EP1239819A1

EP1239819A1 - Composition associating two polyurethane polyethers

Info

Publication number: EP1239819A1
Application number: EP00979707A
Authority: EP
Inventors: Frédéric Legrand
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1999-12-13
Filing date: 2000-11-10
Publication date: 2002-09-18
Also published as: FR2802095A1; FR2802095B1; WO2001043708A1; AU1710701A

Abstract

The invention concerns a composition for bleaching or of keratinous fibres, in particular human keratinous fibres such as hair, comprising, in a medium suitable for bleaching or permanent waving, at least a reducing agent and additionally at least two specific polyurethane polyethers. The invention also concerns methods and devices for bleaching and permanent waving of keratinous fibres using said compositions.

Description

COMPOSITION OF TWO POLYURETHANE POLYETHERS

The present invention relates to a composition for bleaching or permanent deformation of keratin fibers and in particular human keratin fibers such as the hair, comprising at least one reducing agent and at least two particular polyether polyurethanes.

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.

However, 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 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 discoloration or permanent and powerful and homogeneous deformations, if the combination of at least two polyurethane polyethers is introduced into the composition below defined.

These discoveries are the basis of the present invention.

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, that is to say that it can be stored as it is before use or result from extemporaneous mixture of two or more compositions.

The subject of the present invention is thus 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 the combination:

a polyether polyurethane (a) capable of being obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 50 to 500 moles of ethylene oxide,

(ii) at least one C8-C30 fatty alcohol and (iii) at least one diisocyanate and,

- a polyurethane polyether (b) capable of being obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 50 to 500 moles of ethylene oxide, (ii) at least one alcohol fatty C8-C30 different from that of polyether polyurethane (a) and (iii) at least one diisocyanate. When the ready-to-use composition according to the invention results from the extemporaneous mixture of several compositions, the combination of said polyurethane polyethers (a) and (b) may be present in one or more or in all of the compositions mixed In this way , the combination of said polyurethane polyethers may 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 combination of said polyurethane polyethers is present in at least one aqueous composition which is mixed at the time of use with a composition either aqueous or anhydrous in the form of powder or cream and containing at least a reducing agent Another preferred form of the invention is a single composition containing the reducing agent (s) and the combination of said polyurethane polyethers Another object targeted by the present invention is an anhydrous composition containing at least one reducing agent and at least one combination defined above of two polyurethane polyethers (a) and (b), 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 human keratin fibers such as the hair using the bleaching composition or permanent deformation ready for use as described according to invention, the application of said composition being able to 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 I at least two compartments containing at least one reducing agent and at least one of two compartments containing at least the combination defined above of two polyurethane polyethers (a) and (b)

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

The polyurethane polyethers (a) and (b) according to the invention can be prepared according to the methods described in US Patents 4,079,028, 4,180,491, 4,155,892 and 5,281,654

Preferably, polyurethane polyethers (a) and (b) will be used for which the polyethylene glycol contains 150 or 180 moles of ethylene oxide. Preferably also, a polyether polyurethane (a) or (b) will be used. to a sacchande and more particularly to maltodextπne

Still preferably, polyether polyurethanes (a) and (b) will be used for which the diisocyanate is methylene bιs (4-cyclohexylιsocyanate)

A bleaching or permanent deformation composition more particularly preferred according to the invention is a composition as defined above, for which the polyether polyurethane (a) is obtained by polycondensation of at least three compounds comprising, a polyethylene glycol at 150 or 180 moles of ethylene oxide, stearyl alcohol (C18) and methylene bιs (4-cyclohexylιsocyanate), and the polyether polyurethane (b) is obtained by polycondensation of at least three compounds comprising, a polyethylene glycol at 150 or 180 moles of ethylene oxide, decyl alcohol (C10) and methylene bιs (4-cyclohexylιsocyaπate)

Among the polyurethane polyethers (a), mention may be made of the product sold by the company ROHM & HAAS under the trade name

ACULYN 46, which is a polycondensate comprising at least as elements, a polyethylene glycol with 150 or 180 moles of ethylene oxide, alcohol stearyl and methylene bis (4-cyclohexyl-isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%).

Among the polyurethane polyethers (b), mention may be made of the product sold by the company ROHM & HAAS under the trade name: ACULYN 44, which is a polycondensate comprising at least as elements, a polyethylene glycol containing 150 or 180 moles of oxide ethylene, decyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%).

In the compositions according to the invention, the quantity by weight of the polyether polyurethane (a) is preferably between approximately 0.01 and 5%, and even more preferably between 0.02 and 2%, and that of the polyether polyurethane (b) varies preferably between about 0.01 and 5%, and even more preferably between 0.02 and 2%, relative to the total weight of the composition. In these compositions, the weight ratio of the polyether polyurethane (a) to the polyether polyurethane (b) is preferably between 0.1 and 10 and preferably between 0.5 and 5.

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 lonized 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 ⁶ approximately, and preferably between 10 ³ and 3 10 ⁶ approximately

Among the cationic polymers, mention may be made more particularly of polymers of the polyamine poiyaminoamide and poly quaternary ammonium type. These are known products. They are described in particular in French patents No. 2,505,348 or 2,542,997. Among said polymers, mention may be made of

(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)

NOT

\

R; 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 _β , 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 R 2, which may be 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, methacryiamides, diacetones acrylamides, acrylamides and methacryiamides substituted on nitrogen by lower alkyls (CJ -C4), acrylic or methacrylic acids or their esters, vinyllactams such as vinyipyrrolidone or vinylcaprolactam, vinyl esters Thus, among these polymers of the family (1), one can quote

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quatemise with dimethyl sulfate or with a dimethyl hologenide, such as that sold under the name HERCOFLOC by the company HERCULES,

the copolymers of acrylamide and of methacryloyloxyethyltnmethylammonium 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 methacryloyloxyethyltmethylammonium methosulfate sold under the name RETEN by the company HERCULES, the vinyipyrrolidone / acrylate or dialkylaminoalkyl methacrylate quaternized or not, such as the products sold under the name "GAFQUAT" ISP such as 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 / vinyipyrrolidone terpolymers such as the product sold under the name GAFFIX VC 713 by the company ISP,

- the vinyipyrrolidone / methacrylamidopropyl dimethylamine copolymers sold in particular under the name STYLEZE CC 10 by ISP,

- and quaternized dimethylaminopropyl vinyipyrrolidone / methacrylamide copolymers 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 Union Carbide Corporation These polymers are also defined in the CTFA dictionary as quaternary ammonium 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 salt of methacryloylethyl trimethylammonium, of methacryimidopropyl trimethylammonium, of 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-halohydπne, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide or alternatively by an oligomer resulting from the reaction of a reactive bifunctional compound with respect to a bis-halohydnne, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, an epilhalohydnne of a diepoxide or a bis derivative -unsaturated, the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary amine functions, quaternized. 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 tnamine 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 / dimethylammohydroxypropyl / diethylene tnamine 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 Le molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4 4, the resulting polyaminoamide being reacted with epichlorhydπne in a molar ratio of epichlorohydrin relative to the secondary amine group polyaminoamide of between 0.5 1 and 1.8 1. Such polymers are described in particular in American patents 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; R ₉ denotes a hydrogen atom or a methyl radical; R7 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 ( C1-C4), or R7 and RQ can denote jointly with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R7 and R ₈ 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 dimethyidiallylammonium 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:

^R 10 ^R 12

N + -A - N + - B ₁ - (VU)

I 'I'

RRX γ ^"~ RR _1. ₃ _ XY ^"" formula (VII) in which:

^R 10- ^R 11 _> ^R 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 ^ Q, R- | -J, R12 ^{and R} 13 _> together or separately, constitute with the nitrogen atoms to which they are attached heterocycles possibly containing a second heteroatom other than nitrogen or else Rio. ^ 11 - ^R 12 and ^R 13 represent a linear or branched C - -CQ alkyl radical substituted by a nitrile, ester, acyl, amide or -CO-O- R14-D or -CO-NH- R14-D group where R14 is alkylene and D is 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, RJ O and R -12 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition if A1 denotes an alkylene radical or linear or branched, saturated or unsaturated hydroxyalkylene, B1 can also denote a group - (CH2) n-CO-D-OC- (CH2) n- in which D denotes: a) a glycol residue 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 -0) x-CH2-CH ₂ - - [CH2-CH (CH ₃ ) -O] y-CH ₂ -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 the 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 RJ O, 11. ^R 12 ^and 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 about 2 to 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 - (CH ₂ ) p - NH - CO— D - NH- - (CH ₂ ) p - - (CH ₂ ) ₂ - O— (CH ₂ ) ₂ -

CH ₃ 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 - CW ^ -j - CO -, X denotes a chlorine atom, the molecular mass measured by NMR of Carbon 13 (1 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 approximately 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, (molecular weight NMR ^{1 3} C, around 7800) MIRAPOL -175, ( ^{1 3} C NMR molecular weight, about 8000) MIRAPOL-95, ( ^{1 3} C NMR molecular weight, about 12 500) More particularly still, according to the invention, the polymer with units of formula (IX) is preferred in which p is equal to 3, 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 vinyipyrrolidone and of vinylimidazole such as for example the products marketed under the names Luviquat FC 905, FC 550 and FC 370 by the company 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-ι-C4) trιalkyl (Cι- C-4) ammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized by methyl chloride, or by copolymerization of acrylamide with dimethylaminoethylmethacrylate quaternized by methyl chloride, homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylene bis acrylamide It is more particularly possible to use a crosslinked acrylamide / methacryloyloxyethyl trimethylammonium 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 ALLIED COLLOIDS It is also possible to use a crosslink 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 of polymers containing vinylpyridine or vinylpyridinium units, polyamine and epichlorohydrin condensates of 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 the following formulas (W) and (U)

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 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 K and M units distributed statistically in the polymer chain, where K denotes a unit derived 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 deriving from zwitterionic monomers of carboxybetaines or of sulphobetaines; 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 carboxylic groups of which has been caused to react with a polyamine comprising one or more primary or secondary amine groups.

The amphoteric film-forming 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 comprising units derived from: a) at least one monomer chosen from acrylamides or methacryiamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reactants, 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 product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. The N-substituted acrylamides or methacryiamides which are more particularly preferred according to the invention are 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-decylacryiamide, N-dodecylacrylamide and the corresponding methacryiamides.

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 - - (X)

wherein R- _j g 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 a primary or secondary bis amine, and Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents : a) in the proportions of 60 to 100 mol%, the radical

where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this radical deriving from diethylene tnamine, triethylene tetraamine or dipropyiene 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:

\ / c) in the proportions of 0 to 20 mole% of the radical -NH- (CH2) 6-NH- derived 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 amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or an alkane sultone or their salts . The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as, for example, acrylic and methacrylic acids. itaconic acid. 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 can also contain units derived from non-zwitterionic monomers such as acrylate or dimethyl or diethylaminoethyl methacrylate or alkyl acrylates or methacrylates, acrylamides or methacryiamides or vinyl acetate.

By way of example, there may be mentioned the copolymer of methyl methacrylate / dimethyl-carboxymethylammonio-ethylmethacrylate 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 ₂ 5 represents a radical of formula:

R _2β ç - (0) _q - Ç-

in which if q = 0, R26, 27 ^and 28 _> identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue possibly interrupted by one or more atoms of nitrogen and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R26, 27 and R28 being in this case a hydrogen atom; or if q = 1, R26, ^R 27 ^and 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, R3- _j 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 (R3i) 2, R33 representing a group -CH ₂ -CH ₂ -, -CH2-CH2-CH2-, -CH2-CH (CH3) -, R31 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

^" V

N- y and X denote the symbol E or E ', E or E' which are identical or different denote a bivalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the unsubstituted main chain or substituted by hydroxyl groups and which can additionally contain oxygen, nitrogen and sulfur atoms 1 to 3 aromatic and / or heterocyclic rings, the oxygen atoms of nitrogen and sulfur being present in the form of ether groups , thioether, sulfoxide, sulfone, sulfonium, alkylamme alkenylamine, benzyiamine hydroxyl groups, 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 atoms of carbon in the main chain, whether or not substituted by one or more hydroxyl radicals and comprising one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily comprising a or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloroacetate

(9) Alkyl (Cι-C5) vιnylether / maleic anhydride copolymers partially modified by semiamidification with an N, N-dιalkylamιnoalkylamιne such as N, N-dιméthylamιnopropylamιne or by semiesterification with an N, N-dιalkanolamine These copolymers can also 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 preferentially from 0.1% to 3% by weight total composition

The compositions of the invention preferably comprise one or more surfactants

The surfactant (s) may be chosen individually or as a mixture within the 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 activity (ies)

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, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoethersulfates, alkylarylpolyethersulfates, monoglycesulfates, alkyl sulfonates alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates, paraffins (C ₆ -C ₂₄₎ sulfosuccinates, alkyl (C ₆ -C ₄₎ éthersulfosuccinates, alkyl (C ₆ -C ₂₎ amidesulfosuccinates, alkyl (C ₆ -C ₂₄₎ sulfoacetates, acyl (C ₆ -C ₂₄ ) sarcosinates and acyls (C ₆ -C ₂₄ ) glutamates It is also possible to use alkyl esters (C ₆ -C ₂₄ ) of carboxylic polyglycosides such as alkylglucoside citrates, alkylpolyglycoside tartrate and alkylpoiyglycoside su cosuccinates, alkyl sulfosuccmamates, 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 designating a phenyl or benzyl group Among the anionic surfactants still usable, mention may also be made of the salts of fatty acids such as the salts of oleic, πcinoleic, palmitic acids stearic acid from coconut oil or hydrogenated coconut oil; 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 ₂₄ ) alkyl ether acids, the polyoxyalkylenated aikyl acids (C ₆ -C ₂₄ ), the polyoxyalkylenated aryl ether carboxylic acids. ₆ -C ₂ ) polyoxyalkylenated carboxylic amido ether and their salts, in particular those comprising from 2 to 50 alkylene oxide groups, in particular ethylene, and their mixtures.

(ii) Nonionic surfactant (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. Thus, 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 groups or propylene oxide 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 oxyethylenated sorbitan fatty acids 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 amino (C-10-14) alkyl oxides or oxides of N-acylaminopropylmorpholine.

(iii) Amphoteric or zwitterionic surfactant (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 (Ci-Cβ) betaines or (CQ-C20) amidoalkyl (C- | -Cβ) 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 (R35) (R36) (CH ₂ COO-) in which: R34 denotes an alkyl radical of an acid R34-COOH present in hydrolyzed coconut oil, a heptyl, nonyl or undecyl, R35 denotes a beta-hydroxyethyl group and R36 denotes a carboxymethyl group; and

R ₃ 4'-CONHCH ₂ CH2-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 hydrolyzed linseed oil, an alkyl radical, in particular C7, Cg, C-11 or C13, a C alkyl radical -17 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 Lauroamphodipropionate, Disodium

Caprylamphodipropionate, Disodium Capryloamphodipropionate, Lauroampho- dipropionic acid, Cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold under the trade name MIRANOL® C2M concentrated by the company RHODIA

CHEMISTRY.

(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 homopolymers of acrylic acid or acryiamidopropanesulfonic acid and ionic or nonionic associative polymers such as the polymers marketed 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 as well as their derivatives, hydroxyalkylamines and oxyethylenated ethylenediamines and / or oxypropylenes, sodium or potassium hydroxides and the compounds of formula (XIX) below:

R 38 \ 40

N - R - N (XIX) 39 R '41

in which R is a propylene residue optionally substituted by a hydroxyl group or a CC ₄ alkyl radical; R ₃₈ , R ₃₉ , R ₄₀ and R ₄₁ , identical or different, represent a hydrogen atom, a C-ι-C alkyl radical or a Cι-C 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 combination defined above of two polyurethane polyethers (a) and (b) are in anhydrous form (powder or cream), they contain the main agents and additives mentioned above in the form essentially anhydrous solids or liquids. They can also contain at least one additive chosen from the following at a concentration of 0 to 30% by weight of the total weight of the composition: mineral or organic fillers such as silica or clays; binders such as vinyipyrrolidone, oils or waxes, polyalkylene glycols or polyalkylene glycol derivatives; lubricants such as polyol stearates or alkali or alkaline earth metal sterates; dyes or matifiers 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, previously known previously in bleaching or in permanent deformation of keratin fibers, such as various usual adjuvants such as volatile or non-cyclic silicones or linear or branched, organomodified (in particular by amino groups) or non-organomodified preservatives, ceramides, waxes or oils, vegetable, mineral or synthetic, acids and in particular AHAs etc.

Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above, in such a way that the advantageous properties intrinsically attached to the bleaching or permanent deformation composition of the keratmic 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 according to the invention, to the dry or wet keratmic 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 keratmic 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 with shampoo, then rinse them again, and dry them Mechanical means for tensioning the keratmic 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 solution of pH 3 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 deformation of 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 contains at least the association:

- a polyether polyurethane (a) capable of being obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 50 to 500 moles of ethylene oxide, (ii) at least one alcohol fatty C8-C30 and (iii) at least one diisocyanate and,

- a polyurethane polyether (b) capable of being obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 50 to 500 moles of ethylene oxide, (ii) at least one alcohol fatty C8-C30 different from that of polyether polyurethane (a) and (iii) at least one diisocyanate.

2. Composition according to claim 1, characterized in that in the polyurethane polyethers (a) and (b), the polyethylene glycol contains 150 or 180 moles of ethylene oxide.

3. Composition according to claims 1 or 2, characterized in that the diisocyanate used for the preparation of the polyurethane polyethers (a) and (b) is methylene bis (4-cyclohexylisocyanate).

4. Composition according to any one of claims 1 to 3, characterized in that the fatty alcohol C8-C30 polyether polyisocyanate (a) is stearyl alcohol.

5. Composition according to any one of claims 1 to 4, characterized in that the fatty alcohol C8-C30 of the polyether polyisocyanate (b) is decyl alcohol.

6. Composition according to any one of claims 1 to 5, characterized in that the polyether polyurethane (a) or the polyether polyurethane (b) is associated with a saccharide.

7. Composition according to claim 6, characterized in that the saccharide is maltodextrin.

8. Composition according to any one of claims 1 to 7, characterized in that the polyether polyurethane (a) is obtained by polycondensation of at least three compounds comprising, a polyethylene glycol with 150 or 180 moles of ethylene oxide , stearyl alcohol and methylene bis (4-cyclohexylisocyanate), and that the polyether polyurethane (b) is obtained by polycondensation of at least three compounds comprising, a polyethylene glycol with 150 or 180 moles of ethylene oxide, l decyl alcohol and methylene bis (4-cyclohexylisocyanate).

9. Composition according to any one of the preceding claims, characterized in that the weight ratio [polyether polyurethane (a) / polyether polyurethane (b)] is between 0.1 and 10.

10. Composition according to claim 9, characterized in that the weight ratio [polyether polyurethane (a) / polyether polyurethane (b)] is between 0.5 and 5.

11. Composition according to any one of the preceding claims, characterized in that the polyether polyurethane (a) is present in an amount of 0.01 to 5% and preferably in an amount of 0.02 to 2% by weight, by relative to the total weight of the composition.

12. Composition according to any one of the preceding claims, characterized in that the polyether polyurethane (b) is present in an amount of 0.01 to 5% and preferably in an amount of 0.02 to 2% by weight, relative to 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,

19 Composition according to Claim 17, characterized in that the cationic polymer is a quaternary polyammonium polymer constitutes of repeating units corresponding to the following formula (U)

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 dialkyldiallylammoπium salt

21 Composition according to any one of claims 17 to 20, characterized in that the cationic or amphoteric polymer or polymers 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 t ethanolamines as well as their derivatives, hydroxyalkylamines and oxyethylenated and / or oxypropylenated ethylenediamines, sodium or potassium hydroxides and the compounds of formula (XIX) below:

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 ₄₁ , identical or different, represent a hydrogen atom, a C1-C4 alkyl or C1-C4 hydroxyalkyl radical.

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 use an anhydrous composition containing at least one reducing agent and at least one aqueous composition, at least one of the anhydrous or aqueous compositions containing at least the combination of polyether polyurethanes (a) and (b).

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 combination of polyether polyurethanes ( a) and (b). 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 vinyipyrrolidone, 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 combination of polyether polyurethanes (a) and (b) is 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 combination of polyether polyurethanes (a) and (b) defined in any one of claims 1 to 12, and to let it act for a pause time varying from 1 to 60 minutes , and preferably from 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 the deformation permanent, by the 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 optionally washing with shampoo, rinsing again, and drying.

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 of the two compartments containing at least one combination of polyether polyurethanes (a) and (b) defined in any one of claims 1 to 12.