EP0994910A1 - Heterocyclic quaternary polyammonium silicon polymers and their use in cosmetic compositions - Google Patents

Abstract

The invention concerns novel polymers comprising at least units of formula (I) wherein A1+ and A¿2?+, identical or different, represent: a) a quaternary unsaturated heterocyclic compound; or b) a quaternary ammonium and at least one of groups A¿1?+ and A¿2?+ represents a quaternary unsaturated heterocycle; p represents an integer or decimal from 0 to 50; B¿1? represents an α, φ bis alkyl polysiloxane or a hydrocarbon chain, linear or branched, saturated or unsaturated comprising up to 6 consecutive carbon atoms, capable of comprising one or several hydroxyl groups and of being interrupted by one or several oxygen atoms and/or several aromatic cycles; B2 represents a hydrocarbon chain, linear or branched, saturated or unsaturated comprising up to 6 consecutive carbon atoms, capable of comprising one or several hydroxyl groups and of being interrupted by one or several oxygen atoms and/or several aromatic cycles; R1, R2, R3 and R4, identical or different, represent a C1-C6 alkyl radical or the phenyl radical. XΥ represents an anion derived from a mineral or organic acid. The invention also concerns the use of said polymers in cosmetics.

Description

Silicon heterocyclic quaternary polyammonium polymers and their use in cosmetic compositions

The present invention relates to new silicon polymers of heterocyclic quaternary polyammonium, to cosmetic compositions using them, as well as to methods of treating keratin fibers and in particular hair using these polymers.

It has already been proposed to use polyquaternary polysiloxane polymers in order to improve the disentangling of the hair. Such compositions are described in particular in the French patent of the Applicant No. 2,535,730. Document US Pat. No. 4,833,225 describes polyquaternary polysiloxane polymers which are resistant to being washed out and allow easy styling.

Cationic polymers have a great affinity for keratin fibers, such as the hair, due to the interaction of cationic groups with the anionic groups of the hair.

These polymers are deposited on the hair all the more easily as they are more sensitized and their affinity for the hair is often such that they resist elimination by shampooing or by brushing.

It has been found, however, that if the use of such cationic polymers has many advantages in that they facilitate the disentangling of the hair and that they give them qualities of nervousness and a shiny appearance, because of their affinity for keratin, these polymers tend to build up on hair to following repeated applications.

In addition, cationic polymers with quaternary groups often have the disadvantage of being not very compatible with anionic surfactants, which reduces the possibilities of use and imposes their use in two-stage treatments, before or after. shampoo.

The Applicant has discovered that certain silicon quaternary polyammonium polymers, which do not have the drawbacks mentioned above, comprising at least unsaturated quaternary heterocycles were particularly advantageous for the treatment of keratin fibers, and in particular human keratin fibers such as hair.

The Applicant has notably discovered that the use of these polymers makes it possible to protect keratinous fibers, and in particular human keratinous fibers such as the hair, both with respect to attacks, due in particular to the sun, to bad weather, to perspiration that with respect to those resulting from the treatment of keratin fibers, and in particular human keratin fibers such as the hair, such as for example, discoloration, perms or dyes.

It has been found that keratin fibers tend to be weakened when subjected to these treatments; keratin fibers, and in particular human keratin fibers such as the hair, become dry, dull and rough, difficult to disentangle and to style.

The protective agents of the invention are used in particular in any cosmetic process comprising at least one step during which the keratin fibers are liable to be exposed to various attacks and thus make it possible to avoid the drawbacks mentioned above.

These protective agents can be applied to the keratin fibers, during, before or after this stage during which the keratin fibers are subjected to attacks. Preferably, the protective agents of the present invention are used in a process during which at least one application of an alkaline composition to the keratin fibers takes place. The invention therefore relates to new heterocyclic polyquaternary silicon polymers.

The subject of the invention is also the use as a protective agent of keratin fibers of these new heterocyclic polyquaternary silicon polymers. A subject of the invention is also cosmetic compositions using them and in particular compositions intended for permanent shaping of keratin fibers, bleaching compositions and dye compositions.

The subject of the invention is also methods of treating keratin fibers, and in particular human keratin fibers such as the hair, using these compositions.

Other objects of the present application will emerge on reading the description and the examples which follow.

The polymers of the present invention comprise at least recurring units of formula (I):

Θ © Ri R, -Ai-B] -A ₇ - B ₉ - Si ^ O — Si -B, 4- (i)

Θ x ^Θ R> RΛ

X

in which:

• A _j ® and A ₂ ®; identical or different, denote: a) a quaternary unsaturated heterocycle of formula (II): NT / ^" G (+ (II)

in which

E, G, L, J, identical or different, denote a carbon, oxygen, sulfur or nitrogen atom, at least one denoting a nitrogen atom;

E, G, L, J may be substituted, when one or more of these atoms denote a carbon atom, by one or more halogen atoms, hydroxyl groups, nitro, cyano, sulfhydryl, carboxyl, alkyl groups, monohydroxyalkyl, polyhydroxyalkyl , thioalkyl, cyanoalkyl, alkoxy, acyl, acetyloxyl, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkylaryl or by one or more groups -NHR _N in which R _N denotes an acetyl or ureido group;

When E, G, L, or J denote a third nitrogen atom, this can be substituted by a hydrogen, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, aryl substituted or unsubstituted radical or a substituted or unsubstituted alkylaryl radical;

The substituents of two of the atoms E, G, L and J can also form, together with the atoms to which they are attached, a substituted or unsubstituted 5 to 7-membered aromatic ring; or b) a quaternary ammonium of formula (III)

R5

Θ l ⁵ (in)

- NOT-

R _*

in which:

R ₅ and R _6, identical or different, denote a group carboxyl, an alkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl, acetyloxy group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl or a group -NHR _N in which R _N denotes an acetyl or ureido group ;

R ₅ and R ₆ can also form, together with the nitrogen atom to which they are attached, a saturated cycle of 5 to 7 carbon links; and at least one of the groups A _j ® and A ₂ ® denotes a quaternary unsaturated heterocycle of formula (TJ);

• p denotes an integer or decimal number from 0 to 50 and preferably from 0 to 10; p can represent a defined number or an average statistical value;

• B _j denotes a group, ω bis alkyl polysiloxane or a hydrocarbon chain, linear or branched, saturated or unsaturated containing up to 6 consecutive carbon atoms, which can comprise one or more hydroxyl groups and which can be interrupted by one or more atoms of 'oxygen and / or several aromatic cycles;

• B ₂ denotes a hydrocarbon chain, linear or branched, saturated or unsaturated comprising up to 6 consecutive carbon atoms, which can comprise one or more hydroxyl groups and which can be interrupted by one or more oxygen atoms and / or one or more aromatic cycles;

• R _j , R ₂ , R ₃ and R ₄ , identical or different, denote a C _j -C ₆ alkyl radical or the phenyl radical;

• X® denotes an anion derived from a mineral or organic acid.

In the context of the present invention:

The halogen atoms preferentially denote a fluorine, chlorine, bromide or iodine atom.

The alkyl, monohydroxyalkyl, polyhydroxyalkyl and hydrocarbon groups can be linear or branched.

The alkyl groups denote in particular the groups of 1 to 20 carbon atoms, such as for example, the methyl, ethyl, propyl, isopropyl, n-propyl, butyl groups, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, n-hexyl, isohexyl, heptyle, octyl, nonyle, decyle, undecyle, dodecyle and pentadecyle. Preferably, the alkyl groups denote a group of 1 to 6 carbon atoms; Among the hydrocarbon groups, mention may be made of polymethylene groups of 1 to 20 carbon atoms.

Preferably, the hydrocarbon groups denote the polymethylene groups of 2 to 8 carbon atoms.

The hydrocarbon groups may contain linked to or intercalated in the main chain one or more aromatic rings, 1 or more atoms of oxygen, sulfur, nitrogen, one or more groups -SO-, -S0 ₂ -, -SO ₃ H, amino, alkylamino, hydroxyls, quaternary ammonium or ureido.

Among the monohydroxyalkyl groups, mention may in particular be made of hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

Among the polyhydroxyalkyl radicals, mention may, for example, be made of the dihydroxyethyl, dihydroxypropyl, trihydroxypropyl and dihydroxybutyl radicals. The thioalkyl radicals denote a group -R-SH,

R representing an alkyl group as defined above.

Cyanoalkyl radicals denote a group -R-C = N, R representing an alkyl group as defined above.

The alkoxy groups denote a group -O-R, R representing an alkyl group as defined above.

The acyl groups denote a group -OC-R, R representing an alkyl group as defined above.

The acetyloxy groups denote a group -O-CO-R, R representing an alkyl group as defined above. Among the cycloalkyl radicals, mention may in particular be made of cyclohexyl and cyclopentyl.

Among the aryl radicals, mention may in particular be made of phenyl or naphthyl groups.

Among the alkylaryl groups, mention may in particular be made of the benzyl, phenethyl or naphthylmethyl group. Among the aromatic rings, from 5 to 7 members, mention may, for example, be made of the aryl and alkylaryl rings mentioned above. The preferred aromatic rings are phenyl, pyrimidine, pyridine, pyrrole and pyrazole. In the context of the present invention, the cycloalkyl radicals and the aromatic rings can be substituted by one or more halogen atoms, hydroxyl, amino, alkyl or hydroxyalkyl groups at CC ₆ .

X® represents in particular an anion derived from a halogen such as chlorine, bromine, fluorine or iodine, an anion derived from mineral acids such as phosphoric acid or sulfuric acid or an anion derived from an organic sulfonic or carboxylic acid, in particular an alkanoic acid having from 1 to 12 carbon atoms such as acetic acid, a phenylacanoic acid such as phenylacetic acid, benzoic acid, citric acid or paratoluene acid sulfonic. Preferably, X® represents an anion derived from a halogen and more preferably still X® represents a chloride or bromide anion.

In a preferred embodiment of the present invention A _} ® and / or A ₂ ® represents a heterocycle of formula (II) comprising

2 nitrogen atoms and 3 carbon atoms.

In another preferred embodiment of the present invention, at least one of the groups A _j ® or A ₂ ® denotes a quaternary imidazole group of formula (IV):

? 7

N- N— (IV) R ₈ - C - 'C— Rg

in which: R ₇ , Rg and R ₉ , identical or different, denote an atom hydrogen, halogen, a hydroxyl, nitro, cyano, sulfhydryl, carboxyl group, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl, acetyloxyl group, a cycloalkyl, aryl, alkylaryl group or an -NHR group _N in which R _N denotes an acetyl or ureido group; the radicals Rg and Rg can also form, jointly with the atoms to which they are attached, an aromatic ring of 5 to 7 members. In another embodiment of the present invention, at least one of the groups A _χ ® or A ₂ ® denotes a quaternary pyrazole group of formula (V):

-N- -N-

R ιo - C— Ru ç ^(γ)

in which :

R ₁₀ , Ru and R ₁₂ , identical or different, denote a hydrogen or halogen atom, a hydroxyl, nitro, cyano, sulfhydryl, carboxyl group, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl group , acetyloxyl, a cycloalkyl, aryl, alkylaryl group or a group

-NHR _N in which R _N denotes an acetyl or ureido group; two of the radicals R ₁₀ , R or R ₁₂ can also form, together with the atoms to which they are attached, an aromatic ring of 5 to 7 members. In another preferred embodiment of the present invention, the groups A _j ® and A2 simultaneously denote a quaternary imidazole group of formula (IV), in which R ₇ , Rg and R ₉ , identical or different, denote an atom of hydrogen, a hydroxyl, nitro, cyano, sulfhydryl, carboxyl group, an alkyl, monohydroxyalkyl or polyhydroxyalkyl group; the radicals R _g and R ^ can also form, together with the atoms to which they are attached, an aromatic ring of 5 to 7 members;

In another particularly preferred form of the present invention, the groups A _] _® and A2® simultaneously denote a quaternary imidazole group of formula (IV) in which R ₇ , Rg and R ₉ , identical or different, denote an atom of hydrogen, a C _j to C ₆ alkyl group and the radicals R _g and R _g can form, together with the atoms to which they are attached, a phenyl ring.

In another preferred embodiment of the present invention, A _j ® represents a quaternary ammonium of formula (III) in which R ₅ and R ₆ , identical or different, denote a hydrogen atom or a C _j alkyl group with C ₆ or together with nitrogen form a six-membered group and A ₂ ® denotes a quaternary imidazole group of formula (IV) in which R ₇ , Rg and R, identical or different, denote a hydrogen atom, an alkyl in C- _j -Cg and the radicals R _g and R ₉ can also form, together with the atoms to which they are attached, a phenyl ring.

In a preferred embodiment of the invention, B ₁ denotes a group chosen from the following groups:

i) - (CH ₂ ) _n - with n denoting an integer from 2 to 6

ϋ) -CH ₂ -CH = CH-CH ₂ -

iii) -CH ₂ -C≡ C-CH ₂ -

iv) -CH (CH ₃ ) - (CH ₂ ) ₂ -

v) -CH ₂ CHOH-CH ₂ -

vi) - [CH ₂ -CH ₂ -0] _χ -CH ₂ -CH ₂ - with x = 1-15 10

vii) CH,

viii)

CH,

-CH - CHOH-CH - 0 9 // 0-CH ₂ - CHOH CH ₂ I

CH,

R 13r Ris,

I ix) -B, -Si ^• O— Si- B ₃ - II

R _l 4 Rit q

in which R ₁₃ , R ₁ , R ₁₅ and R ₁₆ , identical or different, denote an alkyl radical in CC ₆ or the phenyl radical, q denotes an integer or decimal number from 0 to 50, preferably from 0 to 10 and B ₃ denotes B ₂ or - (CH ₂ ) _t - with t denoting an integer from 1 to 6. In a preferred embodiment of the invention, B ₂ denotes a group - (CH ₂ ) _m - in which m is a whole number from 1 to 6 and preferably from 1 to 4.

Preferably, in the polymers mentioned above

X® represents a halide, and more particularly Cl ^" or Br ^~ and

R _j , R ₂ , R ₃ and R denote a methyl radical.

Particularly preferred polymers are the polymers corresponding to formula (I) in which A _j ® and A ₂ ® simultaneously denote a quaternary group of formula (IV) with R ₇ =

Rg = R ₉ = H, B _j denotes - (CH ₂ ) _n - in which n is an integer of

2 to 6 or //

- CH, - ( ^{7 x} ) - CH, - 11

B ₂ denotes - (CH ₂ ) _m - in which m is an integer from 1 to 4, p is an integer from 0 to 4, R ^ = R2 = CH3 when p = 0 and R ^ = R2 = R3 = R4 = CH3 when p> 0 and X® represents a chloride or bromide anion.

The polymers of the present invention have an average molecular weight preferably between 1,000 and 20,000 by mass, measured by gel permeation chromatography, taking polyethylene glycol as a reference. The synthesis of the compounds of the present invention is carried out in two stages. The first step consists in synthesizing the diamine and the second step consists either in the quaternization of the diamine in the presence of a dihalide or a disulfonate, or in the condensation in the presence of an inorganic or organic acid of the diamine on a diepoxide.

The synthesis of the diamine is carried out by the reaction of the corresponding diazole with a dihalide or a disulfonate in a solvent, in the presence of a base, at a temperature between room temperature and reflux. These solvents can be water, aromatics such as benzene, toluene, dimethyl sulfoxide, tetrahydrofuran, dimethyl oramide.

These solvents can also be used as a mixture. The bases can consist of hydroxides such as sodium hydroxide, potassium hydroxide or amides, carbonates or hydrides.

This synthesis can also take place in phase transfer by the addition of a phase transfer agent.

Syntheses are described in particular in the documents J. Elguero and AU, Journal of Heterocyclic Chemistry 25, 771-782 (1988), Yin-hung So, Macromolecules 25,516-520 (1992) and RG Xie and ail, Chinese Chemical Letters 7, 321-324 (1996).

The quaternization with a dihalide or a disulfonate is carried out according to the following scheme: 12

Ai— B _r -A, + X— B ₂ - Si- -O— Si- ^• B, - XIR, Ri

© © Ri R,

-A 1— B, 1— A ₂ 2— B ₂ 2— S ji -O— S, i -B ₂ - σ)

x ^e x ^{Θ R} ' ^LR P

in which A ^, A ₂ ®, B _lf B ₂ , RR ₂ , R ₃ , R ₄ , X® and p have the same meaning as above.

It is carried out in a solvent at a temperature between room temperature and reflux. The solvents can be chosen from water, alcohols, aromatics such as benzene, toluene or tetrahydrofuran. These solvents can also be used as a mixture. Preferably, they are chosen from water, alcohols and hydroalcoholic mixtures.

Condensation in the presence of a mineral or organic acid of the diamine on a diepoxide takes place according to the following scheme:

^R > R ₃

A, - Bi - A-, ÇH ₂ -CH— B ₂ - -Si - ^• O-Si- ^• B -ÇΉ ^ CH ₂ IIOR ₂ R ₄ O

HX 13

© © -Ai— B -A ₂ - -B, -Si- ^• - Si- B, (I) I

.Θ Θ R ₂ R ₄ -

X X

in which A ^, A ₂ ®, B _lt B ₂ , R ^ R ₂ , R ₃ , R, X ^Θ and p have the same meaning as above.

This condensation is carried out in the presence of 2 equivalents of HA acid relative to the diamine and at temperatures between 40 ° and 120 ° C and in a hydro alcoholic solvent.

The subject of the present invention is in particular the cosmetic use of a polymer as defined above.

The present invention also relates to the use as a protective agent of keratin fibers of a polymer comprising at least recurring units of formula (I) as defined above.

The subject of the invention is also compositions intended for the cosmetic treatment of keratin fibers and in particular hair containing at least one polymer comprising at least recurring units of formula (I) as defined previously.

These compositions generally contain from 0.01 to 10% by weight of polymer, and preferably from 0.2 to 5%.

The cosmetic compositions according to the invention can be aqueous, hydroalcoholic, solvent-based and optionally contain oils and can be in the form of solutions, lotions, creams, dispersions, gels or aerosols.

The cosmetic compositions according to the invention may contain, in addition to the polymer consisting of at least recurring units of formula (I), all the components used in the cosmetic compositions, in particular anionic, cationic, amphoteric, zwitterionic or nonionic surfactants, foam synergists, foam stabilizers, opacifiers, 14

sequestering agents, thickeners, emulsifiers, softeners, preservatives, protein derivatives, natural substances, colorants, perfumes, anionic, cationic, amphoteric and nonionic polymers. Another subject of the invention consists in a method of cosmetic treatment of keratin fibers, in particular of the hair, in which a cosmetic composition as defined above is applied to the keratin fibers.

The polymers consisting of at least recurring units of formula (I) of the present invention are used in particular in compositions used for the permanent deformation of keratin fibers, in particular the hair or in dyeing or bleaching compositions which constitute another object. of the invention.

The most common technique for obtaining permanent deformation of keratin fibers consists firstly in applying a composition containing a reducing agent to the keratin fibers, then in a second stage, to be applied to the keratin fibers previously tensioned by curlers or other means, an oxidizing composition so as to finally give the keratin fibers the desired shape.

The polymers of the present invention can be contained in the reducing and / or oxidizing composition.

The reducing compositions in accordance with the invention comprise, in a medium suitable for the permanent deformation of the keratin fibers, at least one reducing agent capable of breaking the disulphide bonds at the level of the keratin fibers and at least one silicon heterocyclic quaternary polyammonium polymer as defined herein. -above.

The reducing agents are generally chosen from sulfites, bisulfites or thiols.

Among the preferred reducing agents, oh can cite cysteine, cysteamine and their derivatives such as their salts 15

cosmetically acceptable such as hydrochlorides, hydrobromides, citrates, acetates, sulfates, thiolactic acid, thioglycolic acid, as well as their cosmetically acceptable esters, in particular glycerol thioglycolate. The reducing agents are present in proportions sufficient to reduce the disulfide bonds of keratin, preferably between 1 and 25%, and in particular between 1 and 10% by weight.

The polymers of the present invention may be present in proportions of between 0.01% and 10% by weight of the reducing composition, and preferably between 1% and 5%.

The pH of the reducing compositions is adjusted so as to obtain a pH of between 6.5 and 11.5.

The alkaline agents are preferably chosen from monoethanolamine, diethanolamine, triethanolamine, isopropylamine, 2-methyl-amino-propanol-1, propane diamine 1,3, an alkali or ammonium carbonate or bicarbonate, ammonia, an organic carbonate such as guanidine carbonate or an alkali hydroxide, used alone or as a mixture. This reducing composition can also contain nonionic, anionic, cationic or amphoteric surfactants, commonly used in such compositions. Among these may be mentioned alkyl sulfates, alkylbenzenesulfates, alkylethersulfates, alkylsulfonates, quaternary ammonium salts, alkylbetaines, oxyethylenated alkylphenols, alkylpolyglucosides, fatty acid alkanolamides, oxyethylenated fatty acid esters , as well as nonionic surfactants from the family of hydroxypropyl ethers.

These surfactants are generally used in maximum proportions of 30%, and preferably between 0.5 and 10% by weight relative to the total weight of the composition.

These compositions can also contain thickening agents such as guar gum, tera gum, spruce flour. These compositions can also contain agents 16

treating agents such as volatile or non-volatile, linear or cyclic silicones or their mixtures. Among the silicones, mention may be made of polydimethylsiloxanes, quaternized polyorganosiloxanes as described in FR-A-2,535,730, polyorganosiloxanes containing an aminoalkyl group modified with alkoxycarbonylalkyl groups as described in US Pat. No. 4,749,732 , polyorganosiloxanes such as polydimethylsiloxane-polyoxyalkyl copolymers such as dimethicone copolyol, a polydimethylsiloxane with stearoxy- (stearoxydimethicone) groupings, a polydimethylsiloxane dialkylammonium acetate copolymer or a polydimethylsiloxane2 polyalkyl copolymer, polyalkyl 2-polyoxyalkyl 2-polyoxyalkylinoxylethane 2 polyalkyl 2-polyoxyethyl 2-alkoxyl 2-polyoxyethyl 2-alkoxyl 2-polyoxyalkyl 2 organomodified by mercapto or mercapto-alkyl groups as described in FR-B-1 530 369 and EP-A-0 295 780, as well as silanes such as stearoxy-trimethylsilane. Other ingredients which can be used in the reducing compositions containing the polymers of the invention are chosen from waxes, the polymers chosen from cosmetically acceptable polymers, anionic, cationic other than those of the invention, nonionic or amphoteric, agents of swelling and penetration making it possible to reinforce the effectiveness of the reducing agent such as dimethylisosorbitol, urea and its derivatives, pyrrolidone, n-alkyl-pyrrolidone, thiamorpholinone, alkyl ethers of alkylene glycol or of dialkylene glycol such as for example propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, C ₃ -C ₆ alkane diols such as propanediol-1,2, imidazolidinone-2, as well as other compounds such as fatty alcohols, derivatives lanolin, ceramides, in particular the ceramides themselves, the glycerocamides, the pseudoceramides described in particular in FR-A-95 12399, and in DO NING Journal of Lipid Research, Vol. 35, p. 2060, 1994, or in FR-A-2 673 179, EP-A-0227994, WO-94/07844,

WO-92/05764, active ingredients such as pantothenic acid, panthenol, anti-hair loss agents, anti-dandruff agents, suspending agents, sequestering agents, opacifying agents, dyes, sunscreens, silicone or not, as well as perfumes and preservatives. 17

The silicon polymers of the present invention can also be present in oxidizing compositions used during the permanent shaping of keratin fibers. The invention therefore also relates to an oxidizing composition for the permanent shaping of keratin fibers comprising, in a medium suitable for perming, at least one oxidizing agent and at least one polymer as defined above.

The oxidizing agents can be chosen from hydrogen peroxide, urea peroxides, bromates such as alkali bromates, persalts or a mixture of alkali bromates and a persalt.

When the oxidizing agent consists of hydrogen peroxide, it is present in proportions of between 1 and 10 volumes, and preferably of the order of 8 volumes.

When the bromates are used, the concentration of alkaline bromates is from 1 to 12% and that of persalts from 0.1 to 15% by weight relative to the total weight of the oxidizing composition.

The protective agents of the present invention can be present in proportions of between 0.01% and 10% by weight of the oxidizing composition, and preferably between 1% and 5% by weight.

The pH of these compositions is usually between 2 and 9, and preferably between 3 and 8; it is preferably acidic.

When hydrogen peroxide is used, it can be stabilized by phenacetin, acetaniline, mono- and trisodium phosphates or by 8-hydroxyquinoline sulfates.

Another object of the invention is a process for the permanent shaping of keratin fibers and in particular of the hair, essentially characterized by the fact:

- a keratin reducing composition is applied to the keratin fibers, preferably wet, the reducing composition being applied to the shaped fibers,

- that after a sufficient exposure time to reduce the keratin, an oxidizing composition is applied,

- rinse, preferably with water, after a sufficient exposure time to fix the shaped and reduced fibers 18

during the first stage in a permanent form; the reducing composition and / or the oxidizing composition being as defined above.

The keratin fibers are shaped by various means such as rollers, pliers, hook bands, or simply by hand.

Another object of the present invention is a composition for the direct dyeing of keratin fibers and in particular human keratin fibers such as the hair, comprising in a medium suitable for dyeing, at least one polymer as defined above and at minus a direct dye.

Among the direct dyes conventionally used, there may be mentioned benzene nitro dyes, such as nitrophenylenediamines, ni trodipheny lamines, nitroanilines, nitrated phenol ethers or nitrophenols, nitropyridines, anthraquinone dyes, mono- or di -azoic, triarylmethanic, azinic, acridinic and xantheneic or metalliferous dyes. The direct dyes more particularly preferred according to the invention are chosen from the following: i) the benzene nitro dyes of formula (A) below:

(AT)

in which

- R ₃ denotes an NH ₂ , amino radical monosubstituted by an alkyl, monohydroxyalkyl, polyhydroxyalkyl, aminoalkyl, or amino radical disubstituted by radicals, identical or different, alkyl, mono- or poly-hydroxyalkyl, or aminoalkyl, - R ₄ denotes hydrogen , hydroxy, alkoxy, mono- or poly- 19

hydroxyalkyloxy, or the same meanings designated above for R ₃ , with the exception of the disubstituted amino radical,

- R ₅ denotes hydrogen, alkyl, nitro, or halogen,

ii) the anthraquinone dyes of formula (B) below:

R ₁₀ NH R ₆

(B)

in which

R ₆ denotes hydrogen, a monohydroxyalkyl or polyhydroxyalkyl radical,

- R ₇ denotes hydrogen, an alkyl or alkoxy radical,

Rg denotes hydrogen, a hydroxy, amino or monohydroxyalkylamino or polyhydroxyalkylamino radical,

- R ₉ and R ₁₀ , identical or different, are hydrogen, hydroxy or amino,

iii) the azo dyes of formula (C) below:

12.

(VS)

R 11 _ N =: N- // \

in which:

- R ^ denotes a nitro, amino, amino radical mono- or disubstituted by alkyls, 20

- R ₁₂ denotes hydrogen or an alkyl radical,

- R ₁₃ denotes an amino radical, amino mono- or di-substituted by monohydroxyalkyls, it being understood that the alkyl and alkoxy radicals mentioned above in formulas (A), (B) and (C) are in C _j - C ₄ and that they can be linear or branched, and the cosmetically acceptable salts of all these compounds.

By C _j -C ₄ alkyl is meant in particular the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl radicals.

The term “cosmetically acceptable salts” denotes more particularly the hydrochlorides, hydrobromides and sulphates.

Even more advantageously, according to the present invention, it is preferable to use the following direct dyes: - l-armno-2-nitro-4-N- (β-hydroxyemyl) -amino-5-methyln-benzene,

- 1,4,5,8-tetraaminoanthraquinone,

- 1,4-bis-N, N '- [(β, γ-dihydroxypropyl) -amino] -anthraquinone,

- 1,4,4-N-tris (β-hydroxyethyl) -1,4-diamino-2-nitro-benzene,

- l-N- (β-hydroxyethyl) -amino-2-nitro-4-arnino-benzene, - l-hydroxy-3-nitro-4-amino-benzene

- 1-hydroxy-3-nitro-4-N- (β-hydroxyethyl) -amino-benzene,

- l- (β-hydroxyethyloxy-3-methylamino-4-nitro-benzene,

- l-methylamino-2-nitro-5-β, γ -dihydroxypropyloxy-benzene,

- lN- (β-aminoethyl-anιino-2-nitro-4-β-hydroxyethyloxy-benzene, - 4- [N-ethyl-N- (β-hydroxyethyl) -amino] -lN- (β-hydroxyethyl) -amino -

2-nitro-benzene 1-4'-amino-diphenylazo) -2-methyl-4-N-bis- (β-hydroxyethyl-amino-benzene,

- l-methoxy-3-N- (β-aminoemyl) -amino-4-nitro-benzene, - l-amino-2-nitro-4-N- (β-hydroxyethyl) -amino-benzene,

- 1-amino-2-nitro-4-N-bis- (β-hydroxyethyl) -amino-benzene,

- 1, 4-N-bis (β-hydroxyethyl) -amino-5-nitro-benzene,

1,4-diamino-anthraquinone, and their cosmetically acceptable salts Other preferred cationic dyes are those of the type

ARIANOR (BASIC BROWN 17, BASIC BROWN 16, BASIC 21

YELLOW 57, BASIC BLUE 99) as well as the cationic dyes described in the CIBA patents WO 95/01772, WO 95/15144 and EP 714 954.

The direct dyes, in base or salified form, are generally present in the dye composition according to the invention in proportions which can range from approximately 0.001 to approximately 10%, and preferably from approximately 0.05 to approximately 5%. weight relative to the total weight of the composition.

An object of the invention is also a process for dyeing keratin fibers in which is applied to these keratin fibers, in an amount sufficient to produce a coloration, a composition for direct dyeing as defined above which is left act for a period of between 10 and 60 minutes approximately. The keratin fibers are then rinsed. It is also possible to carry out direct stains without rinsing.

The present invention also relates to compositions for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, containing in a medium suitable for dyeing, at least one polymer as defined above and at least one oxidation dye precursor and / or melanin precursors.

The oxidation dye precursors can in particular be chosen from paraphenylenediamines, para-aminophenols, orthophenylenediamines and heterocyclic bases such as for example pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrazolo-pyrimidine derivatives, indoles or indolines and their acid addition salts.

These compositions can also contain couplers which can in particular be chosen from meta-phenylenediamines, meta-aminophenols, metadiphenols, heterocyclic couplers such as, for example, indole derivatives, indolinic derivatives, benzimidazole derivatives, benzomorpholine derivatives , sesamol derivatives, pyridine, pyrimidine and pyrazole derivatives, and their addition salts with an acid. 22

In general, the addition salts with an acid which can be used in the context of the dye compositions are in particular chosen from hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates and acetates. The medium suitable for direct dyeing or oxidation

(or support) generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water.

Mention may be made, as organic solvent, of lower alkanols such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products and mixtures thereof.

When they are present, the oxidation base or bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition.

When they are present, the coupler (s) preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dye composition.

The polymers of the invention preferably represent from 0.01 to 10% by weight approximately of the total weight of the direct or oxidizing dye composition, and preferably from 0.1 to 5%. The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The pH of the dye compositions is generally between 3 and 12 approximately, and preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers.

Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids 23

such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of following formula:

R4 R ₅

\ /

N - WN p Re / ^H 7 in which W is a propylene residue optionally substituted by a hydroxyl group or a C _j -C ₆ alkyl radical; R _4, R _5, R ₆ and R _7, identical or different, represent a hydrogen atom, a C _j -C ₈ hydroxyalkyl or C-Cg.

The dye compositions comprising a polymer of the present invention may also contain various adjuvants conventionally used in compositions for dyeing keratin fibers, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic, cationic polymers other than those of the invention, nonionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, antioxidants, penetration agents, sequestering agents, perfumes, buffers, agents dispersants, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

The oxidizing compositions used in oxidation dyeing can also contain a heterocyclic quaternary polyammonium silicon polymer as defined above and at least one oxidizing agent, and constitute as such another object of the invention.

These oxidizing agents can in particular be chosen from 24

hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases and two-electron oxidoreductases. The use of hydrogen peroxide or enzymes is particularly preferred.

The oxidizing compositions can also contain various adjuvants conventionally used in compositions for dyeing keratin fibers, such as those defined above.

The subject of the invention is also a process for dyeing keratin fibers, in particular hair, in which is applied to these keratin fibers, in an amount sufficient to dye the keratin fibers, a composition for the oxidation dye as defined above, optionally with an oxidizing composition. In the latter case, only the composition containing the dye precursors or the oxidizing composition can contain a polymer according to the invention.

The composition for the oxidation dye is generally diluted at the time of use with the oxidizing composition in a ratio ranging from 0.5 to 5 and preferably from 1 to 3 volume. The composition thus obtained is left to act for a time of between 5 and 45 minutes approximately and preferably between 15 and 30 minutes, then the keratin fibers are rinsed.

The polymers in accordance with the invention are particularly advantageous in their use as a protective agent in compositions for bleaching keratin fibers, in particular the hair.

The present invention therefore also relates to a bleaching composition containing, in a medium suitable for bleaching, at least one agent bleaching keratin fibers, and in particular human hair and at least one polymer as defined above.

The medium suitable for bleaching can also contain the same constituents as those of the medium suitable for direct or oxidative dyeing. 25

The bleaching compositions can also be in the form of powders.

For bleaching keratin fibers, bleaching agents known per se are used, such as hydrogen peroxide, persulfates, alkaline percarbonates, perborates.

In general, using hydrogen peroxide, compositions which may contain up to 60 volumes of hydrogen peroxide and preferably 10 to 40 volumes are used.

Another subject of the invention is a process for bleaching keratin fibers, and in particular human keratin fibers such as the hair, in which a bleaching composition as defined above is applied to the keratin fibers in an amount and during sufficient time to discolor keratin fibers. The keratin fibers are then washed, rinsed, and dried.

The following examples are intended to illustrate the invention:

Table 1 below is intended to illustrate the preparation of polymers used according to the invention.

This table successively reproduces the indications relating to the structure of the compound of the polymer of formula (I).

A ® ^B l ^B 2 ^R l ^R 2 P ^R 3 R ₄ X ^Θ £

A ₂ ® OJ

00

Ex. Imidazole of imidazole of 1 formula (IV) formula (IV)

0 - - with R ₇ = Rg with R ₇ = Rg (CH ₂ ) ₄ CH ₂ CH ₃ CH ₃ cr mc = R ₉ = H = R ₉ = H

Ex. Imidazole of imidazole of m 2 foπnule (IV) foπnule (IV) σ CH ₂ ) ₃ CH ₃ CH ₃ 1 CH ₃ CH ₃ m with R ₇ = Rg with R ₇ = Rg (CH ₂ ) ₄ (CΓ

70 = R ₉ = H = Rç ₎ = H m

E.g. ammonium imidazole of H

3 quaternary of form (IV)> W

> formula (III) with R = Rg (CH ₂ ) ₃ (CH ₂ ) ₃ CH ₃ CH ₃ 1 CH ₃ CH ₃ cr om with R ^ = Rg = R ₉ = H

> m = CH ₃ z Ex. imidazole of imidazole of

70 4 formula (IV) formula (IV) m with R = Rg with R ₇ = Rg - CH-— ^ ^ -CU, - (CH ₂ ) ₃ CH ₃ CH ₃ 1 CH ₃ CH ₃ Cl ^" O

= R ₉ = H m = R ₉ = H ι Ex. Σ> imidazole of imidazole of Ç ^H 2

5 formula (IV) formula (IV) ÇHOH with R ₇ = Rg with R = Rg - cιι ₂ - —cu ₂ - - CH ₃ CH ₃ 8 CH ₃ CH ₃ AcO ^"

2

= R ₉ = H = R ₉ = H Ô- (CH ₂ ) ₃

E.g. imidazole from o imidazole

H 6 formula (IV) formula (IV) with R ₇ = Rg with R = Rg - ai; - y - cii; - (CH ₂ ) ₃ CH ₃ CH 5 CH ₃ CH ₃ cr

VO

= R ₉ = H = R ₉ = HO O

27

1) Synthesis of Example 1 a) Synthesis of the diamine 1,1 '- (1,4-

Butanediyl) bis (imidazole)

5 35.4 g (0.52 mole) of imidazole, a solution of 100 g (2.5 moles) of sodium hydroxide are introduced into a reactor equipped with mechanical stirring, a thermometer and a condenser. 100 ml of water, 5.15 g of tetrabutylammonium bromide, and 54 g (0.26 mol) of dibromo 1,4-butane dissolved in 240 ml of toluene. This _IQ mixture is brought to reflux for 6 hours. After cooling, the expected diamine crystallizes, it is filtered, the cake obtained is washed with 100 ml of toluene, then with 2 times 50 ml of ice water. The product thus washed is recrystallized from 200 ml of water. After drying, 44 g of light beige powder are obtained (yield: 89%).

15

DMSO proton NMR analysis gave the following results:

6 1.61-1.68 (m, 4H); δ 3.96-4.02 (m, 4H); δ 6.91 (m, 2H); δ 7.17

(m, 2H); δ 7.64 (m, 2H)

B) Synthesis of the polymer:

A mixture of 21.09 g (0.1 mole) of 1.1 '- (1,4-Butanediyl) bis (imidazole) obtained above containing 6.6% of water, 30 ml of methanol and 15.7 g (0.1 mole) of bis (chloromethyl) dimethylsilane at reflux of methanol for 14 hours. The assay with silver nitrate of a test sample shows that 94.6% of the chlorides are in ionic form. The reaction medium is concentrated and dried under vacuum. The very hygroscopic product is put in water so as to obtain a 20% solution of active material.

30

Determination of chlorides by AgN0 ₃ : 1.15 meq C17g of solution.

35 28

2) Summary of Example 2:

A mixture of 10.5 g (0.05 mole) of l, l - (1,4-Butanediyl) bis (imidazole) containing 6.6% water, 40 ml, is brought to 120 ° C. for 38 hours. methanol and 14.35 g (0.05 mole) of 1,3-bis (chloropropyl) tetramethyldisiloxane in a hermetically sealed reactor. The reaction medium is concentrated and then the residue is washed with diisopropyl ether and then dried under a vacuum of 0.1 mmHg at 120 ° C. A vitreous brown, water-soluble polymer is obtained.

Determination of chlorides by AgN0 ₃ : 14.9% (theory: 14.8%).

3) Synthesis of Example 3 a) Synthesis of (3-Imidazol-1-yl-propyl) -dimethylamine

Dimethylaminochloropropylamine hydrochloride (31.6 g, 0.2 mole), imidazole (13.6 g, 0.2 mole) and bromide are introduced into a reactor equipped with a thermometer and a condenser. of tetrabutyl ammonium (4.4 g) in 100 ml of toluene. 80 g of sodium hydroxide dissolved in 80 ml of water are introduced dropwise at a temperature below 50 ° C. The mixture is left stirring at ordinary temperature for 10 hours. 200 ml of toluene and 50 ml of water are added. The intermediate phase is taken up in dichloromethane and dried. After removal of the solvent, the oil obtained is dried under vacuum and is subjected to vacuum distillation of 0.1 mm Hg. The fraction distilling at 91-92 ° C is (3-Imidazol-1-yl-propyl) -dimethylamine.

DMSO proton NMR analysis gave the following results: δ 1.70 (m, 2H), δ 1.97 (t, 2H); δ 2.00 (s, 6H), δ 3.85 (t, 2H); δ 6.76 (m, 1H); δ 7.05 (m, 1H); δ 7.48 (m, 1H). 29

b) Synthesis of the polymer in aqueous solution:

A mixture of 7.66 g (0.05 mol) of 1H-imidazole-1-propanamine N, N-dimethyl 96%, 40 g of methanol and 14.35 g (0.35 g) is brought to 120 ° C. for 28 hours. 0.05 mole) of 1,3-bis (chloropropyl) tetramethyldisiloxane in a hermetically sealed reactor. After cooling, the reaction medium is concentrated. The pale yellow oil obtained is taken up in water and the mixture is concentrated to remove the residual methanol. After assaying the chlorides with AgN0 ₃ , complete with water to obtain 40.4 g of a 50% solution of active material of the polymer.

4) Synthesis of Example 4 a) Synthesis of N, N'-Terephthalylidenebis (imidazole)

In a reactor equipped with a thermometer and a condenser, sodium hydroxide (32 g, 0.8 mole) is introduced into 100 ml of tetrahydrofuran and then an imidazole solution (39.5 g,

0.58 moles) in 300 ml of tetrahydrofuran. After 40 minutes of stirring at room temperature, the initially colorless medium becomes orange-pink. The mixture is brought to 60 ° C. and dichloro-p-xylene (49 g, 0.28 mole) is added in portions over 25 minutes, then the mixture is left to stir for 8 hours at 60 ° C. The reaction mixture which contains an insoluble material is cooled, then 1.4 l of water are added thereto. The NaCl precipitate dissolves, then another white precipitate appears.

We filter it. After drying, 49.9 g (yield: 74.8%) of an off-white powder of N, N'-Terephthalylidenebis (imidazole) are obtained.

DMSO proton NMR analysis gave the following results: δ 5.01 (s, 4H); δ 6.74 (s, 2H); δ 7.01 (s, 2H); δ 7.08 (m, 4H); δ 7.58 (s, 2H). 30

b) Synthesis of the polymer in aqueous solution

A mixture of 7.66 g (0.05 mole) of N, N'-terephthalylidenebis (imidazole), 40 g of methanol and 14.35 g (0.05 mole) of l is brought to 120 ° C. for 28 hours. , 3-bis (chloropropyl) tetramethyldisiloxane in a hermetically sealed reactor. After cooling, the reaction medium is concentrated. The pale yellow oil obtained is taken up in water and the mixture is concentrated to remove the residual methanol. After assaying the chlorides with AgN0, complete with water to obtain 42 g of a 50% solution of active material of the polymer.

5) Summary of Example 5

We add to a solution of N, N'-

Terephthalylidenebis (imidazole) (1.19 g, 0.005 mole) in 7 g of water and 0.64 g of acetic acid brought to 60 ° C in 20 minutes from the, α diepoxypropoxypropyldiorganodimethylsiloxane (DMS-E12 (p = 9 ) of

GELEST, 5 g, 0.005 mole). 5 ml of isopropanol are added and after 1 hour, the mixture is transferred to a hermetically sealed reactor and the whole heated to 120 ° C. for 10 hours. After cooling and evaporation of the solvents, a viscous orange-yellow polymer oil is obtained, the NMR spectrum of the DMSO proton is in accordance with the expected formula.

31

6) Synthesis of Example 6 in aqueous solution

A mixture of 1.13 g (0.01 mole) of N, N'-Terephthalylidenebis (imidazole), 20 g of isopropanol and 5.83 g (0.01) mole d is brought to 120 ° C. for 20 hours. ', o chloropropyl-dodecamethyl-hexasiloxane in a hermetically sealed reactor. After cooling, the reaction medium is concentrated. The yellow oil obtained is taken up in water and the mixture is concentrated to remove the residual isopropanol. After determination of chlorides by

AgN0 ₃ , complete with water to obtain 13.5 g of a 50% solution of active polymer material.

The following examples are intended to illustrate the compositions and the application of the polymers in accordance with the invention.

32

APPLICATION EXAMPLE 1

The following composition is prepared:

2,6-dimethyl 1,4-diaminobenzene dihydrochloride 0.3 g

1-amino 4-hydroxybenzene 0.15 g

1,3-dihydroxybenzene 0.15 g

1-hydroxy 3-amino benzene 0.1 g

Tertiobutylhydroquinone 0.04 g Thiolactic acid 0.4 g

Mixed ethyl and stearyl alcohols 50/50 17.0 g

2-octyl dodecanol 2.8 g

Cetyl stearyl alcohol with 15 moles of ethylene oxide 2.8 g

Ammonium lauryl sulfate at 30% M.A. 11.5 g Aqueous solution of the polymer of Example 2 3.0 g M.A.

Ammonia at 22 ° Be 12.0 g

Water qs 100 g

This composition is used for the oxidation dye of the hair.

The composition obtained is mixed with 1.5 times its weight of hydrogen peroxide at 20 volumes and whose pH is 3.

The mixture thus produced is applied to dark blond hair for 30 minutes.

The hair is then rinsed, washed with a standard shampoo and then dried. The hair has a light blond coloring and is soft to the touch, shiny and easily disentangled. 33

APPLICATION EXAMPLE 2

The following composition is prepared:

Oleocetyl alcohol oxyethylenated with 30 moles of ethylene oxide 7 g

Lauric alcohol with 12 moles of ethylene oxide 8 g

Decyl alcohol with 3.5 moles of ethylene oxide 22 g

Cetylstearyl alcohol 5 g Aqueous solution of the polymer of Example 2 1 g M.A,

Propylene glycol 6 g

20% NH ₃ aqueous ammonia solution 10 g

Paraphenylenediamine 0.4 g m-aminophenol 0.5 g Hydroquinone 0.1 g

1-phenyl 3-methyl 5-pyrazolone 0.1 g

35% MA aqueous sodium bisulfite solution 1.3 g

Perfume, sequestering qs

Water qs 100 g

This composition is used for the oxidation dye of the hair. The composition obtained is mixed, weight for weight, with hydrogen peroxide titrating 20 volumes and whose pH is 3.

The mixture thus produced is applied to bleached hair for 30 minutes.

The hair is then rinsed, washed with a standard shampoo and then dried.

The hair has a purple color and is soft to the touch, shiny and easily disentangled. 34

APPLICATION EXAMPLE 3

The following composition is prepared:

2 amino 5β hydroxy ethyloxynitrobenzene 0.35 g 2 amino 4 methyl 5N β hydroxyethylamino nitrobenzene 0.05 g

Nonylphenol with 9 moles of EO 8 g

Diethanolamine lauric 2 g

Aqueous solution of the polymer of Example 2 0.8 g M.A. Monomethyl ether of propylene glycol 10 g

2 amino 2 methylpropanol qs pH 9.5

Demineralized water qs 100.0 g

This composition is used for direct dyeing of the hair.

It is applied 20 minutes to gray hair with 90% white.

The hair is then rinsed and dried.

The hair has a golden copper color and is soft to the touch, shiny and easily disentangled.

Claims

35 CLAIMS

1. Polymers comprising at least units of formula (I):

θ Θ

-A _χ - Bi— A ₂ - B ₂ - - îSi ¹ (I)

1 - -O— S | i- -B ₂ Θ e R ₂

^• y YLR ₄ _ P

_I Q in which:

• A _j ® and A ₂ ®; identical or different, denote: a) a quaternary unsaturated heterocycle of formula (II):

15 -N VÇ

I! + (II)

in which

E, G, L, J, identical or different, denote a carbon, oxygen, sulfur or nitrogen atom, at least one denoting a nitrogen atom;

E, G, L, J may be substituted, when one or more of these atoms denote a carbon atom, by one or more atoms

25 halogen, hydroxyl groups, nitro, cyano, sulfhydryl, carboxyl, alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl, acetyloxyl, substituted or unsubstituted cycloalkyl groups, alkylaryl substituted or not or by one or more groups - NHR _N in which R _N denotes a

30 acetyl or ureido group; when E, G, L, or J denote a third nitrogen atom, 36

this can be substituted by a hydrogen, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, substituted or unsubstituted aryl radical or a substituted or unsubstituted alkylaryl radical, the substituents of two of the atoms E, G, L and J can also form jointly with the atoms to which they are attached a substituted or unsubstituted 5 to 7-membered aromatic ring; or b) a quaternary ammonium of formula (III)

Rs ® l (III)

- NOT-

R.

in which:

R ₅ and R _{6, which are} identical or different, denote a carboxyl group, an alkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl, acetyloxy group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl, substituted or unsubstituted alkylaryl or a group - NHR _N in which R _N denotes an acetyl or ureido group;

R ₅ and R ₆ can also form, together with the nitrogen atom to which they are attached, a saturated cycle of 5 to 7 carbon links; and at least one of the groups A _j ® and A ₂ ® denotes a quaternary unsaturated heterocycle of formula (II);

• p denotes an integer or decimal number from 0 to 50;

• B _j denotes an α, ω bis alkyl polysiloxane group or a hydrocarbon chain, linear or branched, saturated or unsaturated containing up to 6 consecutive carbon atoms, which can comprise one or more hydroxyl groups and which can be interrupted by one or more atoms oxygen and / or more aromatic rings;

• B ₂ denotes a hydrocarbon chain, linear or branched, saturated or unsaturated containing up to 6 consecutive carbon atoms, 37

may have one or more hydroxyl groups and may be interrupted by one or more oxygen atoms and / or more aromatic rings.

• R _j, R _2, R ₃ and R _4, identical or different, denote an alkyl radical in C C _g or phenyl.

• X® denotes an anion derived from a mineral or organic acid.

2. Polymers according to claim 1, characterized in that at least one of the groups A _j ® or A2® denotes a quaternary imidazole group of formula (IV):

Pr

VS

- N 'VN- (IV)

-_-. '

C- ^• Rα

in which

R ₇ , Rg and R ₉ , identical or different, denote a hydrogen or halogen atom, a hydroxyl, nitro, cyano, sulfhydryl, carboxyl group, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl, alkoxy, acyl group , acetyloxyl, a cycloalkyl, aryl, alkylaryl group or a group

-NHR _N in which R _N denotes a hydrogen atom, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, acetyl or ureido group; the radicals R ₈ and R ₉ can also form, together with the atoms to which they are attached, an aromatic ring of 5 to 7 members.

3. Polymers according to claim 1 or 2, characterized in that a n aauu mmooiinnss ddeess ggrroouuppeemmeennttss AA _j ^ ®®oovu. ^, denotes a quaternary pyrazole group of formula (V): 38

-N- - N—

Rio— • R 12 f (T)

^ 11

in which :

I Λ R ₁₀ , R ^ and R ₁₂ , identical or different, denote a hydrogen or halogen atom, a hydroxyl, nitro, cyano, sulfhydryl, carboxyl group, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, thioalkyl, cyanoalkyl group, alkoxy, acyl, acetyloxyl, a cycloalkyl, aryl, alkylaryl group or an ir -NHR _{N group} in which R _N denotes a hydrogen atom, an alkyl, monohydroxyalkyl, polyhydroxyalkyl, acetyl or ureido group; two of the radicals R ₁₀ , R or R ₁₂ can also form, together with the atoms to which they are attached, an aromatic ring of 5 to 7 members.

20

4. Polymers according to claim 1 or 2, characterized in that the groups A _j ® and A ₂ ® simultaneously denote a quaternary imidazole group of formula (IV), in which R ₇ , Rg and R ₉ , identical or different, denote a hydrogen atom, a hydroxyl, nitro, cyano, sulfhydryl, carboxyl group, an alkyl, monohydroxyalkyl or polyhydroxyalkyl group; the radicals Rg and R ₉ can also form, jointly with the atoms to which they are attached, an aromatic ring of 5 to 7 members;

30

5. Polymers according to any one of claims 1, 2 or 4, characterized in that A _j ® and A ₂ ® simultaneously denote a quaternary imidazole group of formula (IV) in which R ₇ , Rg and R ₉ , identical or different, denote a hydrogen atom, a

3 C _j to C ₆ alkyl group and the radicals R ₈ and R ₉ can 39

also form together with the atoms to which they are attached a phenyl ring.

6. Polymers according to claim 1 or 2, characterized in that A _j ® represents a quaternary ammonium of formula (III) in which R ₅ and R ₆ , identical or different, denote a hydrogen atom, a C alkyl group _j to C ₆ or jointly form a 6-membered ring and A ₂ ® denotes a quaternary imidazole group of formula (IV) in which R ₇ , Rg and R ₉ , identical or different, denote a hydrogen atom, alkyl in

C _j -Cg and the radicals Rg and R ₉ can also form, together with the atoms to which they are attached, a phenyl ring.

7. Polymers according to any one of claims 1 to 6, characterized in that B _j denotes a group chosen from the following groups:

i) - (CH ₂ ) _n - with n = 2-6

ϋ) -CH ₂ -CH = CH-CH ₂ -

iii) -CH ₂ -C ^ C-CH ₂ -

iv) -CH (CH ₃ ) - (CH ₂ ) ₂ -

v) -CH ₂ CHOH-CH ₂ -

vi) - [CH ₂ -CH _r O] _χ -CH ₂ -CH ₂ - with x = 1-15

vii) -CH, -CH, - 40

viii)

CH,

- CH ₂ - CHOH-CH ₂ - 0 & C ((y 0-CH ₂ - CHOH CH ₂

CH ₃

R 13r R 15-, II ix) - B, -Si ^• O— Si- B ₃ - IR ₁₄ Ri 6 ^

in which R ₁₃ , R ₁₄ , R ₁₅ or R _16> identical or different, denote a C _j -C ₈ alkyl radical or the phenyl radical, q denotes an integer or decimal number from 0 to 50 and B ₃ denotes B ₂ as defined in claim 1 or - (CH ₂ ) _t - with t = 1-6.

8. Polymers according to any one of claims 1 to 7, characterized in that B ₂ denotes a group - (CH ₂ ) _m - and m denotes an integer from 1 to 6.

9. Polymers according to any one of claims 1 to 8, characterized in that R _j , R ₂ , R ₃ and R ₄ denote CH ₃ .

10. Polymers according to any one of claims 1, 2,

4, 5 and 7 to 9, characterized in that the groups A ^ θ ° and A ₂ θ simultaneously denote a quaternary imidazole group of formula (IV) as defined in claim 2 with R ₇ = R _g = R ₉ = H, _λ denotes - (CH ₂ ) _n - with n = 2-6, or

-CH- CH, -

B ₂ denotes - (CH ₂ ) _m - with m = 1-4, p is an integer from 0 to 4, when p = 0 then R _! = R ₂ = CH ₃ and as p> 0 then R = R ₂ = R ₃ = R ₄ = CH ₃ and X® represents a chloride anion or. bromide. 41

11. Cosmetic use of a polymer as defined in any one of claims 1 to 10.

12. Use as protective agent of keratin fibers of a polymer as defined in any one of claims 1 to 10.

13. Composition intended for the cosmetic treatment of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it contains at least one polymer as defined in any one of claims 1 to 10.

14. Composition according to claim 13, characterized in that it contains from 0.01% to 10% by weight of polymer as defined in any one of claims 1 to 10.

15. Reducing composition for the permanent shaping of keratin fibers, characterized in that it contains in a medium suitable for the permanent, at least one reducing agent and at least one polymer as defined in any one of claims 1 to 10.

16. Composition according to claim 15, characterized in that the reducing agent is chosen from sulfites, bisulfites and thiols.

17. Reducing composition according to claim 15 or 16, characterized in that the reducing agents are chosen from cysteine, cysteamine and their cosmetically acceptable salts, thiolactic acid, thioglycolic acid and their cosmetically acceptable esters.

18. Reducing composition according to any one of claims 15 to 17, characterized in that it contains 0.01 to 10% by weight of polymer as defined in any one of claims 1 to 10.

19. Oxidizing composition for the permanent shaping of keratin fibers, characterized in that it contains, in a medium suitable for the perm, at least one oxidizing agent and at least one polymer as defined in any one of the claims 1 to 10. 42

20. Oxidizing composition according to claim 19, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxides, bromates such as alkali bromates, persalts or a mixture of alkali bromates and d 'a parsley.

21. Oxidizing composition according to claim 19 or 20, characterized in that it contains from 0.01 to 10% by weight of a polymer as defined in any one of claims 1 to 10.

22. A process for permanently forming keratin fibers, characterized in that a reducing composition is applied to the keratin fibers, that after an exposure time sufficient to reduce the keratin, an oxidizing composition is applied and that rinsing is carried out, after an exposure time sufficient to fix the keratin fibers in a permanent form; the reducing composition and / or the oxidizing composition being respectively as defined in any one of claims 15 to 18 and as defined in any one of claims 19 to 21.

23. Composition for the direct dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing, at least one polymer as defined in one any of claims 1 to 10 and at least one direct dye.

24. Composition according to Claim 23, characterized in that the direct dye is chosen from azo dyes, anthraquinone dyes and nitro derivatives of the benzene series.

25. Process for coloring keratin fibers, and in particular human keratin fibers such as the hair, characterized in that the composition as defined in is applied to the keratin fibers, in an amount sufficient to produce a coloring claim 23 or 24, which the composition is left to act for a period of between 10 and 60 minutes approximately and that the keratin fibers are optionally rinsed.

26. Composition for the oxidation dyeing of fibers 43

keratin, in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing, at least one polymer as defined in any one of claims 1 to 10 and at least an oxidation dye precursor and / or a melanin precursor.

27. Composition according to Claim 26, characterized in that the precursors of oxidation dyes are chosen from paraphenylenediamines, paraaminophenols, orthophenylenediamines and heterocyclic bases.

28. Composition according to claim 26 or 27, characterized in that it also contains couplers.

29. Composition according to claim 28, characterized in that the couplers are chosen from metaphenylenes diamines, metaaminophenols, metadiphenols, heterocyclic couplers, indolinic derivatives, benzomidazole derivatives, benzomorpholine derivatives, sesamol derivatives , pyridine, pyrimidine and pyrazole derivatives and their acid addition salts.

30. Dye composition according to any one of claims 23, 24 and 26 to 29, characterized in that it contains from 0.01% to 10% by weight of a polymer as defined in any one of claims 1 to 10.

31. Oxidizing composition for the oxidation dyeing of keratin fibers, characterized in that it contains, in a medium suitable for dyeing, at least one oxidizing agent and at least one polymer as defined in any one of claims 1 to 10.

32. Oxidizing composition according to claim 31, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases and two-electron oxidoreductases.

33. Process for the cosmetic treatment of keratin fibers, in particular of the hair, characterized in that it is applied to 44

keratin fibers a composition as defined in claim 13 or 14.

34. Process for dyeing keratin fibers, and in particular human keratin fibers such as the hair, characterized in that a composition for dyeing is applied to the keratin fibers, in an amount sufficient to dye the keratin fibers for oxidizing keratin fibers containing a dye precursor, diluted at the time of use with an oxidizing composition, allowing the composition thus obtained to act for a period of between 5 and 45 minutes and rinsing the keratin fibers ; the composition for the oxidation dye of keratin fibers and / or the oxidizing composition being respectively as defined in any one of claims 26 to 30 and as defined in claim 31 or 32.

35. Bleaching composition, characterized in that it contains, in a medium suitable for bleaching, at least one agent which bleaches keratin fibers and at least one polymer as defined in any one of claims 1 to 10.

36. Composition according to claim 35, characterized in that the bleaching agent is chosen from hydrogen peroxide, persulfates, sodium percarbonates and perborates.

37. Process for bleaching keratin fibers, characterized in that the bleaching composition defined in claim 35 or 36 is applied to the keratin fibers in an amount and for a duration sufficient to discolor the keratin fibers and that then rinse.