structures built around a generally versatile central pattern. Around this central motif, branched chain length patterns are chained in concentric layers and according to a perfectly determined structure thus giving rise to symmetrical, monodispersed macromolecules having a well-defined chemical and stereochemical structure.

It may also be dendritic polymers of the hyperbranched polymer type. Examples of polymers are described in patent applications WO 93 17 060 and WO 96 12754.

It may also be dendrons as defined in the article by D. A. Tomalia.

The non-saccharide polymers other than the photoactivatable compounds of the invention may be water-soluble, water-dispersible or fat-soluble.

By water-soluble or water-soluble or liposoluble homopolymer or copolymer is meant a homopolymer or copolymer which, at the concentration of 0.1% by weight of active material, respectively in water or in an oil such as isopropyl myristate or Vaseline oil, at 25 ° C., spontaneously or after neutralization with an acid or a base to a solution or suspension macroscopically homogeneous, transparent or translucent, that is to say having a transmittance at a wavelength of 500 nm, through a 1 cm thick sample.

SUBSTANTIFIC CONDITIONING POLYMERS

NON-SILICONE FIXING POLYMERS

The non-silicone fixing polymers that are suitable in the invention are chosen in particular from cationic, anionic, amphoteric and nonionic non-silicone fixing polymers and mixtures thereof.

The cationic non-silicone 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 connected thereto, and having a molecular mass. number average between 500 and about 5,000,000, and preferably between 1,000 and 3,000,000.

Among these polymers, mention may be made more particularly of the following cationic polymers:

R ₅ R ₅

(1) homopolymers or copolymers of acrylate or methacrylic esters or amides with amino functions, comprising at least one of the following units of formula: embedded image in which:

R 1 and R ₂ , which may be identical or different, each represent a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms;

R ₃ denotes a hydrogen atom or a CH ₃ group;

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

R ₄ , R ₅ , Re, identical or different, represent an alkyl group having 1 to 18 carbon atoms or a benzyl group;

X denotes a methosulphate anion or a halide such as chloride or bromide. The copolymers of family (1) also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone-acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyl groups (C _1-4). ), groups derived from acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters. Thus, among these copolymers of the family (1), mention may be made of:

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

- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride-ethyl-trimethyl ammonium described, for example, in patent application EP-A-080 976 and sold under the name Bina Quat P 10O ^® by Ciba Geigy,

- copolymers of acrylamide and of methacryloyloxy-ethyl trimethyl ammonium methosulfate, such as that sold under the name Reten ^® by the company Hercules, - vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, quaternized or otherwise, such as the products sold under the name "GAFQUAT ^® " by ISP, 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 Patent Nos. 2,077,143 and 2,393,573,

- the fatty-chain polymers and vinylpyrrolidone unit, such as the products sold under the name Styleze ^® W20 and STYLEZE ^® W10 by ISP, the dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone such as the product sold under the name Gaffix ^® VC 713 by ISP, and

vinylpyrrolidone / dimethylaminopropyl methacrylamide quaternized copolymers, such as in particular the product sold under the name

"GAFQUAT ^® HS 100" by the company ISP;

(2) cationic polysaccharides, preferably quaternary ammonium, such as those described in US Pat. Nos. 3,589,578 and 4,031,307, such as guar gums containing cationic trialkylammonium groups. Such products are marketed under the trade names Jaguar ^® C13 S, Jaguar ^® C15, Jaguar ^® C17 by MEYHALL;

(3) quaternary copolymers of vinylpyrrolidone and vinylimidazole;

(4) chitosans or their salts; the salts that can be used are, in particular, chitosan acetate, lactate, glutamate, gluconate or pyrrolidonecarboxylate. These compounds include the chitosan having a degree of deacetylation of 90.5% by weight sold under the name ^® KYTAN Brut Standard by the company Aber Technologies, chitosan pyrrolidone carboxylate sold under the name KYTAMER ^® PC by AMERCHOL company.

(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 especially in US Pat. No. 4 131 576, such as hydroxyalkylcelluloses, such as hydroxymethyl-, hydroxyethyl or hydroxypropyl cellulose grafted in particular with a salt of methacryloyloxyethyltrimethylammonium, methacrylamidopropyltrimethylammonium, dimethyldiallylammonium salt.

The marketed 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 anionic non-silicone fixing polymers generally used are polymers comprising 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:

in which n is an integer from 0 to 10, Ai 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 group -CH ₂ -COOH, phenyl or benzyl.

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 anionic non-silicone fixing polymers with preferred carboxylic groups according to the invention are:

A) Homo- or copolymers of acrylic or methacrylic acid or their salts and in particular the products sold under the names VERSICOL ^® E or K by the company Allied Colloid and Ultrahold ^® by the company BASF, copolymers of acrylic acid and of acrylamide sold in the form of their sodium salt 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, 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 Luxembourg Patent Application Nos ⁷⁵³⁷⁰ and 75371 or sold under the name Quadramer ^® by the company American Cyanamid. May also be mentioned the copolymers of acrylic acid and alkyl methacrylate, C ₁ -C ₄ and terpolymers of vinylpyrrolidone, acrylic acid-alkyl methacrylate CrC ₂ O, for example, lauryl, such as that marketed by the company ISP under the name Acryli DONE ^® LM, and methacrylic acid / ethyl acrylate / butyl acrylate terpolymers such as the product sold under the name Luvimer ^® 100 P by the company BASF. Mention may also be methacrylic acid / acrylic acid / ethyl acrylate / methyl methacrylate copolymer in aqueous dispersion sold under the name ^® Amerhold DR 25 by the company Amerchol.

C) Crotonic acid copolymers, such as those comprising in their chain vinyl acetate or propionate units, and optionally other monomers such as allyl or methallyl esters, vinyl ethers or vinyl esters of a saturated carboxylic acid, linear or branched, long hydrocarbon chain, such as those comprising at least 5 carbon atoms, these polymers may optionally be grafted or crosslinked, or another monomer vinyl ester, allyl or methallylique of a carboxylic acid α- or β-cyclic . Such polymers are described eg in the French patent n ^0E 1222944, 1580545, 2265782, 2265781, 1564 1 10 and 2 439 798. Commercial products coming within this class are the resins 28- 29-30, 26-13-14 and 28-13-10 marketed by the company National Starch. D) The copolymers of monounsaturated carboxylic acids or anhydrides in

C ₄ -C ₈ selected 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 names Gantrez AN or ES by ^® 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 patents Nos. ^2,350,384 and 2,357,241 of the applicant.

E) Polyacrylamides having carboxylate groups. Homopolymers and copolymers comprising 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 weight of between about 1,000 and 100,000, as well as copolymers with a comonomer unsaturated 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 names Flexan ^® 500 and Flexan ^® 130 by National Starch. These compounds are described in patent FR 2 198 719.

- polyacrylamide-sulphonic acid salts such as those mentioned in U.S. Patent 4,128,631, especially the sulfonic acid polyacrylamidoéthylpropane- sold under the name Cosmedia Polymer HSP ^® 1180 by Henkel.

As another anionic fixing polymer unusable silicone according to the invention include the anionic polymer sequence plugged sold under the name Fixate G100 ^® by Noveon.

According to the invention, non-silicone anionic fixing polymers are chosen from acrylic acid copolymers such as the acrylic acid / 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 company NATIONAL STARCH, polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as methylvinylether / maleic anhydride copolymers monoesterified sold, for example, under the name GANTREZ ^® by the Corporation 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 the BASF and the vinyl acetate / crotonic acid copolymers sold under the name Luviset ^® CA 66 by the company BASF and the vinyl acetate / crotonic acid copolymers grafted with polyethylene glycol sold under the name Aristoflex ^® A by the company BASF, the polymer sold under the name Fixate G100 ^® by Noveon.

Among the non-anionic silicone fixing polymers mentioned above, are more particularly preferred use in the context of the present invention the methyl vinyl ether / maleic anhydride copolymers sold under the name Gantrez ^® ES 425 by the company ISP, the acrylic acid / acrylate ethyl / 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 vinyl butylbenzoate / crotonic acid and the crotonic acid / vinyl acetate / 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 the company BASF, the vinylpyrrolidone / acrylic acid / methacrylate lauryl sold under the name ACRYLIDONE ^® LM by ISP, the polymer sold under the name Fixate G100 ^® by Noveon.

The non-silicone 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 comprising one or more carboxylic or sulphonic groups, or B and C may denote groups derived from zwitterionic monomers of carboxybetaines or of sulphobetaines;

B and C may also designate 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 B and C are part of a chain of an ethylene-α, β-dicarboxylic-containing polymer, one of which has been reacted with a polyamine having one or more primary or secondary amine groups.

The non-silicone amphoteric fixing polymers corresponding to the definition given above, which are more particularly preferred, are chosen from the following polymers:

(1) copolymers with acidic vinyl units and basic vinyl units, such as those 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-chloroacrylic acid, and 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 U.S. 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) with at least one acidic comonomer containing one or more several 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 sulfate or diethyl. The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are the 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.

Particularly The copolymers whose CTFA (4th Ed. 1991) is octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer such as the products sold under the name AM PHOM ^® ER or Lovocryl ^® 47 by the company National Starch.

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

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 thamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol%, the group (IV) 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- (CH ₂ ) 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 amino group of the polyaminoamide, and acylated by the action of acrylic acid, chloroacetic acid or a 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 acids, terephthalic acids, and double acids. 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 Rn denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, Ri ₂ and Ri ₃ represent a hydrogen atom, a methyl or ethyl group; or propyl, R ₄ and R ₁ 5 represent a hydrogen atom or an alkyl group such that the sum of carbon atoms in R ₄ and R15 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 alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.

Examples include copolymers of methyl methacrylate / methyl methacrylate dimethylcarboxymethylammonioethyl, such as the product sold under the name Diaformer® ^® Z301 by Sandoz. (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:

in which if q = 0, Ri ₇ , Ri ₈ and Ri ₉ , which may be 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 a plurality of nitrogen atoms and / or optionally substituted by one or more amino, hydroxyl, carboxyl, alkylthio, sulphonic groups, an alkylthio radical whose alkyl group carries an amino residue, at least one of the groups Ri ₇ , Ris and R ₁ 9 being in this case a hydrogen atom; or if q = 1, R ₁₇ , R ₁₈ and R 19 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 (V) are, for example, described in French Patent 1,400,366:

in which R ₂ o represents a hydrogen atom, a group CH ₃ O, CH ₃ CH ₂ O, phenyl, R ₂₁ denotes a hydrogen atom or a lower alkyl group such as methyl, ethyl, R ₂₂ denotes an atom of hydrogen or lower alkyl in C _r C ₆ such that 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 ₂ 2) 2, R 2 ₄ 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. (7) polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethyl-chitosan or N-carboxybutyl chitosan sold under the name ΕVALSAN ^® "by the company Jan Dekker.

(8) Amphoteric polymers of the -D-X-D-X 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:

-DXDXD- (Vl) 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: -DXDX- (Vl ') 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 necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betaineized by reaction with the acid; chloroacetic acid or sodium chloroacetate. (9) (C ₁ -C ₅ ) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as

N, N-dimethylaminopropylamine or by semi-esterification with N, N-dialkylaminoalkanol. These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam.

Among the amphoteric non-silicone fixing polymers described above, the most particularly preferred according to the invention are those of the family (3) such as the copolymers whose CTFA name is octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer, such as the products sold under the AM P denominations HOM ER ^®, Amphomer ^® LV 71 or Lovocryl ^® 47 by the company National Starch and those of family (4) such as copolymers of methyl methacrylate / methyl dimethylcarboxymethylammonioethyl methacrylate, sold, for example in the denomination DIAFORMER ^® Z301 by the company SANDOZ.

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

polyalkyloxazolines;

homopolymers of vinyl acetate;

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

- homopolymers and copolymers of acrylic esters such as, for example, alkyl acrylates and copolymers of alkyl methacrylates, such as the products sold by the company Rohm & Haas under the names Primal AC-261 K ^® and EUDRAGIT ^® NE 30 D, by 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 alkyl (meth) acrylates; 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 such as, for example, copolymers of styrene and of alkyl (meth) acrylate such as Mowilith LDM ^® products 691 1 Mowilith ^® DM 61 1 and Mowilith ^® LDM 6070 sold by the company Hoechst, the RHODOPAS ^® SD 215 and RHODOPAS ^® DS 910 products offered by RHONE POULENC; copolymers of styrene, alkyl methacrylate and alkyl acrylate; copolymers of styrene and butadiene; or copolymers of styrene, butadiene and vinylpyridine;

polyamides; - homopolymers of vinyllactam vinylpyrrolidone homopolymers, such as polyvinyl caprolactam sold under the name Luviskol ^® Plus by BASF; and vinyllactam copolymers such as a poly (vinylpyrrolidone / vinyllactam) copolymer sold under the trade name Luvitec ^® VPC

55K65W by BASF, poly (vinylpyrrolidone / vinyl acetate) 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), for example, that marketed under the name Luviskol ^® VAP 343 by the company

BASF.

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

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

The polyurethanes particularly targeted by the present invention are those described in the applications EP 0 751 162, EP 0 637 600, EP 0 648 485 and FR 2 743 297 of which the applicant is the holder, as well as in the applications EP 0 656 021 and WO 94/03510 of the company BASF, and EP 0 619 11 1 of the company National Starch.

As polyurethanes that are suitable in the present invention include the product sold under the name LUVISET ^® PUR by BASF.

THICKENING POLYMERS

For the purposes of the present invention, the term "thickening polymer" is understood to mean a polymer which is introduced at 1% in a pure aqueous or aqueous-alcoholic solution containing 30% of ethanol, and at pH = 7, makes it possible to attain a viscosity of at least 100 cps, preferably at least 500 cps, at 25 ^° C. and at a shear rate of 1 s ^-1 This viscosity can be measured using a cone / plane viscometer (Haake R600 Rheometer or the like).

Preferably, these polymers increase by their presence the viscosity of the compositions in which they are introduced by at least 50 cps, preferably 200 cps, at 25 ° C, and at a shear rate of 1 s- ¹ . Thickening polymers may be ionic polymers or not, associative or not.

As regards the non-associative thickening polymers, it is first of all pointed out that for the purposes of the present invention, the non-associative thickening polymers are thickening polymers not containing a C 10 -C 30 fatty chain. Among the non-associative thickening polymers present, mention may be made of crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked homopolymers of 2-acrylamido-2-methylpropanesulphonic acid and their crosslinked acrylamide copolymers, homopolymers of ammonium acrylate or copolymers of ammonium acrylate and acrylamide, nonionic guar gums, biopolysaccharide gums of microbial origin, gums derived from plant exudates, celluloses, in particular hydroxypropyl- or carboxymethylcelluloses; pectins and alginates, alone or in mixtures.

A first family of suitable nonassociative thickening polymers is represented by crosslinked acrylic acid homopolymers.

Among the homopolymers of this type include those crosslinked with an allyl alcohol of the sugar series ether, such as products sold under the names CARBOPOLS ^® 980, 981, 954, 2984 and 5984 by the company Noveon or the products sold under the names SYNTHALEN ^® M and SYNTHALEN ^® K by the company 3 VSA.

The non-associative thickening polymers may also be copolymers of (meth) acrylic crosslinked such as the polymer sold under the name CARBOPOL ^® AQUA SF1 by Noveon.

The non-associative thickening polymers may be chosen from cross-linked homopolymers of 2-acrylamido-2-methylpropanesulphonic acid and their crosslinked acrylamide copolymers.

With regard to these homopolymers and copolymers, which may be partially or completely neutralized, mention may be made of polymers comprising from 90 to 99.9% by weight, relative to the total weight of the polymer, of units of formula (j) below:

wherein X + denotes a cation or mixture of cations, or a proton.

More particularly, the cations are chosen from alkali metals (such as sodium, potassium), ammonium ions substituted or not by one to three identical or different alkyl radicals, comprising 1 to 6 carbon atoms, optionally carrying at least a hydroxyl radical, the cations derived from N-methylglucamine, basic amino acids such as arginine and lysine. Preferably, the cation is an ammonium or sodium ion.

In addition, the polymer comprises from 0.01 to 10% by weight, relative to the total weight of the polymer, of crosslinking units originating from at least one monomer having at least two ethylenic unsaturation (carbon-carbon double bond). The crosslinking monomers having at least two ethylenic unsaturations are chosen for example from diallyl ether, triallyl cyanurate, diallyl maleate, allyl (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyl oxethanoyl, tetra- or diethylene glycol di (meth) acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylene bis (meth) acrylamide or divinylbenzene allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, and the allylic esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures thereof. compounds.

For more details about these polymers, reference can be made to EP 815828.

Among the crosslinked copolymers of 2-acrylamido-2-methyl-propanesulfonic acid and of acrylamide partially or totally neutralized, mention may be made in particular of the product described in Example 1 of EP 503 853 and it will be possible to refer to this document for these polymers.

The composition may also comprise, as non-associative thickening polymers, homopolymers of ammonium acrylate or copolymers of ammonium acrylate and acrylamide. Examples of ammonium acrylate homopolymers that may be mentioned the product sold under the name MICROSAP ^® PAS 5193 by Hoechst. Among the copolymers of ammonium acrylate and acrylamide, mention may be made of the product sold under the name BOZEPOL C NEW ^® or the MICROSAP ^® PAS 5193 product sold by Hoechst. In particular, documents FR 2 416 723, US 2798053 and US 2923692 may be referred to for the description and preparation of such compounds.

The composition may also comprise homopolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride or copolymers of dimethylaminoethyl methacrylate quaternized with methyl chloride and acrylamide.

Among the homopolymers of this type include the products sold under the names Salcare ^® SC95 and Salcare ^® SC96 by Ciba. Among the copolymers of this family include the product Salcare ^® SC92 sold by CIBA or product MICROSAP NOT ^® 5194 sold by Hoechst. These polymers are in particular described and prepared in EP 395282 to which reference may be made.

As a non-associative thickening polymers include nonionic guar gums, such as unmodified nonionic guar gums sold under the name VIDOGUM ^® GH 175 by Unipectine and under the name Jaguar ^® C by the MEYHALL company. The nonionic guar gums that may be used according to the invention are preferably modified with C ₆ -C ₆ hydroxyalkyl groups. Among the hydroxyalkyl groups, there may be mentioned by way of example, the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. These guar gums are well known in the state of the art and may for example be prepared by reacting corresponding alkene oxides, such as, for example, propylene oxides, with guar gum, so as to obtain guar gum modified with hydroxypropyl groups.

The level of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum, preferably varies from 0.4 to 1.2.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are for example sold under the trade names Jaguar ^® HP8, Jaguar ^® HP60 and Jaguar ^® HP120, Jaguar ^® DC 293 and Jaguar ^® HP 105 by Mehhall or under the name

GALACTASOL ^® 4H4FD2 by the company AQUALON.

As suitable non-associative thickening polymers, mention may also be made of biopolysaccharide gums of microbial origin such as scleroglucan or xanthan gums. Also suitable are gums derived from plant exudates, such as gum arabic, Ghatti gums, Karaya and Tragacanthe gums; celluloses, in particular hydroxypropyl or carboxymethylcelluloses; pectins and alginates.

These polymers are well known to those skilled in the art and are particularly described in the book by Robert L. DAVIDSON entitled "Handbook of Water Soluble Gums and Resins" published by Mc Graw HiII Book Company (1980).

Among the thickeners, it is more particularly preferred to use thickening systems based on associative polymers well known to those skilled in the art and in particular of nonionic, anionic, cationic or amphoteric nature. It is recalled that the associative polymers are hydrophilic polymers capable, in an aqueous medium, to associate reversibly with each other or with other molecules.

Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone. Hydrophobic group is understood to mean a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms, and more preferably from 18 to 30 carbon atoms.

Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene. Among the associative polymers of the anionic type, mention may be made of: - (I) those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly those whose hydrophilic unit consists of an anionic monomer unsaturated ethylenic, more particularly by a vinyl carboxylic acid and very particularly by an acrylic acid or a methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (I):

CH ₂ = C ROH ₂ OB _n R (I)

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

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

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

Among these, the crosslinked terpolymers of methacrylic acid, of ethyl acrylate, of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), in particular those sold by the company CIBA under the trade names SALCARE, are particularly preferred. ^® SC80 and SALCARE ^® SC90 which are 30% aqueous emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10).

(M) those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of the (C 10 -C 30) alkyl ester of unsaturated carboxylic acid type.

Preferably, these polymers are chosen from those whose hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the following monomer of formula (II): CH ₂ = C -C OH I II R ₁ O (H)

Wherein R 1 denotes H or CH ₃ or C ₂ H ₅ , i.e., acrylic acid, methacrylic acid or ethacrylic acid units, and whose hydrophobic unit of the alkyl ester type (CiO- C ₃₀ ) unsaturated carboxylic acid corresponds to the monomer of the following formula

in which, R ₂ denotes H or CH ₃ or C ₂ H ₅ (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH ₃ (methacrylate units), R ₃ denoting a C ₁ -C 30 alkyl radical, and preferably a C ₂ -C ₂₂ alkyl radical.

Alkyl esters (C _O -C _3O) of unsaturated carboxylic acids according to the invention comprise for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate , dodecyl acrylate, and corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

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

Among this type of anionic associative polymers, there will be used more particularly polymers formed from a monomer mixture comprising: essentially acrylic acid, an ester of formula (III) described above and in which R ₂ denotes H or CH ₃ , R ₃ denoting an alkyl radical having from 12 to 22 carbon atoms, and

(iii) a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol di (methacrylate), and methylene-bis- acrylamide.

Among this type of anionic associative polymers, use will more particularly be those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C ₁₀ -C ₃₀ alkyl acrylate (unit hydrophobic), and 0 to 6% by weight of crosslinking polymerizable monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C ₁₀ alkyl acrylate -C ₃ O (hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above. Among said polymers above, the products sold by the company Goodrich under the trade names Pemulen TR1®, Pemulen TR2® and Carbopol are most particularly preferred according to the present invention. 1382®, and even more preferably PEMULEN TR1®, and the product sold by the company SEPPIC under the name COATEX SX®.

Mention may also be made of polymers which, in addition to the monomers of formula (II) and of formula (III), contain one or more other monomers. This additional monomer can be in particular a vinyllactam and in particular vinylpyrrolidone.

As examples of polymer include the acrylic acid / lauryl methacrylate / vinylpyrrolidone commercialized under the appellation ^® Acrylidone LM by the company ISP.

(III) the terpolymers of maleic anhydride / α-olefin C ₃ OC ₃ S / alkyl maleate such as the product (maleic anhydride copolymer / α-olefin in C ₃₀ -

C ₃ s / isopropyl maleate) sold under the name PERFORMA V 1608® by the company NEWPHASE TECHNOLOGIES.

- (IV) acrylic terpolymers comprising:

(a) about 20% to 70% by weight of an α, β-monoethylenically unsaturated carboxylic acid,

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

(c) about 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate, such as those described in the patent application EP-A-0173109 and more particularly that described in Example 3, namely, a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate terpolymer of ethoxylated behenyl alcohol (40OE) in a 25% aqueous dispersion. (V) copolymers comprising among their monomers an α, β-monoethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol.

Preferably, these compounds also comprise, as monomer, an ester of carboxylic acid with α, β-monoethylenic unsaturation and of alcohol in dC ₄ . By way of example of this type of compound, mention may be made of Aculyn 22® sold by the company Rohm and Haas, which is a methacrylic acid / ethyl acrylate / stearyl methacrylate oxyalkylenated terpolymer.

Among the associative polymers of cationic type, mention may be made of:

- (I) cationic associative polyurethanes whose family has been described by the applicant in the French patent application NO009609; it can be represented by the following general formula (IV):

R-X- (P) n- [L- (Y) m] r-L'- (P ') p-X'-R' (IV)

in which : R and R ', which may be identical or different, represent a hydrophobic group or a hydrogen atom;

X and X ', which are identical or different, represent a group comprising an amino function bearing or not a hydrophobic group, or else the group L ";

L, U and L ", identical or different, represent a group derived from a diisocyanate;

P and P ', which may be identical or different, represent a group comprising an amino function bearing or not a hydrophobic group; Y represents a hydrophilic group; r is an integer from 1 to 100, preferably from 1 to 50 and in particular from 1 to 25; n, m, and p are each independently from 0 to 1000; the molecule containing at least one protonated or quaternized amino function and at least one hydrophobic group.

In a preferred embodiment of these polyurethanes, the only hydrophobic groups are the R and R 'groups at the chain ends.

A preferred family of cationic associative polyurethanes is that corresponding to the formula (IV) described above and in which: R and R 'both independently represent a hydrophobic group,

X, X 'each represent a group L ", n and p are between 1 and 1000 and

L, L ', L ", P, P', Y and m have the meaning indicated above Another preferred family of cationic associative polyurethanes is that corresponding to formula (IV) above wherein:

R and R 'are each independently a hydrophobic group, X, X' are each L ", n and p are 0, and L, L ', L", Y and m are as defined above.

The fact that n and p are 0 means that these polymers do not comprise units derived from an amine-functional monomer incorporated in the polymer during the polycondensation. The protonated amine functions of these polyurethanes result from the hydrolysis of isocyanate functional groups, in excess, at the end of the chain, followed by the alkylation of the primary amine functions formed by hydrophobic group alkylation agents, i.e. to say compounds of the type RQ or R ¹ Q, in which R and R 'are as defined above and Q denotes a leaving group such as a halide, a sulphate, etc.

Yet another preferred family of cationic associative polyurethanes is that corresponding to formula (la) above in which:

R and R 'both independently represent a hydrophobic group, X and X' both independently represent a group comprising a quaternary amine, n and p are zero, and

L, L ', Y and m have the meaning indicated above.

The number average molecular weight of the cationic associative polyurethanes is preferably between 400 and 500,000, in particular between 1,000 and 400,000 and ideally between 1,000 and 300,000.

Hydrophobic group is understood to mean a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, which may contain one or more heteroatoms such as P, O, N, S, or a perfluorinated or silicone chain radical. When it refers to a hydrocarbon radical, the hydrophobic group comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.

Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene.

When X and / or X ¹ denote a group containing a tertiary or quaternary amine, X and / or X 'may represent one of the following formulas:

- for X

-R ₂ - -R ₂ -N- -R ₂ - or

in which :

R ₂ represents an alkylene radical having 1 to 20 carbon atoms, linear or branched, with or without a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms may be replaced by a heteroatom chosen from N, S, O, P;

R 1 and R ₃ , which may be identical or different, denote a linear or branched C 1 -C ₃₀ alkyl or alkenyl radical, an aryl radical, at least one of the carbon atoms may be replaced by a heteroatom chosen from N, S, O, P; A ^" is a physiologically acceptable counterion.

The groups L, L 'and L "represent a group of formula: - ZC-NH-R ₄ -NH-CZ-II ⁴ II

O O in which:

Z represents -O-, -S- or -NH-; and

R ₄ represents an alkylene radical having 1 to 20 carbon atoms, linear or branched, with or without a saturated or unsaturated ring, an arylene radical, one or more of the carbon atoms may be replaced by a heteroatom selected from N, S , O and P.

The groups P and P ', comprising an amino function, may represent at least one of the following formulas:

R ₈

-R ₅ -NR ₇ - or - R ₅ -NR ₇ -

R ₆ R ₆ ⁺ A

^R 6, ^R 8

NI or - R ₅ -CH-R ₇ - or - R ₅ -CH-R ₇ -

R ₆ -N ₇ R ₉ A

R ₈

in which :

R ₅ and R ₇ have the same meanings as R ₂ defined above; R ₆ , Rs and R ₉ have the same meanings as R ₁ and R ₃ defined above; R ₁₀ represents an alkylene group, linear or branched, optionally unsaturated and may contain one or more heteroatoms selected from N, O, S and P, and A ^" is a physiologically acceptable counterion.

As regards the meaning of Y, the term "hydrophilic group" means a water-soluble polymeric group or not.

By way of example, non-polymers include ethylene glycol, diethylene glycol and propylene glycol.

When it comes, according to a preferred embodiment, a hydrophilic polymer, there may be mentioned by way of example polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and especially a poly (ethylene oxide) or poly (propylene oxide). The cationic associative polyurethanes of formula (IV) that can be used according to the invention are formed from diisocyanates and from various compounds having functions with a labile hydrogen. The functions with a labile hydrogen may be alcohol, primary or secondary amine or thiol functions giving, after reaction with the diisocyanate functions, respectively polyurethanes, polyureas and polythioureas. The term "polyurethanes" usable according to the present invention encompasses these three types of polymers namely polyurethanes themselves, polyureas and polythioureas as well as copolymers thereof.

A first type of compound used in the preparation of the polyurethane of formula (IV) is a compound comprising at least one amino function unit. This compound can be multifunctional, but preferentially the compound is difunctional, that is to say that according to a preferred embodiment, this compound comprises two labile hydrogen atoms carried for example by a hydroxyl function, primary amine, secondary amine or thiol. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low.

As indicated above, this compound may comprise more than one amino function unit. It is then a polymer carrying a repetition of the amino-functional unit. This type of compound can be represented by one of the following formulas:

HZ- (P) H-ZH, or

HZ- (P ') p-ZH wherein Z, P, P', n and p are as defined above. As an example of an amino-functional compound, mention may be made of N-methyldiethanolamine, N-tert-butyl diethanolamine and N-sulfoethyldiethanolamine.

The second compound used in the preparation of the polyurethane of formula (IV) is a diisocyanate corresponding to the formula:

O = C = NR ₄ -N = C = O in which R ₄ is defined above.

By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.

A third compound used in the preparation of the polyurethane of formula (IV) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (IV).

This compound consists of a hydrophobic group and a function with a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.

By way of example, this compound may be a fatty alcohol, such as in particular stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymeric chain, it may be for example hydrogenated polybutadiene alpha-hydroxyl.

The hydrophobic group of the polyurethane of formula (IV) may also result from the quaternization reaction of the tertiary amine of the compound having at least one tertiary amine unit. Thus, the hydrophobic group is introduced by the quaternizing agent. This quaternizing agent is a compound of the type RQ or R'Q, in which R and R 'are as defined above and Q denotes a leaving group such as a halide, a sulphate, etc.

The cationic associative polyurethane may further comprise a hydrophilic block. This sequence is provided by a fourth type of compound used in the preparation of the polymer. This compound can be multifunctional. It is preferably difunctional. One can also have a mixture where the percentage of multifunctional compound is low.

The functions with a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends by one of these functions with labile hydrogen.

When it is a hydrophilic polymer, mention may be made by way of example of polyethers, sulphonated polyesters, sulphonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and especially a poly (ethylene oxide) or poly (propylene oxide).

The hydrophilic group Y in formula (IV) is optional. Indeed, the quaternary or protonated amine functional units may be sufficient to provide the solubility or hydrodispersibility necessary for this type of polymer in an aqueous solution.

Although the presence of a hydrophilic Y group is optional, cationic associative polyurethanes having such a group are preferred.

(II) quaternized cellulose derivatives and polyacrylates with non-cyclic amine side groups. The quaternized cellulose derivatives are in particular:

quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof,

quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof.

The alkyl radicals borne by the above-quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of C ₈ -C ₃₀ fatty chain quaternized alkylhydroxyethylcelluloses are QUATRISOFT LM 200®, QUATRISOFT LM-X 529-18-A®, QUATRISOFT LM-X 529-18B® (alkyl) Ci ₂ ) and QUATRISOFT LM-X 529-8® (C 1-8 alkyl) marketed by the company AMERCHOL and the products CRODACEL QM®, CRODACEL QL® (C _1-2 alkyl) and CRODACEL QS® (C _1-8 alkyl) marketed by the company CRODA.

(III) the cationic polymer (s) obtained by polymerization of a monomer mixture comprising one or more vinyl monomers substituted with one or more amino groups, one or more hydrophobic nonionic vinyl monomers, and one or more associative vinyl monomers.

In particular, among these cationic polymers, there may be mentioned the compound sold by the company NOVEON under the name CARBOPOL ^® AQUA CC and which corresponds to the INCI name POLYACRYLATE-1 CROSSPOLYMER. POLYACRYLATE-1 CROSSPOLYMER is the product of the polymerization of a monomer mixture comprising:

a di (C ₁ -C ₄ alkyl) amino methacrylate amino (C ₁ -C ₆ alkyl),

one or more C1-C30 alkyl esters and (meth) acrylic acid,

a polyoxyethylene C ₁₀ -C 30 alkyl methacrylate (20-25 moles of ethylene oxide unit),

an allyl ether of polyethylene glycol / polypropylene glycol 30/5,

- a hydroxy methacrylate (C ₂ -C _6), and

an ethylene glycol dimethacrylate.

The amphoteric associative polymers are preferably chosen from those comprising at least one non-cyclic cationic unit. Even more particularly, those prepared from or comprising 1 to 20 mol% of monomer comprising a fatty chain, and preferably 1.5 to 15 mol% and more particularly preferably

1.5 to 6 mol%, based on the total number of moles of monomers.

The preferred amphoteric associative polymers according to the invention comprise, or are prepared by copolymerizing at least one monomer of formula (V) or (VI):

AT-

(V) _flχ)

R

R ₁ -CH = CCZ- (C _n H _2n ) N _v

I M

RR ₂₂ OO R ₄ (VI)

(XX) in which, R ₁ and R ₂ , identical or different, represent an atom hydrogen or a methyl radical, R ₃ , R ₄ and R ₅ , which may be identical or different, represents a linear or branched alkyl radical having from 1 to 30 carbon atoms,

Z represents an NH group or an oxygen atom, n is an integer from 2 to 5, A ^" is an anion derived from an organic or inorganic acid, such as a methosulphate anion or a halide such as chloride or bromide ;

2) at least one monomer of formula (VII)

R ₆ -CH = CR ₇ -COOH _(vπ) in which, R ₆ and R ₇ , identical or different, represent a hydrogen atom or a methyl radical; and

3) at least one monomer of formula (VIII):

R ₆ -CH = CR ₇ -COXR ₈ (VIII) in which R ₆ and R ₇ , which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and Rs denotes a linear or branched alkyl radical having from 1 to 30 carbon atoms; at least one of the monomers of formula (V), (VI) or (VII) comprising at least one fatty chain.

The monomers of formula (V) and (VI) of the present invention are preferably chosen from the group consisting of: dimethylaminoethylmethacrylate, dimethylaminoethylacrylate,

diethylaminoethyl methacrylate, diethylaminoethyl acrylate,

dimethylaminopropylmethacrylate, dimethylaminopropylacrylate,

- Dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, these monomers being optionally quaternized, for example by a C ₁ -C ₄ alkyl halide or a C ₁ -C ₄ dialkyl sulfate.

More particularly, the monomer of formula (V) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.

The monomers of formula (VII) of the present invention are preferably selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. More particularly, the monomer of formula (VII) is acrylic acid.

The monomers of formula (VIII) of the present invention are preferably chosen from the group consisting of C 12 -C 22 alkyl acrylates or methacrylates and more particularly of C 1 -C 18 alkyl acrylates or methacrylates.

The monomers constituting the amphoteric fatty-chain polymers of the invention are preferably already neutralized and / or quaternized.

The ratio of the number of cationic charges / anionic charges is preferably equal to about 1. The amphoteric associative polymers according to the invention preferably comprise from 1 to 10 mol% of the monomer comprising a fatty chain (monomer of formula (V), (VI) or (VIII), and preferably from 1.5 to 6 mol% .

The weight average molecular weight of the amphoteric associative polymers according to the invention can vary from 500 to 50,000,000 and are preferably between 10,000 and 5,000,000.

The amphoteric associative polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C ₁ -C ₄ alkyl acrylates or methacrylates. Amphoteric associative polymers according to the invention are for example described and prepared in the patent application WO9844012.

Among the amphoteric associative polymers according to the invention, acrylic acid / (meth) acrylamidopropyltrimethylammonium chloride / stearyl methacrylate terpolymers are preferred. The nonionic associative polymers that may be used according to the invention are preferably chosen from:

- (1) celluloses modified with groups comprising at least one fatty chain; mention may be made, for example, of: hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C ₈ -C ₂ 2, such as the product Natrosol Plus Grade 330 CS® ₍₆ alkyls) sold by the company Aqualon, and the product Bermocoll EHM 100® sold by the company Berol Nobel,

those modified with alkyl phenol polyalkylene glycol ether groups, such as the product AMERCELL POLYMER HM-1500® (polyethylene glycol (15) nonyl phenol ether) sold by the company Amerchol.

- (2) hydroxypropyl guars modified with groups comprising at least one fatty chain such as the product ESAFLOR HM 22® (C22 alkyl chain) sold by the company Lamberti, and the products RE210-18® (alkyl chain ₄₎ and RE205-1 ® (C ₂ O alkyl chain) sold by the company RHONE POULENC.

(3) copolymers of vinyl pyrrolidone and hydrophobic fatty-chain monomers which may be mentioned by way of example: the ANTARON V216® or GANEX V216® products (vinylpyrrolidone / hexadecene copolymer) sold by the company I. S. P.

products ANTARON V220® or GANEX V220® (vinylpyrrolidone / eicosene copolymer) sold by I. S. P.

(4) copolymers of methacrylates or of C ₆ alkyl acrylates and of amphiphilic monomers comprising at least one fatty chain, such as, for example the methyl acrylate / oxyethylenated stearyl acrylate copolymer sold by GOLDSCHMIDT under the name ANTIL 208®.

(5) copolymers of methacrylates or d ^! hydrophilic acrylates and hydrophobic monomers comprising at least one fatty chain such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer.

(6) polyether polyurethanes comprising in their chain, both hydrophilic sequences most often polyoxyethylenated nature and hydrophobic sequences which may be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences. (7) polymers having an aminoplast ether skeleton having at least one fatty chain, such as the PURE THIX® compounds proposed by the company SUD-CHEMIE.

Preferably, the polyether polyurethanes comprise at least two hydrocarbon-based lipophilic chains having from 6 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block. The polyether polyurethanes may be multiblocked, in particular in the form of a triblock. The hydrophobic sequences may be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These same polymers may also be graft or star. The nonionic polyurethane polyethers with a fatty chain may be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain containing from 50 to 1000 oxyethylenated groups. Nonionic polyurethane polyethers have a urethane bond between the hydrophilic blocks, hence the origin of the name. By extension are also included among the nonionic polyurethane fatty chain polyethers those whose hydrophilic sequences are linked to the lipophilic blocks by other chemical bonds.

As examples of fatty-chain nonionic polyurethane polyethers that may be used in the invention, it is also possible to use also the urea-functional Rheolate 205® sold by Rheox or the Rheolates® 208, 204 or 212, as well as Acrysol RM 184®.

We may also mention the product Elfacos T210® alkyl chain in C ₁₂ _{to 14} and the product Elfacos T212® containing alkyl chain ₈ from Akzo.

The product DW 1206B® from ROHM & HAAS with a C ₂ 0 alkyl chain and a urethane linkage, proposed at 20% solids content in water, can also be used. It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example, such polymers include, for example, Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company

Rheox. It is also possible to use the product DW 1206F® and DW 1206J® proposed by the company Rohm & Haas.

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

More particularly still it is preferred to use a polyether polyurethane obtainable by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) alcohol stearyl or decyl alcohol and (iii) at least one diisocyanate.

Such polyether polyurethanes are sold in particular by the company ROHM &

HAAS under the names Aculyn 46® and Aculyn 44® [ACULYN 46® is a polyethylene glycol polycondensate containing 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene bis (4-cyclohexyl-isocyanate) ( SMDI), 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI), at 35% by weight in a propylene glycol mixture ( 39%) and water (26%)].

Preferably, the thickening polymers according to the invention are chosen from nonionic guar gums and associative polymers.

Among the associative polymers, the compounds of family (II) are preferred and particularly the terpolymers acrylic acid / lauryl methacrylate / vinylpyrrolidone.

FILMOGENIC HYDROPHOBIC POLYMERS

The film-forming polymer may be chosen from the film-forming polymers described in application WO 04/028487, the contents of which are incorporated herein by reference. The hydrophobic film-forming polymer may in particular be chosen from: a) homopolymers and copolymers of olefins; cycloolefins; butadiene; isoprene; styrene; ethers, esters or vinyl amides; esters or amides of (meth) acrylic acid containing an alkyl group in the form of

C ₂ O, linear, branched or cyclic, a C ₆ -C ₁₀ aryl group or a C ₂ -C ₆ hydroxyalkyl group.

Such homopolymers and copolymers can be obtained from monomers selected from the group consisting of isooctyl (meth) acrylate,

iso-nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isopentyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, (meth) acrylate tert-butyl, tridecyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl or phenyl acrylate. or mixtures thereof. As amides of acid monomers include (meth) acrylamides, and especially N-alkyl (meth) acrylamides, alkyl in particular C ₂ -C ₂ such as N-ethyl acrylamide, N-t- butyl acrylamide, N-octyl acrylamide; N-dialkyl (CrC ₄ ) (meth) acrylamides, perfluoroalkyl (meth) acrylates. The above polymers may also contain as monomers small amounts of an unsaturated carboxylic or sulfonic acid such as acrylic acid, methacrylic acid, AMPS, provided that the overall character of the polymer remains hydrophobic.

Other vinyl monomers that can be used include:

N-vinylpyrrolidone, vinylcaprolactam, vinyl N-alkyl (d-C6) pyrroles, vinyl-oxazoles, vinyl-thiazoles, vinylpyrimidines, vinylimidazoles,

olefins such as ethylene, propylene, butenes, isoprene, butadienes.

The vinyl polymer may be crosslinked with one or more difunctional monomers, in particular comprising at least two ethylenic unsaturations, such as ethylene glycol dimethacrylate or diallyl phthalate.

For example, mention may be made of the alkyl acrylate / cycloalkyl acrylate copolymer sold by PHOENIX CHEM. under the name GIOVAREZ® AC-5099 ML, the acrylates / Ci ₂ copolymer. ₂₂ alkyl methacrylate marketed by ROHM AND HAAS under the name SOLTEX® OPT and copolymers of vinylpyrrolidone, such as copolymers of a C ₂ to C ₃₀ alkene, such as C ₃ to C ₂₂ , and combinations of those can be used. As examples of PV copolymers that can be used in the invention, the copolymer of VP / vinyl laurate, VP / vinyl stearate, polyvinylpyrrolidone (PVP) butylated, VP / hexadecene marketed by ISP under the name can be used. Ganex® V216, VP / eicosene marketed by ISP under the name Ganex® V220, VP / triacontene or VP / acrylic acid / lauryl methacrylate. Mention may also be made of copolymers whose CTFA name (4th Ed., 1991) is

Octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, such as the products sold under the name AMPHOMER® or LOVOCRYL® 47 by National Starch and the copolymers whose CTFA name is Acrylates / octylacrylamide copolymer, such as the products sold under the name DERMACRYL® LT or DERMACRYL® 79 by the company NATIONAL STARCH. Particular polymers that may be mentioned include: (i) polymers bearing fluorinated groups belonging to one of the classes described in the above text, in particular the Fomblin® described in US Pat. No. 5,948,393, the copolymers of (meth) ) Alkyl acrylate / perfluoroalkyl (meth) acrylate described in EP 0 815 836 and US 5 849 318. ii) polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer, comprising one or more ethylenic bonds, preferably conjugated (or dienes). As polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer, it is possible to use vinyl, acrylic or methacrylic copolymers.

In one embodiment, the film-forming polymer is a block copolymer comprising at least one block consisting of styrene units or styrene derivatives (for example methylstyrene, chlorostyrene or chloromethylstyrene). The copolymer comprising at least one styrene block may be a diblock or triblock copolymer, or even a multiblock, star or radial copolymer. The copolymer comprising at least one styrene block may also comprise, for example, an alkylstyrene block (AS), an ethylene / butylene (EB) block, an ethylene / propylene (EP) block, a butadiene block (B), an isoprene block. (I), an acrylate block (A), a methacrylate block (MA) or a combination of these blocks. The copolymer comprising at least one block consisting of styrene units or styrene derivatives may be a diblock or triblock copolymer, and in particular of the polystyrene / polyisoprene or polystyrene / polybutadiene type, such as those sold or manufactured under the name "Luvitol® HSB" by BASF and those of the polystyrene / copoly (ethylene-propylene) or alternatively of the polystyrene / copoly (ethylene / butylene) type, such as those sold or manufactured under the trademark "Kraton®" by Shell Chemical Co., or Gelled Permethyl 99A® by Penreco, can be used.

Examples include Kraton® G1650 (SEBS), Kraton® G1651 (SEBS), Kraton® G1652 (SEBS), Kraton® G1657X (SEBS), Kraton® G1701 X (SEP), Kraton® G1702X (SEP), Kraton® G1726X (SEB), Kraton® D-1 101 (SBS), Kraton® D-1 102 (SBS), Kraton® D-1 107 (SIS), Gelled Permethyl 99A- 750®, Gelled Permethyl 99A-753-58® (star-block polymer and triblock polymer blend), Gelled Permethyl 99A-753-59® (star-block polymer and triblock polymer blend), Versagel® MD 970 and Versagel® MD 960 from Penreco (a blend of star polymer and triblock polymer in isododecane). Styrene-methacrylate copolymers may also be used, such as the polymers sold under the references OS 129880, OS 129881 and OS 84383 from Lubrizol (styrene-methacrylate copolymer).

In one embodiment, the film-forming polymer is chosen from vinyl ester copolymers (the vinyl group being directly connected to the oxygen atom of the ester group and the vinyl ester having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl ester group) and at least one other monomer chosen from vinyl esters (different from the vinyl ester already present), α-olefins (having from 8 to 28 carbon atoms), alkylvinyl ethers (of which the alkyl group has 2 to 18 carbon atoms), or allyl or methallyl esters (having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl ester group).

These copolymers may be partially crosslinked by means of crosslinking agents which may be of the vinyl type, or of the allyl or methallyl type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and octadecanedioate. of divinyl.

Examples of such copolymers include copolymers: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecylvinylether , vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, stearate of vinyl viny / allyl acetate, 2,2-dimethyl-2 vinyl octanoate / vinyl laurate, 2,2-dimethyl-2 allyl pentanoate / vinyl laurate, vinyl dimethyl propionate / vinyl stearate, allyl dimethyl propionate / vinyl stearate, vinyl propionate / vinyl stearate, crosslinked with 0.2% divinyl benzene, vinyl dimethyl propionate / vinyl laurate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% tetra llyloxyethane, vinyl acetate / allyl stearate, cross-linked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 cross-linked with 0.2% divinyl benzene and allyl propionate / allyl stearate crosslinked with 0 2% divinyl benzene. iii) polyalkenes, copolymers of C ₂ -C ₂ ₂ alkenes, in particular polybutene. iv) Polymers of natural origin, possibly modified, which may be chosen from shellac resin, sandarac gum, dammars, elemis and copals. polysaccharides comprising alkyl side chains (ether or ester), in particular alkylcelluloses having a linear or branched, saturated or unsaturated C ₁ -C ₈ alkyl radical, such as ethylcellulose and propylcellulose.

The film-forming polymer of natural origin may be chosen in particular from cellulosic polymers such as nitrocellulose, cellulose acetate, cellulose acetate butyrate and cellulose acetopropionate. Mention may be made, for example, of ethyl cellulose marketed by Aqualon under the reference Aqualon Ethylcellulose N200, the cellulose acetate butyrate marketed by Eastman Chemical under the reference CAB-381-0.5, cellulose acetate propionate marketed by Eastman Chemical under the references CAP. -482-20 and CAP-504-0.2. v) polycondensates.

Among the polycondensates, mention may be made of nonionic polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea / polyurethanes, and mixtures thereof. The polyurethanes may be, for example, an aliphatic, cycloaliphatic or aromatic polyurethane copolymer of polyurea / polyurethane.

The polyurethanes as defined in the invention can also be obtained from branched or unbranched polyesters or from alkyds comprising mobile hydrogens which are modified by means of a polyaddition with a diisocyanate and a bifunctional co-reactive compound. organic (for example dihydro, diamino or hydroxy-amino).

Mention may also be made of polyesters, polyesteramides, fatty-chain polyesters, polyamides and epoxyester resins. The polyesters can be obtained in known manner by means of the polycondensation of aliphatic or aromatic diacids with aliphatic or aromatic diols or with polyols. Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid or sebacic acid can be used as aliphatic diacids. Terephthalic acid or isophthalic acid, or even a derivative such as phthalic anhydride, can be used as aromatic diacids. Ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol and 4,4-N- (1-methylpropylidene) bisphenol can be used as aliphatic diols.

The polyesteramides can be obtained analogously to polyesters by means of the polycondensation of diacids with amino alcohols. The polyamides can be obtained in a manner analogous to polyesters, by means of the polycondensation of diacids with diamines.

As a particular polyester, mention may be made of aliphatic polyesters having C ₄ -C 50 alkyl side chains or polyesters resulting from the condensation of fatty acid dimers, or even polyesters comprising a silicone segment in the form of a sequence, graft or terminal group, as defined in patent application FR 0 1 13 920.

As silicone polymer that can be used in accordance with the invention, mention may be made especially of those described in document FR 2 834 209. They may be soluble or insoluble in water, volatile or nonvolatile, and they may be in particular polyorganosiloxanes. insoluble in water. They can be in the form of oils, waxes, resins or gums.

Polyorganosiloxanes are further defined in Walter NOLL's "Chemistry and Technology of Silicones" (1968) Academy Press.

When they are volatile, the silicone polymers are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and more particularly between:

(i) cyclic silicone polymers containing from 3 to 7 silicon atoms and, preferably, from 4 to 5. It is, for example, octamethylcyclotetrasiloxane marketed in particular under the name "VOLATILE SILICONE 7207®" by UNION CARBIDE or "SILBIONE® 70045 V 2" by RHODIA, decamethylcyclopentasiloxane sold under the name "VOLATILE SILICONE 7158®" by UNION CARBIDE, "SILBIONE® 70045 V 5" by RHODIA.

Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the "VOLATILE SILICONE FZ 3109®" marketed by UNION CARBIDE, of chemical structure:

with D: " ^~ 0-

(ii) linear volatile silicone polymers having 2 to 9 silicon atoms and having a viscosity of less than or equal to 5.10-6 m 2 / s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by Toray Silicone. Silicone polymers in this class are also described in the article published in Cosmetics and toilethes, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile silicone fluids for cosmetics".

Among the non-volatile silicone polymers, there may be mentioned polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, gums and silicone resins, polyorganosiloxanes modified with organofunctional groups.

The organomodified silicone polymers that can be used in accordance with the invention are silicone polymers as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

Among the organomodified silicone polymers, mention may be made of polyorganosiloxanes comprising:

polyoxyethylene and / or polyoxypropylene groups optionally containing C ₆ -C ₂₄ alkyl groups such as the products known as dimethicone-copolyol sold by the company Dow Corning under the name DC 1248 or the oils SILWET® L 722, L 7500, L 77, L 71 1 of the company UNION CARBIDE and the alkyl (Ci ₂ ) -methicone-copolyol marketed by the company Dow Corning under the name Q2 5200;

substituted or unsubstituted amine groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company

GENESEE or the products marketed under the names Q2 8220 and DOW CORNING 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C ₁ -C ₄ aminoalkyl groups;

thiol groups, such as the products sold under the names "GP 72 A" and "GP 71" from GENESEE; alkoxylated groups, such as the product marketed under the name "Silicone Copolymer F-755®" by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company GOLDSCHMI DT;

hydroxyl groups, such as the hydroxyalkyl-functional polyorganosiloxanes described in the French patent application FR-A-85 16334. acyloxyalkyl groups such as, for example, the polyorganosiloxanes described in US Pat. No. 4,957,732.

anionic groups of the carboxylic acid type, for example, in the products described in patent EP 186 507 of the company Chisso Corporation, or of the alkyl-carboxylic type, such as those present in the product X-22-3701 E of the company SHIN-ETSU; 2-hydroxyalkylsulfonate; 2-hydroxyalkylthiosulphate such as the products sold by GOLDSCHMIDT under the names "ABIL® S201" and "ABIL® S255".

hydroxyacylamino groups, such as the polyorganosiloxanes described in patent application EP 342 834. Mention may be made, for example, of the product Q2-8413 from the company Dow Corning.

Generally, the silicone or non-silicone non-saccharide polymer or polymers as described above, present in the cosmetic compositions of the invention and different from the photoactivatable polymers of the invention, represent between 0.01 and 90% and preferably between 0.01 and 20% by weight of the total weight of the composition. The cosmetic composition according to the invention may also comprise one or more non-polymeric cosmetic active ingredients.

Generally, the cosmetic active agent (s) possibly present in the composition according to the invention are chosen from reducing agents, non-silicone fatty substances, plasticizers, softeners, anti-foam agents, moisturizing agents, UV filters, perfumes, anionic, cationic, nonionic or amphoteric surfactants, direct or oxidation dyes, pigments and pearlescent agents.

The subject of the invention is also a first cosmetic treatment method comprising a step of applying to the keratin materials of a composition according to the invention, and a step of exposing said keratin materials to radiation of one or more lengths. wavelengths between 300 and 450 nm, preferably between 300 and 380 nm, better between 350 and 380 nm, or natural light.

This exposure can be done on the entire hair for example or be located at will on a previously defined surface area. According to a first embodiment, the method according to the invention may comprise, after the step of applying the composition according to the invention and before the step of exposure to radiation or natural light, a drying step hair, preferably by means of a hair dryer or a helmet. According to a second embodiment, the first method according to the invention comprises, after the step of applying the composition according to the invention and before the step of exposure to radiation or natural light, a pre-drying step keratin materials, preferably by means of a hair dryer, and then a step of applying a heating flat iron or a curling iron. The subject of the invention is also a second method of cosmetic treatment comprising the following steps:

- Application on the keratin materials of one or more photoactivatable compounds as defined above in a cosmetically acceptable medium,

- Application to the keratin materials of one or more non-saccharide polymers as defined above, different from the polyamine polymers, in a cosmetically acceptable medium,

exposure of said keratin materials to radiation of one or more wavelengths between 300 and 450 nm, preferably between 300 and 380 nm, better still between 350 and 380 nm, or with natural light. The second method according to the invention generally comprises a step of drying the keratin materials after the application of the photoactivatable compound and before the application of the non-saccharide polymer or polymers different from the polyamine polymers.

According to a first embodiment, the second method according to the invention comprises a step of drying the keratin materials after the application of the non-saccharide polymer or polymers different from the polyamine polymers and before the exposure of the keratin materials to radiation or light. natural.

According to a second embodiment, the second method according to the invention comprises, after the step of applying the non-saccharide polymer or polymers different from the polyamine polymers, and before the step of exposure to radiation or natural light, a step pre-drying the keratin materials and then a step of applying a flat iron or a curling iron.

The first method according to the invention or the second method according to the invention may comprise a preliminary treatment step of the keratinous materials chosen from the group consisting of treatments using a reducing composition, and staining with oxidation dyes. , discolorations, alkaline straighteners, shampoos, styling treatments.

The present invention is illustrated by the following examples.

EXAMPLES Per g of gray hair at 90% white, 0.2 g of product marketed under the name DOW CORNING® 1501 Fluid (polydimethylsiloxane-α, ω-dihydroxylated / cyclopentadimethylsiloxane) is applied.

Without intermediate rinsing, polyethyleneimine diazirine (10) is then always applied at a rate of 0.2 g per g of hair.

The hair is then dried with a hair dryer and then irradiated at a wavelength of 365 nm (twice 500 mJ / cm ² ).

A durable grafting of the silicone compound on the hair is obtained. These are then smoothed, untangled easily, and have a silicone remanent touch to many shampoos.

Claims

1. Cosmetic composition characterized in that it comprises, in a cosmetically acceptable medium, a) one or more photoactivatable compounds obtained from polyamine polymers containing at least two amino -NH- and / or ^~ N- units, on which covalently bound at least two photoactivatable diazirine groups, and b) one or more non-saccharide polymers different from the compounds a).

2. Composition according to claim 1, characterized in that the polyamine polymer is chosen from:

the polyalkyleneimines, preferably the poly (C ₂ -C ₅ alkyleneimines),

polymers grafted with a (C ₂ -C 5) alkyleneimine, preferably polymers grafted with ethyleneimine, better polyamidoamines, crosslinked or not, grafted with ethyleneimine, copolymers based on aminoalkyl (C ₁ -C 5); C ₄ ) (meth) acrylate, preferably based on aminoethyl (meth) acrylate,

polyallylamines,

the polycondensates of at least one compound chosen from piperazine, 1 - (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, 1-alkyl (dC ₂ 5) piperazine, 1 , 4-di (alkyl (Ci-C ₂ 5)) piperazine, 1 - (2-hydroxy (alkyl (C ₂ -C ₂₅₎₎₎ piperazine, imidazole, alkylimidazole the -C _25, or mixtures thereof, with at least one compound chosen from a C ₆ -C ₂₂ alkylene dihalide, an epihalohydrin and / or a C ₈ -C ₂₂ bisepoxide,

polymers containing in their structure at least 2 successive units of the same basic amino acid, polyamidoamines,

dendrimers containing primary amines in the terminal position.

3. Composition according to claim 1 or 2, characterized in that the photoactivatable compounds are obtained from a polyamine chosen from polyethyleneimines, polylysines and polyalkylamines.

4. Composition according to any one of the preceding claims, characterized in that the diazirine groups are obtained by grafting onto the polyamine polymer of a diazirine of formula:

in which R 1 is selected from the group consisting of a hydrogen atom, a linear or branched C ₁ to C ₁₀ alkyl radical, a linear or branched C ₂ to C ₁₀ alkenyl radical, a linear or branched C ₂ -C ₁₀ alkynyl, CF ₃ , CCI ₃ , CBr ₃ , NR ' ₃ +, SR' ₂ +, SH ₂ +, NH ₃ +, NO ₂ , SO ₂ R ', ON, COOH, F , Cl, Br, I ₁ OR, COOR ', SO ₃ H, COR', SH, SR ', OH, where R' is a linear or branched C ₁ -C 10 alkyl radical,

Z is a single covalent bond or a spacer group which is a linear, branched or cyclic, saturated or unsaturated C ₁ -C 100 carbon chain, preferably CrC ₅ O, which chain may be interrupted by hetero atoms such as sulfur, oxygen, nitrogen, silicon or phosphorus and may also include one or more substituents such as hydroxyl groups, amines, thiols, carbamates, ethers, acids, esters, amides, cyano, ureido. Y represents a function selected from the group formed by alcohols, amines, thiols, thiosulfates, carboxylic acids and its derivatives such as anhydrides, acid chlorides, esters, acetals and hemi-acetals, aminals and hemi-amines, ketones, aldehydes, alpha-hydroxyketones, epoxidized alpha-haloketones, lactones, thiolactones, azalactones, isocyanates, thiocyanates, imines, imides (succinimides, glutimides), imidoesters, aziridines, imidates, oxazine and oxazoline, oxazinium and oxazolinium, halogens (fluorine, chlorine, iodine, bromine), chlorotriazines, chloropyrimidines, chloroquinoxalines, chlorobenzotriazoles, sulfonyl halides (X = F, Cl, I or Br); SO ₂ X, siloxanes, silanols, silanes, pyridyldithio, N-hydroxysuccinimide esters, activated or unactivated vinyls, including acrylonitriles, acrylic and methacrylic esters, crotonic acids and esters, cinnamic acids and esters, styrenes, butadienes, vinyl ethers, vinyl ketone, maleic esters, maleimides, vinyl sulfones, hydrazines, phenyl glyoxals, epoxies, Ar represents an aromatic ring selected from the group consisting of:

in which R ₂ , R 3, R ₄ and R ₅ represent, independently of one another, radicals chosen from the group formed by a hydrogen atom, a linear or branched C ₁ -C ₁₀ alkyl radical, an alkenyl C ₂ to C ₁ 0 straight or branched alkynyl, C ₂ to C ₁ 0 straight or branched, CF _3, CCI _3, CBr _3, NR _'3 +, SR' ₂ +, SH ₂ +, NH ₃ +, NO ₂ , SO ₂ R ', C≡N, COOH, F, Cl, Br, I ₁ OR, COOR ¹ , SO ₃ H, COR', SH, SR ', OH, where R ¹ is a linear or branched C ₁ -C ₁₀ alkyl radical.

5. Composition according to any one of the preceding claims, characterized in that the photoactivatable compound comprises a unit of formula (3) and a unit of formula (A), the weight average molecular weight of the photoactivatable compound is between 2,000 and 100,000, and preferably the molar ratio of the unit of formula (3) and the unit of formula (A) is between 1: 50 and 1: 2:

6. Composition according to any one of claims 1 to 4, characterized in that the photoactivatable compound comprises a unit of formula (4), a unit of formula (B) and a unit of formula (B '), the weight average molecular weight of the photoactivatable compound is between 2000 and 150 000, and preferably the molar ratio of the unit of formula (4) and units of formula (B) and (B ') is between 1: 50 and 1: 2:

7. Composition according to any one of claims 1 to 4, characterized in that the photoactivatable compound comprises a unit of formula (6), a unit of formula (C) and a unit of formula (C), the mass weight average molecular weight of the photoactivatable compound is between 2,000 and 150,000, and preferably the molar ratio of the unit of formula (6) and units of formulas (C) and (C) is between 1: 50 and 1: 2:

8. Composition according to any one of claims 1 to 4, characterized in that the photoactivatable compound comprises a unit of formula (7) and a unit of formula (A), the weight average molecular weight of the compound activatable is from 2,000 to 100,000, and preferably the molar ratio of the unit of formula (7) to the unit of formula (A) is from 1:50 to 1: 2:

9. Composition according to any one of claims 1 to 4, characterized in that the photoactivatable compound comprises a unit of formula (8), a unit of formula (B) and a unit of formula (B '), the mass weight average molecular weight of the photoactivatable compound is between 2000 and 150 000, and preferably the molar ratio of the unit of formula (8) and of units of formula (B) and (B ') is between 1: 50 and 1: 2:

10. Composition according to any one of claims 1 to 4, characterized in that the photoactivatable compound comprises a unit of formula (9), a unit of formula (C) and a unit of formula (C), the mass weight average molecular weight of the photoactivatable compound is between 2,000 and 150,000, and preferably the molar ratio of the unit of formula (9) and units of formulas (C) and (C) is between 1: 50 and 1: 2:

1. Composition according to any one of the preceding claims, characterized in that the photoactivatable compound (s) represent (s) between 0.01% and 90% by weight of the total weight of the composition.

12. Composition according to any one of the preceding claims, characterized in that the non-saccharide polymer different from the polyamine polymers is a silicone or non-silicone polymer; said silicone polymer being soluble or insoluble in water and being in the form of oil, resin, wax or gum; and said non-silicone polymer being selected from the random, block, or alternating, random homopolymers and copolymers, preferably from the substantive conditioning polymers, the fixing polymers, the thickening polymers and the film-forming hydrophobic polymers.

13. Composition according to any one of the preceding claims, characterized in that the non-saccharide silicone or non-silicone polymer is contained in an amount of between 0.01% and 90% and preferably between 0.01 and 20% by weight. relative to the total weight of the composition.

14. Cosmetic treatment process, characterized in that it comprises a step of application to the keratin materials of a composition as defined in claims 1 to 13, a step of exposing said keratin materials to a radiation of one or more wavelengths between 300 and 450 nm, preferably between 300 and 380 nm, better between 350 and 380 nm or natural light, and preferably after the step of application of the composition and before the step of exposure to radiation or natural light, a step of pre-drying the keratin materials, preferably by means of a hair dryer, then a step of applying a heated flat iron or a curling iron.

15. Cosmetic treatment process comprising the following steps:

- Application on the keratin materials of a photoactivatable compound as defined in any one of Claims 1 to 11, in a cosmetically acceptable medium,

- Application to the keratin materials of at least one non-saccharide polymer as defined in claim 12 or 13, different from the polyamine polymers, in a cosmetically acceptable medium,

exposure of said keratin materials to radiation of one or more wavelengths between 300 and 450 nm, preferably between 300 and 380 nm, better still between 350 and 380 nm, or in natural light.