EP1237528A1

EP1237528A1 - Composition for permanent bleaching or deformation of keratin fibers comprising a thickened polymer with an aminoplastic ether sk eleton

Info

Publication number: EP1237528A1
Application number: EP00979710A
Authority: EP
Inventors: Frédéric Legrand; Delphine Allard
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1999-12-08
Filing date: 2000-11-10
Publication date: 2002-09-11
Also published as: FR2802093A1; AU1711001A; JP2003516335A; US6984250B1; FR2802093B1; WO2001041722A1

Abstract

The invention relates to a composition for permanent bleaching or deformation of keratin fibers, especially human keratin fibers such as hair. The inventive composition comprises at least one reducing agent and at least one thickening polymer with an aminoplastic ether skeleton in an appropriate medium for bleaching or deformation. The invention also relates to methods and devices for permanent bleaching or deformation of keratin fibers by means of said composition.

Description

COMPOSITION FOR BLEACHING OR PERMANENT STRAIN FIBER KERATINI _Q UES WITH POLYMER thickened SKELETON AMINOPLAST-ETHER

The present invention relates to a composition for bleaching or permanently deforming keratin fibers and in particular human keratin fibers such as the hair, comprising at least one reducing agent and at least one thickening polymer with an aminoplast-ether skeleton.

It is known to bleach keratin fibers and in particular human hair, with bleaching compositions containing one or more oxidizing agents. Among the oxidizing agents conventionally used, mention may be made of hydrogen peroxide or of compounds capable of producing hydrogen peroxide by hydrolysis, such as urea peroxide or persalts such as perborates, percarbonates and persulfates, hydrogen peroxide and persulfates being particularly preferred.

But it is also known to bleach human keratin fibers such as the hair and in particular the hair artificially dyed with exogenous dyes, using reducing agents such as ascorbic acid or thiols such as cysteine.

It is also known to carry out permanent deformation of the hair by applying to the latter compositions containing one or more reducers, the hair having preferably been previously tensioned, in particular using mechanical devices such as curlers, the hair thus reduced then being reoxidized in the desired shape, most often after rinsing, by means of the oxygen in the air, but more generally via an oxidant which is preferably chosen from hydrogen peroxide or alkaline bromates. The reducing agents preferably used in the context of permanent deformation of the hair are thiols such as thioglycolic acid, its salts and esters, thiolactic acid and its salts, cysteine or cysteamine, and sulfites. The compositions intended for bleaching the hair using reducing agents are mainly in the form of ready-to-use compositions consisting of anhydrous products (powders or creams) containing the reducing agent (s) which are mixed at the time. use with an aqueous composition optionally containing a pH agent. The bleaching compositions are also in the form of aqueous ready-to-use compositions containing the reducing agent (s) at the appropriate pH.

The reducing compositions for the permanent deformation of the hair are generally in the form of aqueous compositions ready for use or in the form of anhydrous powdery or liquid compositions which are mixed at the time of use with an aqueous composition at the appropriate pH.

To locate the product of discoloration or permanent deformation when applied to the hair, so that it does not run on the face or outside the areas which it is proposed to treat, we have so far used the use of traditional thickeners such as crosslinked polyacrylic acid, hydroxyethylcelluloses, certain polyurethanes, waxes, and in addition, in the case of bleaching compositions, with mixtures of nonionic surfactants of HLB (Hydrophilic Lipophilic Balance), which, suitably chosen, generate the gelling effect when diluted with water and / or surfactants.

However, the Applicant has found that the thickening systems mentioned above did not make it possible to obtain sufficiently powerful and homogeneous discolourations or permanent deformations. Furthermore, it also found that the compositions for bleaching or permanent deformation of the hair, ready to use, containing the reducing agent or agents, and in addition the thickening systems of the prior art did not allow a sufficiently precise application. without drips or drops in viscosity over time. Now, after significant research carried out on the question, the Applicant has now discovered that it is possible to obtain compositions for bleaching or permanent deformation of the hair containing at least one reducing agent, ready to use, which do not flow and therefore remain well located at the point of application, and which also make it possible to obtain permanent and powerful and homogeneous discolourations or deformations, if an effective amount of a polymer with an aminoplast-ether skeleton is introduced into the composition.

These discoveries are the basis of the present invention.

The present invention thus relates to a ready-to-use composition for bleaching or permanent deformation of keratin fibers, in particular human keratin fibers, such as the hair, comprising, in a medium suitable for bleaching or permanent deformation , at least one reducing agent, which is characterized in that it also contains at least one polymer with an aminoplast-ether backbone.

By “ready-to-use composition” is meant, within the meaning of the invention, the composition intended to be applied as it is to keratin fibers, ie it can be stored as it is before use or result from extemporaneous mixture of two or more compositions.

When the ready-to-use composition according to the invention results from the extemporaneous mixture of several compositions, the polymer with an aminoplast-ether skeleton may be present in one or more or in all of the mixed compositions.

In this way, the polymer with an aminoplast-ether backbone can be present in an anhydrous composition in the form of preferably powdery powder or cream and / or in one or more aqueous compositions.

Preferably according to the invention, the polymer or polymers with an aminoplast-ether skeleton are present in at least one aqueous composition which is mixed with moment of use with a composition either aqueous or anhydrous in the form of powder or cream and containing at least one reducing agent. Another preferred form of the invention is a unique composition containing the reducing agent (s) and the polymer (s) with an aminoplast-ether skeleton. Another object targeted by the present invention is an anhydrous composition containing at least one reducing agent and at least one polymer with an aminoplast-ether skeleton, said composition being intended to be diluted before application to the fibers.

The invention also relates to a bleaching process or a process for permanent deformation of keratin fibers, and in particular of human keratin fibers such as the hair using the bleaching or permanent deformation composition ready for use as described according to invention, the application of said composition can be followed, in the case of permanent deformation, by the application, optionally after rinsing, of an oxidizing composition.

The invention also relates to bleaching devices or "Kits" for packaging containing such a ready-to-use composition.

Thus, a device with two compartments comprises a first compartment containing at least one powder or an anhydrous cream or an aqueous composition, and the second compartment an aqueous composition, at least one of the two compartments containing at least one reducing agent and the at least one of the two compartments containing at least one polymer with an aminoplast-ether skeleton.

However, other characteristics, aspects, objects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.

By aminoplast-ether is understood within the meaning of the present invention, any product resulting from the condensation of an aldehyde with an amine or an amide. By aminoplast-ether is also meant in the sense of the present invention, any structural unit formed of an aminoplast residue and a divalent hydrocarbon residue linked to the aminoplast residue by an ether bond.

The polymers with an aminoplast-ether skeleton used according to the invention are preferably chosen from those containing at least one unit of structure (I) below:

in which :

-AMP is an aminoplast residue with alkylene units,

-R denotes a hydrogen atom, a C1C4 alkyl radical or an acyl radical

C1C4,

-RO1 is a divalent alkyleneoxy residue,

-p denotes a positive integer, the OR group or groups being linked to the alkylene units of the AMP residue.

Preferably, the polymers with an aminoplast-ether skeleton are chosen from those containing at least one unit of structure (II) as follows:

in which :

-AMP, R, RO-i and p have the same meaning as above,

- RO2 is a hydrophobic group different from RO linked to AMP via a heteroatom and comprising at least two carbon atoms, and, -q is a positive integer. Even more preferably, the polymers of the invention have the following formulas (III) and (III) bis:

in which :

AMP, R, RO- _j , RO2, P and q have the same meaning as before, R2 or

R3, identical or different, represent a terminal group which can denote a hydrogen atom, a group RO-j H, a group RO2H, a group AMP (OR) p or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl , alkyloxyalkyle, aryloxyalkyle, cycloalkoxyalkyle, a being a number greater than 1 and preferably greater than 2.

The aminoplast residues carrying their OR groups integrated into the polymers of the invention can be chosen without limitation from the following structures (IV) to (XV):

in which :

R has the same meaning as before,

R1 denotes C1C4 alkyl, y is a number at least equal to 2, x denotes 0 or 1.

Preferably, the aminoplast residue (s) carrying their OR groups are chosen from those of structure (XVI) below:

in which R, p, and x have the same meanings as before.

The divalent alkyleneoxy residues are preferably those corresponding to the diols of general formula (XVII) below: HO- (ZO) y- (Z1 (Z2O) w) t- (Z'O) y'-Z3OH (XVII), y and y 'being numbers ranging from 0 to 1000, t and w being numbers ranging from 0 to 10,

Z, Z ', Z2 and Z3 are C2C4 alkylene radicals and preferably radicals

-CH2-CH (Z4) - and -CH2-CH (Z4) -CH2-, Z1 being a linear or cyclic radical, branched or not, aromatic or not, comprising or not one or more heteroatoms and having from 1 to 40 carbon atoms,

Z4 denoting a hydrogen atom or a C1C4 alkyl radical or a C1C3 acyl radical, it being understood that at least one of the radicals Z4 of the radicals Z, Z ', Z2 and Z3 is different from acyl.

Preferably Z4 denotes a hydrogen atom or a methyl radical.

Even more preferably t = 0 and Z, Z 'and Z3 denote -CH2CH2-, and at least one of y or y' is different from 0. The compounds of formula (XVII) are then polyethylene glycols. The aminoplast ether polymers of formula (I) according to the invention are in particular described in US Pat. No. 5,914,373, the content of which forms an integral part of the invention.

As polymers with an aminoplast-ether skeleton of formula (I), mention may in particular be made of the products PURE-THIX L [PEG-180 / Octoxynol-40 / TMMG Copolymer (INCI name)], PURE-THIX M [PEG-180 / Laureth-50 / TMMG Copolymer (INCI name)], and PURE-THIX HH [Polyether-1 (INCI name)] sold by the company SUD-CHEMIE.

The polymers with an aminoplast-ether skeleton are preferably used in an amount which can vary from approximately 0.01 to 10% by weight of the total weight of the discoloration or permanent deformation composition ready for use. More preferably, this amount varies from about 0.1 to 5% by weight.

The reducing agents which can be used according to the invention are preferably chosen from thiols such as cysteine, thioglycolic acid, thiolactic acid, their salts and their esters, cysteamine and its salts or sulphites. In the case of compositions intended for bleaching, it is also possible to use ascorbic acid, its salts and its esters, erythorbic acid, its salts and its esters, sulfinates such as sodium hydroxymethanesulfinate.

These reducers are used in said ready-to-use compositions in concentrations of between 0.1 and 30% approximately, preferably between 0.5 and 20% by weight, by adding to the total weight of the composition.

More particularly, the compositions according to the invention may also contain, at least one cationic or amphoteric substantive polymer.

Within the meaning of the present invention, the expression “cationic polymer” designates any polymer containing cationic groups and / or groups which can be ionized into cationic groups. The cationic polymers which can be used in accordance with the present invention can be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in patent application EP-A-337 354 and in French patents FR- 2,270,846, 2,383,660, 2,598,611, 2,470,596 and 2,519,863.

The preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and / or quaternary amine groups which can either be part of the main polymer chain or be carried by a lateral substituent directly connected thereto.

The cationic polymers used generally have a number average molecular mass of between 500 and 5.10 ° approximately, and preferably between 10 ³ and 3.10 ⁶ approximately.

Among the cationic polymers, mention may more particularly be made of polymers of the polyamine, polyaminoamide and quaternary polyammonium type. These are known products. They are described in particular in French patents 2,505,348 or 2,542,997. Among the said polymers, there may be mentioned:

(1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formulas (I), (II), (III) or (IV):

in which:

R3, identical or different, denote a hydrogen atom or a CH3 radical;

A, identical or different, represent an alkyl group, linear or branched, from 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group from 1 to 4 carbon atoms;

R4, R5. ^R 6 _> identical or different, represent an alkyl group having from 1 to

18 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms;

R-1 and R2, identical or different, represent hydrogen or an alkyl group having from 1 to 6 carbon atoms and preferably methyl or ethyl;

X denotes an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide.

The polymers of family (1) can also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls (C1-C4) , acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

Thus, among these polymers of family (1), there may be mentioned:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl hologenide, such as that sold under the name HERCOFLOC by the company HERCULES, the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described for example in patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY,

- the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium ammonium methosulfate sold under the name RETEN by the company Hercules,

- vinylpyrrolidone / acrylate or dialkylaminoalkyl methacrylate copolymers, quaternized or not, such as the products sold under the name "GAFQUAT" by the company ISP, for example "GAFQUAT 734" or "GAFQUAT 755" or else the products called "COPOLYMER 845, 958 and 937 ". These polymers are described in detail in French patents 2,077,143 and 2,393,573,

- dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers such as the product sold under the name GAFFIX VC 713 by the company ISP, - vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymers sold in particular under the name STYLEZE CC 10 by ISP,

- and vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymers quaternized such as the product sold under the name "GAFQUAT HS 100" by the company ISP.

(2) Derivatives of cellulose ethers comprising quaternary ammonium groups described in French patent 1,492,597, and in particular the polymers marketed under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by the Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose having reacted with an epoxide substituted by a trimethylammonium group.

(3) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl- , hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a methacryloylethyl salt trimethylammonium, methacryimidopropyl trimethylammonium, dimethyl-diallylammonium.

The marketed products meeting this definition are more particularly the products sold under the name "Celquat L 200" and "Celquat H 100" by the National Starch Company.

(4) The cationic polysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups. Guar gums modified with a salt (eg chloride) of 2,3-epoxypropyl trimethylammonium are used, for example.

Such products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company MEYHALL.

(5) Polymers consisting of piperazinyl units and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen atoms or by aromatic or heterocyclic rings, as well as the products of oxidation and / or quaternization of these polymers. Such polymers are described in particular in French patents 2,162,025 and 2,280,361.

(6) Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-halide of alkyl or also with an oligomer resulting from the reaction of a bifunctional compound reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, d 'an epilhalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amino group of the polyaminoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary, quaternized amino functions. Such polymers are described in particular in French patents 2,252,840 and 2,368,508.

(7) Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation by bifunctional agents. Mention may be made, for example, of the adipic acid-diacoylaminohydroxyalkoyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl, propyl. Such polymers are described in particular in French patent 1,583,363.

Among these derivatives, there may be mentioned more particularly the adipic acid / dimethylaminohydroxypropyl / diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz.

(8) The polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are described in particular in the patents American 3,227,615 and 2,961,347. Polymers of this type are in particular sold under the name "Hercosett 57" by the company Hercules Inc. or else under the name of "PD 170" or "Delsette 101" by the company Hercules in the case of the adipic acid copolymer / epoxypropyl / diethylenetriamine.

(9) Cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (V) or (VI):

formulas in which k and t are equal to 0 or 1, the sum k + t being equal to 1; Rg denotes a hydrogen atom or a methyl radical; R ₇ and R ₈ , independently of one another, denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (C-1-C4), or R7 and Rs can denote, jointly with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R7 and Rs, independently of one another, preferably denote an alkyl group having from 1 to 4 carbon atoms; Y ^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are described in particular in French patent 2,080,759 and in its certificate of addition 2,190,406.

Among the polymers defined above, there may be mentioned more particularly the homopolymer of dimethyldiallylammonium chloride sold under the name "Merquat 100" by the company Calgon (and its low molecular weight average counterparts) and the chloride chloride copolymers diallyidimethylammonium and acrylamide marketed under the name "MERQUAT 550".

(10) The quaternary diammonium polymer containing recurring units corresponding to the formula: - formula (VII) in which:

^R 10 _> ^R 11 _> 12 ^{and R} 13 _> identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or else R _Π Q. ^R 1 1 _> R- I2 and R13, together or separately, constitute with the nitrogen atoms to which they are attached heterocycles possibly containing a second heteroatom other than nitrogen or else RJ Q. ^R 1 1, R12 ^{and R} 13 represent a C 1 alkyl radical - _| -Cβ linear or branched substituted by a nitrile, ester, acyl, amide or -CO-O- R14-D or -CO-NH- R14-D group where R-14 is an alkylene and D a quaternary ammonium group;

A1 and B1 represent polymethylenic groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings, or one or more atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

X ^" denotes an anion derived from a mineral or organic acid;

A1, R ^" ιo and R-12 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 can also denote a group - (CH2) n-CO-D-OC- (CH2) n- in which D denotes: a) a residue of glycol of formula: -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas:

- (CH2-CH ₂ -O) x-CH ₂ -CH2- - [CH ₂ -CH (CH ₃ ) -O] y-CH2-CH (CH3) - where x and y denote an integer from 1 to 4 , representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or else the bivalent radical

-CH2-CH2-S-S-CH2-CH2-; d) a ureylene group of formula: -NH-CO-NH-.

Preferably, X ^" is an anion such as chloride or bromide. These polymers have a number average molecular weight generally between 1000 and 100,000.

Polymers of this type are described in particular in French patents 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and US patents 2,273,780, 2,375,853, 2,388,614, 2,454,547 , 3.206.462, 2.261.002, 2.271.378, 3.874.870, 4.001.432, 3.929.990, 3.966.904, 4.005.193, 4.025.617, 4.025.627, 4.025.653, 4.026.945 and 4.027 .020.

It is possible to use more particularly the polymers which consist of recurring units corresponding to the following formula (VIII):

in which Rio. ^R 11> ^R 12 ^{and R} _13. identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms approximately, n and p are whole numbers varying from 2 to approximately 20 and, X ^" is an anion derived from a mineral or organic acid.

(11) Quaternary polyammonium polymers consisting of units of formula (IX): CH, CH,

. _N ⁺ _ _(C H ₂ ) p - NH - CO— D-NH - (CH ₂ ) p - N- (CH ₂ ) ₂ - O— (CH ' ₂ 2)> 2

CH, 2X ^" CH,

(IX) in which: p denotes an integer varying from 1 to 6 approximately,

D may be zero or may represent a group - (CH2) _r - CO in which r denotes a number equal to 4 or 7, and

X "is an anion derived from a mineral or organic acid.

The cationic polymers comprising units of formula (IX) are described in particular in patent application EP-A-122 324 and can be prepared according to the methods described in US patents No. 4,157,388, 4,390,689, 4,702,906 , 4,719,282.

Among these polymers, those of molecular mass measured by NMR of Carbon 13 less than 100,000 are preferred, and in the formula of which: p is equal to 3, and, a) D represents a group - (CH2) 4 - CO -, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13 (NMR ^{1 3} C) being approximately 5600; a polymer of this type is proposed by the company MIRANOL under the name of MIRAPOL-AD1, b) D represents a group - (CH2) 7 - CO -, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13 ( ³ C NMR) being about 8100; a polymer of this type is offered by the company MIRANOL under the name of MIRAPOL-AZ1, c) D denotes the value zero, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13, (NMR ^{1 3} C) being about 25,500; a polymer of this type is sold by the company MIRANOL under the name MIRAPOL-A15, d) a "Block Copolymer" formed of units corresponding to the polymers described in paragraphs a) and c), offered by the company MIRANOL under the names MIRAPOL- 9 ( ³ C NMR molecular weight, approximately 7800) MIRAPOL-175, ( ^{1 3} C NMR molecular weight, approximately 8000) MIRAPOL-95, ( ^{1 3} C NMR molecular weight, approximately

12500).

More particularly still, according to the invention, the polymer with units of formula (IX) in which p is equal to 3 is preferred, D denotes the value zero, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13, (NMR ^{1 3} C) being approximately 25500.

(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as for example the products marketed under the names Luviquat

FC 905, FC 550 and FC 370 by B.A.S.F.

(13) Polyamines such as Polyquart H sold by HENKEL, referenced under the name of "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary.

(14) Crosslinked polymers of methacryloyloxyalkyl (C- | -C4) trialkyl (C _π - C4) ammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized by methyl chloride, homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylene bis acrylamide. One can more particularly use a crosslinked acrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is marketed under the name of

"SALCARE® SC 92" by the company ALLIED COLLOIDS. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyl trimethylammonium chloride containing approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are marketed under the names of "SALCARE® SC 95" and "SALCARE® SC 96" by the company ALLIED COLLOIDS. Other cationic polymers which can be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.

Among all the cationic polymers capable of being used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10) (11) and (14) and even more preferably the polymers of formulas (W) and (U) below:

CH ₃ CH ₃

- f- N * - (CH ₂ ) ₃ -U ⁺ - {CH ₂ ) ₆ -] (W)

" ^• I ci- I cι-

CH ₃ CH ₃ and in particular those whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900;

CH ₃ C ₂ H ₅

i- N- ~ (CH ₂ ) ₃ - ⁺ - CH ₂ ) ₃ (U)

Br I Br-

CH ₃ C ₂ H ₅ and in particular those whose molecular weight, determined by gel permeation chromatography, is approximately 1200.

The concentration of cationic polymer in the compositions according to the present invention can vary from 0.01 to 10% by weight relative to the total weight of the composition, preferably from 0.05 to 5% and even more preferably from 0.1 to 3%.

The amphoteric polymers which can be used in accordance with the present invention can be chosen from polymers comprising distributed K and M units statistically in the polymer chain, where K denotes a unit deriving from a monomer comprising at least one basic nitrogen atom and M denotes a unit deriving from an acid monomer comprising one or more carboxylic or sulphonic groups, or else K and M may denote groups derived from zwitterionic monomers of carboxybetaines or sulfobetaines; K and M can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical, or although K and M form part of a chain of a polymer with an α, β-dicarboxylic ethylene unit, one of the carboxyl groups of which has been reacted with a polyamine comprising one or more primary or secondary amine groups.

The amphoteric polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:

(1) The polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and of a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, the dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US Pat. No. 3,836,537. Mention may also be made of the sodium acrylate / acrylamide propyl trimethyl ammonium chloride copolymer sold under the name POLYQUART KE 3033 by the company HENKEL.

The vinyl compound can also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. The copolymers of acrylic acid and of the latter monomer are offered under the names MERQUAT 280, MERQUAT 295 and MERQUAT PLUS 3330 by the company CALGON.

(2) Polymers containing units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen with an alkyl radical, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides more particularly preferred according to the invention are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl-acrylamide, N-tertiooctyl-acrylamide , N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides. The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.

The preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.

Copolymers are particularly used, the name CTFA (4th Ed., 1991) being Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.

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

- ^ CO - R ₁₉ - CO - Z -T- (X)

in which R-jg represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or of a radical derived from the addition of any one of said acids with an amin _e bis-primary or bis-secondary, and Z denotes a radical of a polyamine polyaikylène bis-primary, mono- or bis-secondary and preferably represents: a) in proportions of 60 to 100 mol%, the radical

U (CH 2> x N - (XI) H

where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this radical deriving from diethylene triamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol% the radical (XI) above, in which x = 2 and p = 1 and which derives from ethylenediamine, or the radical deriving from piperazine:

N - \ / c) in the proportions of 0 _^ to 20 mol% the radical -NH- (CH2) 6-NH- deriving from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins , diepoxides, dianhydrides, bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent by amino group of the polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or a sultone alkane or of 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 acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids.

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

(4) Polymers comprising zwitterionic units of formula:

in which R20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R21 and R22 represent a hydrogen, methyl, ethyl or propyl atom, R23 and R24 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.

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

By way of example, there may be mentioned the copolymer of methyl methacrylate / methyl dimethyl-carboxymethylammonio-ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.

(5) polymers derived from chitosan comprising monomer units corresponding to formulas (XIII), (XIV), (XV) below:

R ^ -COOH

(XIII) (XIV) (XV)

the motif (XIII) being present in proportions of between 0 and 30%, the motif (XIV) in proportions of between 5 and 50% and the motif F in proportions of between 30 and 90%, it being understood that in this unit (XV), R ₂₅ represents a radical of formula: R 27 R 28

R 26 (0) _q - ç-

in which if q = 0, R26, R27 and R28. identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkoyiamine residue or a dialkoyiamine residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted by one or more amino groups , hydroxyl, carboxyl, alkylthio, sulfonic, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R26, R27 and R28 in this case being a hydrogen atom; or if q = 1, R26. ^R 27 ^{and R} 28 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(6) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by the company JAN DEKKER.

(7) The polymers corresponding to the general formula (XI) such as those described for example in French patent 1,400,366:

in which R29 represents a hydrogen atom, a CH3O radical, CH3CH2O, phenyl, R30 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R31 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R32 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R33 "N (31) 2> ^R 33 representing a group -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH (CH ₃ ) -, R ₃₁ having the meanings mentioned above, as well as the higher homologs of these radicals and containing up to 6 carbon atoms.

(8) Amphoteric polymers of the type -D-X-D-X- chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloroacetate on the compounds comprising at least one unit of formula:

-D-X-D-X-D- (XVII)

where D denotes a radical

\ / and X denote the same or different symbol E or E ', E or E' denote a bivalent radical which is a straight or branched chain alkylene radical containing up to 7 carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups and which may also contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane;

b) polymers of formula:

-D-X-D-X- (XVIII) where D denotes a radical

\ / and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising a or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloracetate.

(9) (C -] - C5) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidification with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine. These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.

The amphoteric polymers which are particularly preferred according to the invention are those of the family (1).

According to the invention, the amphoteric polymer (s) can represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and even more preferably from 0.1% to 3% by weight , of the total weight of the composition.

The compositions of the invention preferably comprise one or more surfactants. The surfactant (s) can be chosen either, alone or as a mixture, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.

The surfactants which are suitable for carrying out the present invention are in particular the following:

(i) Anionic surfactant (s): By way of example of anionic surfactants which can be used, alone or as mixtures, in the context of the present invention, there may be mentioned in particular (non-limiting list) the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amin _e s salts, amino alcohol salts or magnesium salts) of the following compounds: alkyl sulphates, alkyl ether sulphates, alkylamido, alkylarylpolyether sulphates, monoglyceride sulphates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin-sulfonates, paraffin-sulfonates; (C ₆ -C ₂₄ ) alkyl sulfosuccinates, (C ₆ -C ₂ ) alkyl ethersulfosuccinates, (C ₆ -C ₂ ) alkyl amidesulfosuccinates; (C ₆ -C ₂₄ ) alkyl sulfoacetates; acyl (C ₆ -C ₂₄ ) sarcosinat.es and acyl (C ₆ -C ₂ ) glutamates. It is also possible to use the alkyl esters (C ₆ -C ₂ ) carboxylic polyglycosides such as the alkylglucoside citrates, the alkylpolyglycoside tartrate and the alkylpolyglycoside sulfosuccinates., The alkylsulfosuccinamates; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably containing from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants which can still be used, mention may also be made of the salts of fatty acids such as the salts of oleic, ricinoleic, palmitic, stearic acids, coconut oil or hydrogenated coconut oil acids; acyl lactylates whose acyl radical contains 8 to 20 carbon atoms. It is also possible to use the alkyl D galactoside uronic acids and their salts, the polyoxyalkylenated (C ₆ -C ₂ ) alkyl ether carboxylic acids, the polyoxyalkylenated (C ₆ -C ₂₄ ) aryl ether carboxylic acids, the alkyl (C ₆ -C ₂ ) polyoxyalkylenated carboxylic amido ether and their salts, in particular those comprising from 2 to 50 alkylene oxide groups, in particular ethylene groups, and their mixtures.

(ii) Non-ionic surfactants (s):

Non-ionic surfactants are also well known compounds per se (see in particular in this regard "Handbook of Surfactants" by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178) and their nature is not, in the context of the present invention, critical. So, they can in particular be chosen from (nonlimiting list) alcohols, alpha-diols, polyethoxylated, polypropoxylated alkylphenols, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of ethylene oxide or oxide groups propylene which can range in particular from 2 to 50. Mention may also be made of copolymers of ethylene oxide and of propylene, condensates of ethylene oxide and of propylene on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1, 5 to 4; esters of fatty acids of oxyethylenated sorbitan having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkyl glucamine derivatives, amine oxides such as alkyl (C10-14) amino oxides or oxides of N-acylaminopropylmorpholine.

(iii) Surfactant (amphoteric (s) or zwitterionic (s ^

Amphoteric or zwitterionic surfactants, the nature of which is not critical in the context of the present invention, may in particular be (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a chain linear or branched having 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of (C8-C20) alkyl betaines, sulfobetaines, (C8-C20) alkyl amidoalkyl (C1-C5) betaines or (Cs-C20) amidoalkyl (C- | -Ce) sulfobetaines alkyl.

Among the amine derivatives, mention may be made of the products sold under the name Miranol, as described in patents US-2,528,378 and US-2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates of respective structures: R34 -CONHCH ₂ CH ₂ -N (R ₃ 5) (R36) (CH ₂ COO-) in which: R34 denotes an alkyl radical of an acid R34-COOH present in the hydrolyzed coconut oil, a heptyl, nonyl or undecyl radical, R35 denotes a beta-hydroxyethyl group and R36 denotes a carboxymethyl group; and R ₃ 4'-CONHCH2CH ₂ -N (B) (C) in which:

B represents -CH2CH2OX ', C represents - (CH2) _Z -Y', with z = 1 or 2, X 'denotes the group -CH2CH2-COOH or a hydrogen atom Y' denotes -COOH or the radical -CH ₂ - CHOH - SO3H R34 'denotes an alkyl radical of an acid R37 -COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, especially in C7, Cg, C < _| 1 or C13, a C17 alkyl radical and its iso form, an unsaturated C-17 radical.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroampho- diacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionatepropodopropodampropodopropionampropodampropodampropylamphodipropionate . By way of example, mention may be made of the cocoamphodiacetate sold under the trade name MIRANOL® C2M concentrated by the company RHODIA CHIMIE.

(iv) Cationic surfactants

Among the cationic surfactants that may be mentioned in particular (nonlimiting list): the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium; imidazoline derivatives; or amine oxides of a cationic nature. The amounts of surfactants present in the ready-to-use composition according to the invention can vary from 0.01 to 30% and preferably from 0.1 to 20% of the total weight of the composition.

The compositions according to the invention may also contain other rheology adjusting agents such as cellulosic thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, etc.), guar gum and its derivatives (hydroxypropylguar, etc.), microbial origin (xanthan gum, scleroglucan gum, etc.), synthetic thickeners such as crosslinked homopoiymers of acrylic acid or acrylamidopropanesulfonic acid and ionic or nonionic associative polymers such as the polymers sold under the names PEMULEN TR1 or TR2 by the company GOODRICH, SALCARE SC90 by the company ALLIED COLLOIDS, ACULYN 22, 28, 33, 44, or 46 by the company ROHM & HAAS and ELFACOS T210 and T212 by the company AKZO.

These additional thickeners can represent from 0.05 to 10% by weight of the total weight of the composition.

The pH of the ready-to-use composition is generally between approximately

1, 5 and 12.

More preferably, the pH of the ready-to-use compositions of the invention intended for bleaching is between approximately 1, 5 and 10, and even more preferably between approximately 1, 5 and 7. More preferably, the pH of the compositions of the ready-to-use invention intended for permanent deformation is between approximately 6 and 12 and even more preferably between approximately 7 and 11.

This pH can be adjusted to the desired value by means of acidifying or basifying agents well known in the state of the art in discoloration or in permanent deformation of keratin fibers.

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali or ammonium carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, oxyethylenated and / or oxypropylenated hydroxyalkylamines and ethylenediamines, sodium or potassium hydroxides and the compounds of formula (XIX) below:

R, MO

³⁸ N - R - N (XIX)

R ₃₉ ^ ^ ^R 41

in which R is a propylene residue optionally substituted by a hydroxyl group or a Cι-C ₄ alkyl radical; R ₃₈ , R ₃ g, R40 and R ₄₁ , identical or different, represent a hydrogen atom, a Cι-C ₄ alkyl or CC ₄ hydroxyalkyl radical.

The acidifying agents are conventionally, for example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, or acids sulfonic.

The basifying or acidifying agents may represent approximately 0.01 to 30% by weight of the total weight of the discoloration or permanent deformation composition.

The compositions of the invention can also contain sequestering agents such as for example ethylenediamine tetraacetic acid (EDTA).

When the compositions containing the reducing agent and the polymer with an aminoplast-ether skeleton are in anhydrous form (powder or cream), they contain the main agents and additives mentioned above in the form of essentially anhydrous solids or liquids. They can also contain mineral or organic fillers such as silica or clays. They can also contain binders such as vinylpyrrolidone, oils or waxes, polyalkylene glycols or derivatives of polyalkylene glycols. They can also contain lubricants such as polyol stearates or alkali or alkaline earth metal sterates, as well as coloring or matifying agents such as titanium oxides.

When the medium containing the reducing agent is an aqueous medium, it may optionally contain cosmetically acceptable organic solvents, including more particularly alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as the diethylene glycol alkyl ethers such as, for example, the monoethyl ether or the monobutyl ether of diethylene glycol, in concentrations of between approximately 0.5 and 20% and, preferably, between approximately 2 and 10% by weight relative to the total weight of the composition.

The bleaching or permanent deformation composition according to the invention may also contain an effective amount of other agents, also previously known in bleaching or in permanent deformation of keratin fibers, such as various usual adjuvants such as volatile or non-volatile silicones, cyclic or linear or branched, organomodified (in particular by amino groups) or not organomodified, preservatives, ceramides, waxes or oils, vegetable, mineral or synthetic, acids and in particular AHAs etc.

Of course, a person skilled in the art will take care to choose the optional compound (s) mentioned above, so that the advantageous properties intrinsically attached to the bleaching or permanent deformation composition of the keratin fibers according to the invention do not are not, or not substantially, altered by the planned addition (s).

Preferably, the bleaching process according to the invention consists in applying the ready-to-use reducing composition to the dry or wet keratin fibers, and to leaving it to act for a pause time varying, preferably, from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, to rinse the fibers, then optionally to wash them in shampoo, then to rinse them again, and to dry them.

Preferably, the permanent deformation method according to the invention consists in applying the reducing composition ready for use to the dry or wet keratin fibers, to leaving it to act for a pause time varying, preferably, from 1 to 60 minutes. approximately, and more preferably from 10 to 45 minutes approximately, optionally rinsing the fibers, then applying an oxidizing composition and leaving to act for a pause time of between 1 and 20 minutes and preferably between 1 and 10 minutes, then optionally at wash them in shampoo, then rinse again, and dry them. Mechanical means for tensioning the keratin fibers can be used before, during or after application of the reducing composition and removed before or after rinsing the oxidizing composition.

Concrete examples illustrating the invention are indicated below, without however being limiting in nature.

EXAMPLE 1:

The following ready-to-use aqueous bleaching composition was prepared (expressed in grams):

MA * = Active Matter

The above bleaching composition allowed for regular bleaching of artificially dyed hair with an oxidation dye.

EXAMPLE 2:

The following permanent deformation composition (expressed in grams) was prepared:

MA * = Active Matter

The above permanent deformation composition was applied for 15 minutes to wet hair previously wound on styling rollers, then rinsed thoroughly with water. An 8-volume hydrogen peroxide and .pH 3 solution was then applied for 5 minutes, then rinsed again, the rollers were removed and dried. The hair presented a beautiful homogeneous crimp.

Claims

1. Ready-to-use composition for bleaching or deforming keratin fibers, in particular human keratin fibers such as the hair, comprising, in a medium suitable for bleaching, at least one reducing agent, characterized in that 'it also contains at least one thickening polymer with an aminoplast-ether skeleton.

2. Composition according to Claim 1, characterized in that the aminoplast-ether polymer (s) are chosen from those containing at least one unit of structure (I) below:

in which: -AMP is an aminoplast residue with alkylene units,

-R denotes a hydrogen atom, a C-1 C4 alkyl radical or an acyl radical

C1C4,

-RO-i is a divalent alkyleneoxy residue,

3. Composition according to claims 1 or 2, characterized in that the polymer or polymers with an aminoplast-ether skeleton are chosen from those containing at least one unit of structure (II) below:

in which -AMP, R, RO-1 and p have the same meaning as in claim 2,

RO2 is a hydrophobic group different from RO linked to AMP via a heteroatom and comprising at least two carbon atoms, and,

-q is a positive integer.

4. Composition according to Claim 3, characterized in that the aminoplast-ether polymer (s) are chosen from the following polymers of structure (III) or (IIIb):

R2- (lllbis)

in which :

AMP, R, RO1, RO2, P and q have the same meaning as in the claims

2 and 3,

R2 or R3, identical or different, represent a terminal group which can denote a hydrogen atom, a ROiH group, a RO2H group, an AMP (OR) p group or any monofunctional group such as alkyl, cycloalkyl-, aryl, aralkyl, alkylaryl , alkyloxyalkyle, aryloxyalkyle, cycloalkoxyalkyle, a being a number greater than 1 and preferably greater than 2.

5. Composition according to any one of claims 2 to 4, characterized in that the aminoplast residues carrying their OR groups are chosen from those of structures (IV) to (XV) below:

R having the same meaning as in claim 2, R1 denotes C1C4 alkyl, y is a number at least equal to 2, x denotes 0 or 1.

6. Composition according to any one of claims 2 to 4, characterized in that the aminoplast residues carrying their OR groups are chosen from those of structure (XVI) below:

in which R, p, and x have the same meanings as in claims 2 and 5.

7. Composition according to any one of claims 2 to 6, characterized in that the alkyleneoxy residues are those corresponding to the diols of general formula (XVII) below:

HO- (ZO) y- (Z1 (Z2O) w) t- (Z'O) y'-Z3OH (XVII), y and y 'being numbers ranging from 0 to 1000, t and w being numbers ranging from 0 to 10, Z, Z ', Z2 and Z3 are C2C4 alkylene radicals and preferably radicals

-CH2-CH (Z4) - and -CH2-CH (Z4) -CH2-, Z1 being a linear or cyclic radical, branched or not, aromatic or not, comprising or not one or more heteroatoms and having from 1 to 40 carbon atoms, Z4 denoting a hydrogen atom or a C-1 C4 alkyl radical or a C1 C3 acyl radical being understood that at least one of the radicals Z4 of the radicals Z, Z ^' , Z2 and Z3 is different from acyl.

8. Composition according to Claim 7, characterized in that the radical Z4 denotes a hydrogen atom or a methyl radical.

9. Composition according to Claims 7 and 8, characterized in that t = 0 and that Z, Z 'and Z3 denote -CH2CH2-, at least one of y or y' being different from O.

10. Composition according to any one of the preceding claims, characterized in that the polymers with an aminoplast-ether skeleton are chosen from the following products:

PEG-180 / Octoxynol-40 / TMMG Copolymer, PEG-180 / Laureth-50 / TMMG Copolymer, Polyether-1.

11. Composition according to any one of claims 1 to 10, characterized in that the polymers with an aminoplast-ether skeleton are used in an amount which can vary from 0.01 to 10% by weight of the total weight of the composition.

12. Composition according to claim 11, characterized in that the polymers with an aminoplast-ether skeleton are used in an amount which can vary from 0.1 to 5% by weight of the total weight of the composition.

13. Composition according to any one of the preceding claims, characterized in that the reducing agent or agents are chosen from thiols such as cysteine, thioglycolic acid, thiolactic acid, their salts and their esters, cysteamine and its salts, or sulfites.

14. Composition according to any one of claims 1 to 12, characterized in that the reducing agents are chosen from ascorbic acid, its salts and its esters, erythorbic acid, its salts and its esters.

15. Composition according to any one of claims 13 or 14, characterized in that the concentration of reducing agent can vary from 0.1 to 30% by weight relative to the total weight of the composition.

16. Composition according to Claim 15, characterized in that it can vary from 0.5 to 20% by weight relative to the total weight of the composition.

17. Composition according to any one of the preceding claims, characterized in that it also contains at least one cationic or amphoteric polymer.

18. Composition according to Claim 17, characterized in that the cationic polymer is a quaternary polyammonium polymer consisting of recurring units corresponding to the following formula (W):

CH, CH,

i- N - (CH ₂ ) ₃ -N ⁺ - (CH ₂ ) ₆ (W) cι- ^'"" i cι- ι i

CH ₃ CH ₂

19. Composition according to Claim 17, characterized in that the cationic polymer is a quaternary polyammonium polymer consisting of recurring units corresponding to the following formula (U): -LLU)

CH ₃ C ₂ H ₅

20. Composition according to Claim 17, characterized in that the amphoteric polymer is a copolymer comprising at least as monomers of acrylic acid and a dimethyldiallylammonium salt.

21. Composition according to any one of claims 17 to 20, characterized in that the cationic or amphoteric polymer (s) represent from 0.01% to 10%, preferably from 0.05% to 5%, and even more preferably from 0.1% to 3% by weight, of the total weight of the composition.

22. Composition according to any one of the preceding claims, characterized in that it contains at least one surfactant chosen from anionic, cationic, nonionic or amphoteric surfactants.

23. Composition according to claim 22, characterized in that the surfactants represent 0.01 to 30% and preferably from 0.1 to 20% by weight, of the total weight of the composition.

24. Composition according to any one of the preceding claims, characterized in that it contains at least one additional thickening agent.

25. Composition according to claim 24, characterized in that the additional thickening agent is a cellulose derivative, a guar derivative, a gum of microbial origin, a synthetic thickener.

26. Composition according to claims 24-25, characterized in that the additional thickening agent (s) represent 0.05 to 10% by weight of the total weight of the composition.

27. Composition according to any one of the preceding claims, characterized in that it also contains at least one basifying or acidifying agent in amounts ranging from 0.01 to 30% by weight of the total weight of the composition.

28. Composition according to Claim 27, characterized in that the basifying agent is chosen from ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, hydroxyalkylamines and ethylenediamines oxyethylenated and / or oxypropylenated, sodium or potassium hydroxides and the compounds of formula (XIX) below:

R ₃ 8 \. R MO

N - R - N (XIX)

R ^K 39 / "\ R 41

in which R is a propylene residue optionally substituted by a hydroxyl group or a Cι-C ₄ alkyl radical; R ₃₈ , R ₃₉ , R ₄₀ and R ι, identical or different, represent a hydrogen atom, an alkyl radical in CC or hydroxyalkyl in dC ₄ .

29. Composition according to claim 27, characterized in that the acidifying agent is chosen from mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid or sulfonic acids.

30. Composition according to any one of claims 1 to 29, characterized in that it is obtained by extemporaneous mixing at the time of the use of an anhydrous composition containing at least one reducing agent and at least one composition aqueous, at least one of the anhydrous or aqueous compositions containing at least one polymer with an aminoplast-ether skeleton.

31 _. Anhydrous composition for bleaching or deformation of keratin fibers, in particular human keratin fibers such as the hair, comprising at least one reducing agent, characterized in that it additionally contains at least one thickening polymer with an aminoplast-ether skeleton defined in any one of claims 2-12.

32. Composition according to claims 30 or 31, characterized in that the anhydrous composition is in pulverulent form.

33. Composition according to claims 30, 31 or 32, characterized in that the anhydrous composition contains at least one additive chosen from mineral or organic fillers such as silica or clays, binders such as vinylpyrrolidone, oils or waxes, polyalkylene glycols or derivatives of polyalkylene glycols, lubricants such as polyol stearates or stearates of alkali or alkaline earth metals and coloring or matifying agents such as titanium oxides.

34. Composition according to claim 33, characterized in that each of the additives is present at a concentration ranging from 0 to 30% by weight of the total weight of the composition.

35. Composition according to any one of claims 1 to 29, characterized in that it is aqueous.

36. Composition according to claim 35, characterized in that the aqueous medium contains one or more organic solvents.

37. Composition according to claim 36, characterized in that the concentration of solvent (s) varies from 0.5 to 20% and, preferably, from 2 to 10% by weight relative to the total weight of the composition.

38. Composition according to any one of claims 1-30 and 32-37, characterized in that the composition has a pH ranging from 1.5 to 12.

39. Composition for bleaching according to any one of claims 1-30 and 32-38, characterized in that the pH is between 1, 5 and 10 and preferably between 1, 5 and 7.

40. Composition for permanent deformation according to any one of claims 1-30 and 32-38, characterized in that the pH is between 6 and 12 and preferably between 7 and 11.

41. Composition according to claim 30, characterized in that the polymer with an aminoplast-ether skeleton is present in an aqueous composition.

42. Process for bleaching or permanently deforming keratin fibers, in particular human keratin fibers such as the hair, consisting in applying to the fibers, dry or wet, a ready-to-use composition containing, in a medium suitable for the discoloration, at least one reducing agent and at least one polymer with an aminoplast-ether skeleton defined in any one of claims 2 to 12, and to let it act for a pause time varying from 1 to 60 minutes, and preferably of 10 to 45 minutes, optionally rinsing the fibers, washing them with shampoo, then rinsing them again, and drying them, the application of said composition being able to be followed, in the case of permanent deformation, by application, optionally after rinsing, of an oxidizing composition which is left to act for a pause time of between 1 and 20 minutes and preferably between 1 and 10 minutes, then washing optionally with shampoo, rinse again, and dry.

43. Device with two compartments or “Kit” for bleaching or permanent deformation of keratin fibers and in particular human keratin fibers such as the hair, characterized in that the first compartment contains at least one powder or an aqueous composition, and the second compartment an aqueous composition, at least one of the two compartments containing at least one reducing agent and at least one two compartments containing at least one polymer with an aminoplast-ether skeleton defined in any one of claims 2-12.