FR2818546A1 - REDUCING COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIALS BASED ON AMPHIPHILIC POLYMERS OF AT LEAST ONE SULFONICALLY GROUPED ETHYLENE UNATURATION MONOMER COMPRISING A HYDROPHOBIC PART - Google Patents

Abstract

The invention concerns a cosmetic composition for treating keratinous materials comprising in a carrier suitable for keratinous materials: (a) at least an amphiphilic polymer comprising at least an ethylenically unsaturated monomer with sulphonic group, in free form or partly or completely neutralised and further at least a hydrophobic part; (b) at least a reducing agent. The invention also concerns methods and devices for bleaching or permanent waving of keratinous fibres using said composition.

Description

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REDUCING COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIALS BASED ON AMPHIPHILIC POLYMERS OF AT LEAST ONE SULFONICALLY GROUPED ETHYLENIC INSATURATION MONOMER
COMPRISING A HYDROPHOBIC PART The present application relates to a cosmetic composition intended for the treatment of keratin materials comprising in a support suitable for keratin materials: (a) at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or completely neutralized and furthermore at least one hydrophobic part, (b) at least one reducing agent.

The present invention relates to a gelled reductive composition intended for the treatment of keratin materials, comprising an amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free or partially or totally neutralized form, and in addition at least one hydrophobic part and that its uses for the fading and the permanent deformation of the human keratinous fibers and more particularly the hair.

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

It is also known to carry out the permanent deformation of the hair by applying thereon compositions containing one or more reducing agents, the hair having preferably been previously put under tension, in particular using mechanical devices such as curlers, the hair thus reduced being then reoxidized in the desired form, most often after rinsing, via oxygen in the air, but more generally via an oxidant which is preferably chosen from hydrogen peroxide or alkaline bromates.

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Reducers preferentially used in the context of permanent hair deformation are thiols such as thioglycolic acid, its salts and esters, thiolactic acid and its salts, cysteine or cysteamine, and sulphites.

The compositions intended for the bleaching of 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 or agents which are mixed at the moment 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 ready-to-use aqueous compositions or in the form of powdery or liquid anhydrous compositions which are mixed at the time of use with an aqueous composition at the appropriate pH.

que l'acide polyacrylique réticulé, les hydroxyéthylcelluloses, certains polyuréthanes, les cires, et en outre, dans le cas des compositions de décoloration, à des mélanges d'agents tensio-actifs non-ioniques de HLB (Hydrophilic Lipophilic Balance), qui, convenablement choisis, engendrent l'effet gélifiant quand on les dilue au moyen d'eau et/ou d'agents tensio-actifs. To locate the product of discoloration or permanent deformation to the application on the hair, so that it does not run on the face or outside the areas that we propose to treat, so far we have resorted to the use of traditional thickeners such

cross-linked polyacrylic acid, hydroxyethylcelluloses, certain polyurethanes, waxes, and in addition, in the case of bleaching compositions, to mixtures of nonionic surfactants of HLB (Hydrophilic Lipophilic Balance), which suitably selected, cause the gelling effect when diluted with water and / or surfactants.

In addition, cosmetic formulations in the form of transparent gels have been sought for many years. This type of presentation is highly appreciated by the consumer for aesthetic reasons and for reasons of ease and comfort of use.

The gel form most often corresponds to a practical concern for the formulator: facilitating the taking of the product out of its packaging without significant loss, limiting the spread of the product to the local treatment zone and being able to use it in sufficient quantities to obtain the desired cosmetic effect. This objective is important for reducing formulations used in discoloration or permanent deformation of the hair. These must spread out and spread out

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façon régulière le long des fibres kératiniques et ne pas couler sur le front, la nuque, le visage ou dans les yeux.

regular way along the keratinous fibers and do not run on the forehead, the neck, the face or in the eyes.

The Applicant has found that thickening systems previously used do not allow to obtain discolorations or permanent deformations sufficiently powerful and homogeneous.

Moreover, it has also found that the compositions of discoloration or permanent deformation of the hair, ready for use, containing the reducing agent (s), 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.

However, after extensive research conducted on the question, the Applicant has now discovered that it is possible to obtain compositions for bleaching or permanent deformation of hair containing at least one reducing agent, ready for use, under form of gels which do not flow and therefore remain well localized at the point of application, and which also make it possible to obtain permanent and homogeneous decolorations or permanent deformations, if an effective amount of an amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulfonic group, in free form or partially or totally neutralized form and in addition at least one hydrophobic part.

These findings are the basis of the present invention.

The subject of the present invention is therefore a cosmetic and / or dermatological composition intended for the treatment of keratinous substances comprising in a support which is suitable for keratin materials: (a) at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulfonic group, in free or partially or completely neutralized form and in addition at least one hydrophobic part and (b) at least one reducing agent.

The invention also relates to the use of these polymers as a thickening and / or gelling agent in cosmetic and / or dermatological compositions comprising at least one reducing agent.

The present invention thus relates to the use of these polymers in a ready-to-use composition for the discoloration or the permanent deformation of the fibers

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kératiniques humaines et en particulier les cheveux, comprenant, dans un milieu approprié pour la décoloration ou la déformation permanente, au moins un agent réducteur.

human keratin and in particular the hair, comprising, in a medium suitable for discoloration or permanent deformation, at least one reducing agent.

For the purposes of the invention, the term "ready-to-use composition" is intended to mean the composition intended to be applied as it is to the keratinous fibers, that is to say that it may be stored as it is before use or as a result of extemporaneous mixture of two or more compositions.

When the ready-to-use composition results from the extemporaneous mixing of several compositions, the polymer according to the invention may be present in one or more or in all of the mixed compositions.

In this way, the polymer according to the invention may be present in an anhydrous composition in the form of powder, preferably powder or cream, and / or in one or more aqueous compositions.

Preferably according to the invention, the polymer or polymers according to the invention are present in at least one aqueous composition which is mixed at the time of use with an aqueous or anhydrous composition in powder or cream form and containing at least one reducing agent.

Another preferred form of the invention is a single composition containing the reducing agent (s) and the polymer (s) according to the invention.

Another object of the present invention is the use of these polymers in an anhydrous composition containing at least one reducing agent, said composition being intended to be diluted before application to the fibers.

The invention also relates to a process for bleaching and a method of permanent deformation of human keratinous fibers and in particular the hair using the composition of permanent fading or deformation ready for use as described above, the application of said composition that 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" packaging containing such a ready-to-use composition.

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Ainsi, un dispositif à deux compartiments comprend un premier compartiment contenant au moins une poudre ou une crème anhydre ou une composition aqueuse, et le deuxième compartiment une composition aqueuse, l'un au moins des deux compartiments contenant au moins un agent réducteur et l'un au moins des deux compartiments contenant au moins un polymère selon l'invention.

Thus, a two-compartment device comprises a first compartment containing at least one anhydrous powder or 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 according to the invention.

But other features, aspects, objects and advantages of the invention will emerge even more clearly on reading the description and examples which follow.

Amphiphilic Polymers According to the Invention The polymers in accordance with the invention are amphiphilic polymers comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or totally neutralized and comprising at least one hydrophobic part.

Amphiphilic polymer is understood to mean any polymer comprising both a hydrophilic part and a hydrophobic part and in particular a fatty chain.

The hydrophobic part present in the polymers of the invention preferably comprises from 6 to 50 carbon atoms, more preferably from 6 to 22 carbon atoms, more preferably still from 6 to 18 carbon atoms, and more particularly from 12 to 18 carbon atoms. carbon atoms.

Preferably, the polymers in accordance with the invention are partially or completely neutralized with a mineral base (sodium hydroxide, potassium hydroxide, aqueous ammonia) or an organic base such as mono-, di- or tri-ethanolamine, aminomethylpropanediol, N- methylglucamine, basic amino acids such as arginine and lysine, and mixtures of these compounds.

The amphiphilic polymers in accordance with the invention generally have a number-average molecular weight ranging from 1000 to 20,000,000 g / mole, preferably ranging from 20,000 to 5,000,000 and still more preferably from 100,000 to 1,500,000 g / mole. mole.

The amphiphilic polymers according to the invention may be crosslinked or non-crosslinked.

Preferably, crosslinked amphiphilic polymers are chosen.

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When they are crosslinked, the crosslinking agents may be chosen from the olefinic polyunsaturated compounds commonly used for crosslinking the polymers obtained by radical polymerization.

propane triacrylate, le méthylène-bis-acrylamide, le méthylène-bis-méthacrylamide, la triallylamine, le triallylcyanurate, le diallylmaléate, la tétraallyléthylènediamine, le tétraallyloxy-éthane, le triméthylolpropane-diallyléther, le (méth) acrylate d'allyle, les éthers allyliques d'alcools de la série des sucres, ou d'autres allyl-ou vinyl-éthers d'alcools polyfonctionnels, ainsi que les esters allyliques des dérivés de l'acide phosphorique et/ou vinylphosphonique, ou les mélanges de ces composés. There may be mentioned, for example, divinylbenzene, diallyl ether, dipropyleneglycoldiallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinonediallyl ether, ethylene glycol or tetraethylene glycol di (meth) acrylate, trimethylol

propane triacrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth) acrylate, ethers allylic alcohols of the series of sugars, or other allyl-or vinyl-ethers of polyfunctional alcohols, as well as the allyl esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures of these compounds.

Methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA) will be used more particularly. The degree of crosslinking will generally vary from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer.

The ethylenically unsaturated monomers containing a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulphonic acid, (meth) acrylamido (C1-C22) alkylsulfonic acids, N- (C1-C22) alkyl (meth) acrylamido acids (Ci - C22) alkylsulphonic acids such as undecyl-acrylamido-methanesulphonic acid and their partially or totally neutralized forms.

méthylpropane-sulfonique, l'acide méthacrylamido-2-méthylpropane-sulfonique, l'acide 2acrylam ido-n-butane-sulfonique, l'acide 2-acrylam ido-2, 4, 4-triméthylpentane-sulfonique, l'acide 2-méthacrylamido-dodécyl-sulfonique, l'acide 2-acrylamido-2, 6-diméthyl-3heptane-sulfonique ainsi que leurs formes partiellement ou totalement neutralisées. More preferably, (meth) acrylamido (C 1 -C 22) alkylsulfonic acids such as, for example, acrylamido-methanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulphonic acid, 2-acrylamido-2- acid

methylpropanesulphonic acid, methacrylamido-2-methylpropanesulfonic acid, 2acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2- methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptane-sulfonic acid and their partially or totally neutralized forms.

More particularly, use 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or completely neutralized forms.

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The amphiphilic polymers in accordance with the invention may especially be chosen from AMPS random amphiphilic polymers modified by reaction with a n-monoalkylamine or a di-n-alkylamine in Ce-C22, and such as those described in the patent application. WO00 / 31154 (forming an integral part of the content of the description).

These polymers may also contain other hydrophilic ethylenically unsaturated monomers chosen for example from (meth) acrylic acids, their ss-substituted alkyl derivatives or their esters obtained with monoalcohols or mono-or poly-alkylene glycols, (meth) acrylamides vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

The preferred polymers of the invention are chosen from AMPS amphiphilic copolymers and at least one hydrophobic ethylenically unsaturated monomer comprising at least one hydrophobic part having from 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms. carbon and more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

These same copolymers may also contain one or more ethylenically unsaturated monomers which do not comprise a fatty chain, such as (meth) acrylic acids, their p-substituted alkyl derivatives or their esters obtained with monoalcohols or mono or polyalkylene glycols, (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures thereof.

These copolymers are described in particular in patent application EP-A-750899, patent US 5089578 and in the following Yotaro Morishima publications: - Self-assembly amphiphilic polyelectrolytes and their nanostructures-Chinese
Journal of Polymer Science Vol. 18, NO40, (2000), 323-336. - Miscellanous formation of random copolymers of 2- (acrylamido) -2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules 2000, Vol. 33,? 10-3694-3704; Solution properties of non-ionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior-Langmuir, 2000,
Flight. 16, NO12, 5324-5332));

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Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido)-2- methylpropanesulfonate and associative macromonomers-Polym. Preprint, Div.

Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and associative macromonomers-Polym. Preprint, Div.

 Polym. Chem. 1999, 40 (2), 220-221.

dans laquelle R1 et R3, identiques ou différents, désignent un atome d'hydrogène ou un radical alkyle linéaire ou ramifié en Ci-Ce (de préférence méthyle) ; Y désigne 0 ou NH ; R2 désigne un radical hydrocarboné hydrophobe comportant au moins de 6 à 50 atomes de carbone et plus préférentiellement de 6 à 22 atomes de carbone et encore plus préférentiellement de 6 à 18 atomes de carbone et plus particulièrement de 12 à 18 atomes de carbone ; x désigne un nombre de moles d'oxyde d'alkylène et varie de 0 à 100. The hydrophobic monomers with ethylenic unsaturation of these particular copolymers are preferably chosen from the acrylates or acrylamides of formula (1) below:

in which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y is 0 or NH; R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms and more preferably 6 to 22 carbon atoms and even more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.

The radical R 2 is preferably chosen from linear (e.g. n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (e.g. cyclododecane (Cree)) alkyl radicals. or adamantane (C10)); C6-C18 perfluorinated alkyl radicals (for example the group of formula - (CH2) 2- (CF2) 9-CF3); the cholesteryl radical (C27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group; polycyclic aromatic groups such as naphthalene or pyrene. Among these radicals, linear alkyl radicals, and more particularly the n-dodecyl radical, are more particularly preferred.

According to a particularly preferred form of the invention, the monomer of formula (1) comprises at least one alkylene oxide unit (x 1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain, preferably, consists of

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 ethylene oxide units and / or propylene oxide units and even more particularly consisting of ethylene oxide units. The number of oxyalkylenated units generally varies from 3 to 100 and more preferably from 3 to 50 and even more preferably from 7 to 25.

Among these polymers, mention may be made of: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C 8 -C 16) alkyl (meth) units acrylamide or (C 8 -C 16) alkyl (meth) acrylate units with respect to the polymer, such as those described in application EP-A-750 899; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C6-C18) alkylacrylamide units, such as those described in US Patent 5089578.

Mention may also be made of copolymers of fully neutralized AMPS and of dodecyl methacrylate, as well as copolymers of AMPS and n-dodecylmethacrylamide which are non-crosslinked and crosslinked, such as those described in the Morishima articles cited above.

dans laquelle X+ est un proton, un cation de métal alcalin, un cation alcalino-terreux ou l'ion ammonium, et de motifs de formule (ici) suivante : More particularly, copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (here) are as follows:

in which X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion, and units of the following formula (here):

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dans laquelle x désigne un nombre entier variant de 3 à 100, de préférence de 5 à 80 et plus préférentiellement de 7 à 25 ; R1 a la même signification que celle indiquée cidessus dans la formule (1) et R4 désigne un alkyle linéaire ou ramifié en C6-C22 et plus préférentiellement en Cio-C22.

in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R1 has the same meaning as that indicated above in formula (1) and R4 denotes a linear or branched C6-C22 and more preferably C10-C22 alkyl.

Particularly preferred polymers are those where x = 25, R1 is methyl and R4 is n-dodecyl; they are described in the articles of Morishima mentioned above.

The polymers for which XI denotes sodium or ammonium are more particularly preferred.

The preferred amphiphilic polymers according to the invention can be obtained according to the conventional methods of radical polymerization in the presence of one or more initiators such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, ABAH (2, 2- azobis- [2-amidinopropane] hydrochloride), organic peroxides such as dilauryl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, etc ..., inorganic peroxidized compounds such as potassium persulfate or ammonium, or H 2 O 2 optionally in the presence of reducing agents.

They are especially obtained by radical polymerization in tert-butanol medium in which they precipitate.

By using precipitation polymerization in tert-butanol, it is possible to obtain a particle size distribution of the polymer which is particularly favorable for its uses.

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La distribution de la taille des particules du polymère peut être déterminée par exemple par diffraction laser ou analyse d'image.

The particle size distribution of the polymer can be determined, for example, by laser diffraction or image analysis.

An interesting distribution for polymer type and determined by image analysis is as follows: 60.2% less than 423 microns, 52.0% less than 212 microns, 26.6% less than 106 microns, 2.6% less than 45 microns and 26.6% greater than 850 microns.

The reaction may be conducted at a temperature between 0 and 150oC, preferably between 10 and 100oC, either at atmospheric pressure or under reduced pressure.

It can also be carried out under an inert atmosphere, and preferably under nitrogen.

According to this process, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or one of its sodium or ammonium salts, with a (meth) acrylic acid ester, has been polymerized, and an oxyethylenated alcohol with 8 moles of ethylene oxide (GENAPOL C-080 from the company HOECHST / CLARIANT), a C11 oxo alcohol oxyethylenated with 8 moles of ethylene oxide; (GENAPOLR UD-080 from the company HOECHST / CLARIANT), a C10 oxo alcohol oxyethylenated with 7 moles of ethylene oxide (GENAPOL UD-070 from the company HOECHST / CLARIANT), -an alcohol in C12-C14 oxyethylenated with 7 moles of ethylene oxide (GENAPOLR LA-070 from Hoechst / Clariant), of a C12-C14 alcohol oxyethylenated with 9 moles of ethylene oxide (GENAPOLR LA-090 from HOECHST / CLARIANT), - a C12-C14 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOLR LA-110 from the company HOECHST / CLARIANT), -an oxyethylenated C16-C18 alcohol by 8 moles d ethylene oxide (GENAPOLR T-080 from the company HOECHST / CLARIANT), a C16-C18 alcohol oxyethylenated with 15 moles of ethylene oxide (GENAPOLR T-150 from the company HOECHST / CLARIANT),

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-d'un alcool en C16-Cl8 oxyéthyléné par 11 moles d'oxyde d'éthylène (GENAPOL T- 110 de la société HOECHST/CLARIANT), -d'un alcool en C16-Cl8 oxyéthyléné par 20 moles d'oxyde d'éthylène (GENAPOLR T- 200 de la société HOECHST/CLARIANT), -d'un alcool en C16-C18 oxyéthyléné par 25 moles d'oxyde d'éthylène (GENAPOLR T- 250 de la société HOECHST/CLARIANT), -d'un alcool en C18-C22 oxyéthyléné par 25 moles d'oxyde d'éthylène et/ou d'un alcool iso C16-C18 oxyéthyléné par 25 moles d'oxyde d'éthylène.

a C16-C18 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOL T-110 from the company HOECHST / CLARIANT), a C16-C18 alcohol oxyethylenated with 20 moles of oxide of ethylene (GENAPOLR T-200 from the company HOECHST / CLARIANT), a C16-C18 alcohol oxyethylenated with 25 moles of ethylene oxide (GENAPOLR T-250 from the company HOECHST / CLARIANT), -of a C18-C22 alcohol oxyethylenated with 25 moles of ethylene oxide and / or a C16-C18 iso alcohol oxyethylenated with 25 moles of ethylene oxide.

The molar concentration in% of the units of formula (11) and units of formula (here) in the polymers according to the invention will vary according to the desired cosmetic application and the desired rheological properties of the formulation. It can vary between 0.1 and 99.9 mol%.

Preferably for the most hydrophobic polymers, the molar proportion in units of formula (1) or (here) varies from 50.1 to 99.9%, more particularly from 70 to 95% and even more particularly from 80 to 90%. .

Preferably for the low hydrophobic polymers, the molar proportion in units of formula (1) or (here) varies from 0.1 to 50%, more particularly from 5 to 25% and even more particularly from 10 to 20%.

The distribution of the monomers in the polymers of the invention may be, for example, alternating, block (including multiblock) or any.

According to the invention, it is preferred that the polymers have pendant heat-sensitive chains whose aqueous solution has a viscosity which, above a certain threshold temperature, increases, or remains substantially constant, as the temperature increases.

More particularly, polymers whose aqueous solution has a viscosity which is low below a first threshold temperature and which above this first threshold temperature increases towards a maximum when the temperature increases, and which, above, a second threshold temperature decreases again as the temperature increases. In this context, it is preferred that the viscosity of the polymer solutions below the first threshold temperature is from 5 to 50%, in particular from 10 to 30% of the maximum viscosity at the second threshold temperature.

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Ces polymères, de préférence, conduisent dans l'eau à un phénomène de démixion par chauffage se traduisant par des courbes présentant, en fonction de la température et de la concentration, un minimum appelé LCST (Lower Critical Solution Temperature).

These polymers, preferably, lead in the water to a demixing phenomenon by heating resulting in curves having, as a function of temperature and concentration, a minimum called LCST (Lower Critical Solution Temperature).

The viscosities (measured at 25 C in the Brookfield needle 7 viscometer) of 1% aqueous solutions are preferably from 20,000 mPas to 100,000 mPas and more preferably from 60,000 mPas to 70,000 mPas.

The amphiphilic polymers in accordance with the invention are present in the compositions in concentrations ranging from 0.01 to 30% by weight, more preferably from 0.1 to 10%, even more preferentially from 0.1 to 5% by weight, and more preferably from 0.5 to 2% by weight.

Reducing agents The reducing agents that 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 bleaching compositions, 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 reducing agents are used in the compositions according to the invention in concentrations of between about 0.1 and 30%, preferably between 0.5 and 20% by weight, by contribution to the total weight of the composition.

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

Cationic Polymers For the purposes of the present invention, the expression "cationic polymer" denotes any polymer containing cationic groups and / or ionizable groups in cationic groups.

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Les polymères cationiques utilisables conformément à la présente invention peuvent être choisis parmi tous ceux déja connus en soi comme améliorant les propriétés cosmétiques des cheveux, à savoir notamment ceux décrits dans la demande de brevet EP-A-337 354 et dans les brevets français FR-2 270 846,2 383 660,2 598 611,2 470 596 et 2 519 863.

The cationic polymers that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in the patent application EP-A-337 354 and in the French patents 2 270 846.2 383 660.2 598 611.2 470 596 and 2 519 863.

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

The cationic polymers used generally have a number-average molecular weight of between about 500 and 5 × 10 6, and preferably between about 103 and 3 × 10 6.

Among the cationic polymers, mention may be made more particularly of the polyamine, polyaminoamide and quaternary polyammonium type polymers.

These are known products. They are in particular described in French Pat. Nos. 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 the following formulas (1), (II), (III) or (IV):

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dans lesquelles : R3, identiques ou différents, désignent un atome d'hydrogène ou un radical CH3 ; A, identiques ou différents, représentent un groupe alkyle, linéaire ou ramifié, de 1 à 6 atomes de carbone, de préférence 2 ou 3 atomes de carbone ou un groupe

hydroxyalkyl de 1 à 4 atomes de carbone ; R4, R5, R6, identiques ou différents, représentent un groupe alkyle ayant de 1 à 18 atomes de carbone ou un radical benzyl et de préférence un groupe alkyle ayant de 1 à 6 atomes de carbone ; R1 et R2, identiques ou différents, représentent hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone et de préférence méthyle ou éthyle ; X désigne un anion dérivé d'un acide minéral ou organique tel qu'un anion méthosulfate ou un halogénure tel que chlorure ou bromure.

in which: R3, which may be identical or different, denote a hydrogen atom or a CH3 radical; A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a group

hydroxyalkyl of 1 to 4 carbon atoms; R4, R5, R6, which may be 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; R1 and R2, identical or different, represent hydrogen or an alkyl group having 1 to 6 carbon atoms and preferably methyl or ethyl; X denotes an anion derived from a mineral or organic acid such as a methosulphate anion or a halide such as chloride or bromide.

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

Thus, among these polymers of family (1), mention may be made of: copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl holognide, such as that sold under the name HERCOFLOC by the company HERCULES the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described for example in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY,

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- le copolymère d'acrylamide et de méthosulfate de méthacryloyloxyéthyltriméthylammonium vendu sous la dénomination RETEN par la société HERCULES, - les copolymères vinylpyrrolidone 1 acrylate ou méthacrylate de dialkylaminoalkyle quaternisés ou non, tels que les produits vendus sous la dénomination"GAFQUAT"par la société ISP comme par exemple"GAFQUAT 734"ou"GAFQUAT 755"ou bien les produits dénommés"COPOLYMER 845,958 et 937". Ces polymères sont décrits en détail dans les brevets français 2.077. 143 et 2.393. 573,

- les terpolymères méthacrylate de diméthyl amino éthyle/vinylcaprolactame/ vinylpyrrolidone tel que le produit vendu sous la dénomination GAFFIX VC 713 par la société ISP, - les copolymère vinylpyrrolidone 1 méthacrylamidopropyl dimethylamine commercialisés notamment sous la dénomination STYLEZE CC 10 par ISP, - et les copolymères vinylpyrrolidone 1 méthacrylamide de diméthylaminopropyle quaternisés tel que le produit vendu sous la dénomination"GAFQUAT HS 100"par la société ISP.

the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate sold under the name Reten by the company Hercules, the vinylpyrrolidone 1 acrylate or dialkylaminoalkyl acrylate or methacrylate quaternized or otherwise, such as the products sold under the name "GAFQUAT" by the company ISP as for example "GAFQUAT 734" or "GAFQUAT 755" or the products called "COPOLYMER 845,958 and 937". These polymers are described in detail in French Patents 2,077. 143 and 2.393. 573

dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP, the vinylpyrrolidone 1 methacrylamidopropyl dimethylamine copolymers sold in particular under the name STYLEZE CC 10 by ISP, and the copolymers vinylpyrrolidone 1 quaternized dimethylaminopropyl methacrylamide such as the product sold under the name "GAFQUAT HS 100" by the company ISP.

(2) The cellulose ether derivatives comprising quaternary ammonium groups described in French Patent 1,492,597, and in particular the polymers sold 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 ammoniums of hydroxyethylcellulose 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 cellulose grafted in particular with a salt of methacryloylethyl trimethylammonium, methacrylmidopropyl trimethylammonium, dimethyl-diallylammonium.

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

(4) The cationic polysaccharides described more particularly in US Pat. Nos. 3,589,578 and 4,031,307, such as guar gums containing groups

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cationiques trialkylammonium. On utilise par exemple des gommes de guar modifiées par un sel (par ex. chlorure) de 2, 3-époxypropyl triméthylammonium.

cationic trialkylammonium. For example, guar gums modified with a salt (eg chloride) of 2,3-epoxypropyltrimethylammonium are used.

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

(5) Polymers consisting of piperazinyl units and straight or branched chain alkylene or hydroxyalkylene divalent radicals, optionally interrupted by oxygen, sulfur, nitrogen or aromatic or heterocyclic rings, as well as oxidation and / or quaternization of these polymers. Such polymers are in particular described in French Patents 2.162. 025 and 2.280. 361.

(6) water-soluble polyamino amines prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or else with an oligomer resulting from the reaction of a bifunctional compound which is reactive with a bis-halohydrin, a bisazetidinium, a bis-haloacyldiamine, an alkyl bis-halide, a epilhalohydrin, a diepoxide or bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 moles 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 in particular described 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 with difunctional agents. Mention may be made, for example, of adipic acid-diacoylaminohydroxyalkyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in French Patent 1,583. 363.

Among these derivatives, mention may be made more particularly of 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 containing two primary amine groups and at least one secondary amine group with a

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acide dicarboxylique choisi parmi l'acide diglycolique et les acides dicarboxyliques aliphatiques saturés ayant de 3 à 8 atomes de carbone. Le rapport molaire entre le polyalkylène polylamine et l'acide dicarboxylique étant compris entre 0, 8 : 1 et 1, 4 : 1 ; le polyaminoamide en résultant étant amené à réagir avec l'épichlorhydrine dans un rapport molaire d'épichlorhydrine par rapport au groupement amine secondaire du polyaminoamide compris entre 0,5 : 1 et 1,8 : 1. De tels polymères sont notamment décrits dans les brevets américains 3.227. 615 et 2.961. 347.

dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio of the polyalkylene polylamine to the dicarboxylic acid is from 0.8: 1 to 1.4: 1; the polyaminoamide resulting therefrom 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 US 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 under the name "PD 170" or "Delsette 101" by the company Hercules in the case of the adipic acid copolymer / epoxypropyl / diethylenetriamine.

formules dans lesquelles k et t sont égaux à 0 ou 1, la somme k + t étant égale à 1 ; Rg désigne un atome d'hydrogène ou un radical méthyle ; R7 et Rg, indépendamment l'un de l'autre, désignent un groupement alkyle ayant de 1 à 22 atomes de carbone, un groupement hydroxyalkyl dans lequel le groupement alkyle a de préférence 1 à 5 atomes de carbone, un groupement amidoalkyle inférieur (Cl-C4), ou R7 et Ra peuvent désigner conjointement avec l'atome d'azote auquel ils sont rattachés, des groupement hétérocycliques, tels que pipéridinyle ou morpholinyl ; R7 et Ra indépendamment l'un de l'autre désignent de préférence un groupement alkyle ayant de 1 à 4 atomes de (9) cyclopolymers of alkyl diallyl amine or of dialkyl diallyl ammonium, such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (V) or (vil):

formulas in which k and t are 0 or 1, the sum k + t being equal to 1; Rg denotes a hydrogen atom or a methyl radical; R7 and Rg, independently of each other, 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 (Cl -C4), or R7 and Ra may designate, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R7 and Ra, independently of one another, preferably denote an alkyl group having from 1 to 4 carbon atoms.

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carbone ; Y- est un anion tel que bromure, chlorure, acétate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. Ces polymères sont notamment décrits dans le brevet français 2.080. 759 et dans son certificat d'addition 2.190. 406.

carbon; 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 his certificate of addition 2.190. 406.

Among the polymers defined above, mention may be made more particularly of the homopolymer of dimethylidenallylammonium chloride sold under the name "Merquat 100" by the company Calgon (and its counterparts of low weight average molecular weight) and the copolymers of sodium chloride. diallyldimethylammonium and acrylamide sold under the name "MERQUAT 550".

formule (Vit) dans laquelle : RiO. Pu. R12 et RI 3, identiques ou différents, représentent des radicaux aliphatiques, alicycliques, ou arylaliphatiques contenant de 1 à 20 atomes de carbone ou des radicaux

hydroxyalkylaliphatiques inférieurs, ou bien R10, Rll, R12 et R13, ensemble ou séparément, constituent avec les atomes d'azote auxquels ils sont rattachés des hétérocycles contenant éventuellement un second hétéroatome autre que l'azote ou bien R1o, R11' R12 et R13 représentent un radical alkyle en Cl-C6 linéaire ou ramifié substitué par un groupement nitrile, ester, acyle, amide ou-CO-0-R-] -D ou-CO-NH- R14-D où R14 est un alkylène et D un groupement ammonium quaternaire ; A1 et B1 représentent des groupements polyméthyléniques contenant de 2 à 20 atomes de carbone pouvant être linéaires ou ramifiés, saturés ou insaturés, et pouvant contenir, liés à ou intercalés dans la chaîne principale, un ou plusieurs cycles aromatiques, ou un ou plusieurs atomes d'oxygène, de soufre ou des groupements sulfoxyde, sulfone, disulfure, amino, alkylamino, hydroxyle, ammonium quaternaire, uréido, amide ou ester, et X- désigne un anion dérivé d'un acide minéral ou organique ;

A1, Rl et R12 peuvent former avec les deux atomes d'azote auxquels ils sont rattachés un cycle pipérazinique ; en outre si A1 désigne un radical alkylène ou hydroxyalkylène linéaire ou ramifié, saturé ou insaturé, B1 peut également désigner un groupement- (CH2) n-CO-D-OC- (CH2) n- dans lequel D désigne : (10) The quaternary diammonium polymer containing recurring units having the formula:

formula (Vit) in which: RiO. Could. R12 and R3, identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or radicals

lower hydroxyalkylaliphatics, or R10, R11, R12 and R13, together or separately, together with the nitrogen atoms to which they are attached constitute heterocycles optionally containing a second heteroatom other than nitrogen or R10, R11 'R12 and R13 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-O-R-] -D or -CO-NH-R14-D group where R14 is an alkylene and D a grouping quaternary ammonium; A1 and B1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more carbon atoms; 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, R1 and R12 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 may also denote a group - (CH2) n -CO-D-OC- (CH2) n- in which D denotes:

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a) un reste de glycol de formule :-0-Z-O-, où Z désigne un radical hydrocarboné linéaire ou ramifié ou un groupement répondant à l'une des formules suivantes : - (CH2-CH2-0) x-CH2-CH2- - [CH2-CH (CH3)-0] y-CH2-CH (CH3)- où x et y désignent un nombre entier de 1 à 4, représentant un degré de polymérisation défini et unique ou un nombre quelconque de 1 à 4 représentant un degré de polymérisation moyen ; b) un reste de diamine bis-secondaire tel qu'un dérivé de pipérazine ; c) un reste de diamine bis-primaire de formule :-NH-Y-NH-, où Y désigne un radical hydrocarboné linéaire ou ramifié, ou bien le radical bivalent -CH2-CH2-S-S-CH2-CH2-; d) un groupement uréylène de formule :-NH-CO-NH-.

a) a glycol residue of formula: -O-ZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: - (CH2-CH2-O) x-CH2-CH2- - [CH2-CH (CH3) -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 a degree of average 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 the divalent radical -CH2-CH2-SS-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 100000.

Polymers of this type are described 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.

dans laquelle R10, R11, R12 et R13, identiques ou différents, désignent un radical alkyle ou hydroxyalkyl ayant de 1 à 4 atomes de carbone environ, n et p sont des nombres entiers variant de 2 à 20 environ et, X- est un anion dérivé d'un acide minéral ou organique. It is more particularly possible to use polymers which consist of recurring units corresponding to the following formula (VIII):

in which R10, R11, R12 and R13, which may be identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms, n and p are integers ranging from 2 to approximately 20 and, X- is an anion derived from a mineral or organic acid.

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

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dans laquelle p désigne un nombre entier variant de 1 à 6 environ, D peut être nul ou peut représenter un groupement- (CH2) r-CO-dans lequel r désigne un nombre égal à 4 ou à 7, X- est un anion ; De tels polymères peuvent être préparés selon les procédés décrits dans les brevets U. S. A. no 4 157388, 4702906, 4719282. Ils sont notamment décrits dans la demande de brevet EP-A-122 324.

wherein p denotes an integer ranging from 1 to about 6, D may be zero or may represent a group - (CH 2) r -CO-- in which r denotes a number equal to 4 or 7, X - is an anion; Such polymers may be prepared according to the processes described in US Pat. Nos. 4,157,388, 4,702,906 and 4,719,282. They are described in particular in patent application EP-A-122,324.

Among them, there may be mentioned, for example, the products "Mirapol A 15", "Mirapol AD1", "Mirapol AZ1" and "MirapoI175" sold by Miranol.

(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as, for example, the products sold 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 "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary.

(14) Crosslinked polymers of methacryloyloxyalkyl (C1-C4) trialkyl (C1-C4) ammonium salts such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized by the methyl chloride, homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. It is more particularly possible to 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 "SALCARE SC 92" by the company ALLIED COLLOIDS. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are

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commercialisées sous les noms de"SALCARE@ SC 95"et"SALCARE SC 96"par la Société ALLIED COLLOIDS.

sold under the names "SALCARE @ SC 95" and "SALCARE SC 96" by the company ALLIED COLLOIDS.

Other cationic polymers that may be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.

et notamment ceux dont le poids moléculaire, déterminé par chromatographie par perméation de gel, est compris entre 9500 et 9900 ;

et notamment ceux dont le poids moléculaire, déterminé par chromatographie par perméation de gel, est d'environ 1200. Among all the cationic polymers that may be used in the context of the present invention, it is preferred to use the polymers of the families (1), (9), (10) (11) and (14) and even more preferentially the recurring pattern polymers of the following formulas (W) and (U):

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

and especially those whose molecular weight, determined by gel permeation chromatography, is about 1200.

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

Amphoteric Polymers The amphoteric polymers that may be used in accordance with the present invention may be chosen from polymers comprising K and M units statistically distributed in the

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chaîne polymère, où K désigne un motif dérivant d'un monomère comportant au moins un atome d'azote basique et M désigne un motif dérivant d'un monomère acide comportant un ou plusieurs groupements carboxyliques ou sulfoniques, ou bien K et M peuvent désigner des groupements dérivant de monomères zwittérioniques de carboxybétaïnes ou de sulfobétaïnes ; K et M peuvent également désigner une chaîne polymère cationique comportant des groupements amine primaire, secondaire, tertiaire ou quaternaire, dans laquelle au moins l'un des groupements amine porte un groupement carboxylique ou sulfonique relié par l'intermédiaire d'un radical hydrocarboné, ou bien K et M font partie d'une chaîne d'un polymère à motif éthylène a, ss-dicarboxylique dont l'un des groupements carboxyliques a été amené à réagir avec une polyamine comportant un ou plusieurs groupements amine primaire ou secondaire.

polymer chain, where K denotes a unit derived from a monomer comprising at least one basic nitrogen atom and M denotes a unit derived from an acidic monomer comprising one or more carboxylic or sulphonic groups, or K and M may designate groups derived from zwitterionic monomers of carboxybetaines or sulfobetaines; K and M may 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 connected via a hydrocarbon radical, or K and M are part of a chain of an α, β-dicarboxylic ethylene-based polymer having one of the carboxylic groups reacted with a polyamine having one or more primary or secondary amine groups.

particulièrement l'acide acrylique, l'acide méthacrylique, l'acide maléique, l'acide alpha-chloracrylique, et d'un monomère basique dérivé d'un composé vinylique substitué contenant au moins un atome basique tel que plus particulièrement les dialkylaminoalkyl méthacrylate et acrylate, les dialkylaminoalkylméthacrylamide et acrylamide. De tels composés sont décrits dans le brevet américain no 3 836 537. The amphoteric polymers corresponding to the definition given above, which are more particularly preferred, are chosen from the following polymers: (1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as more

particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloro acrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in U.S. Patent No. 3,836,537.

Mention may also be made of the acrylate of sodium 1 acrylamidopropyltrimethylammonium chloride copolymer sold under the name Polyquart
KE 3033 by the company HENKEL.

The vinyl compound may also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. Copolymers of acrylic acid and of the latter monomer are available 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 methacrylamides substituted on the nitrogen with an alkyl radical, b) with at least one acidic comonomer containing one or more carboxylic groups reagents, and

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c) d'au moins un comonomère basique tel que des esters à substituants amine primaire, secondaire, tertiaire et quaternaire des acides acrylique et méthacrylique et le produit de quaternisation du méthacrylate de diméthylaminoéthyle avec le sulfate de diméthyle ou diéthyle.

c) at least one basic comonomer such as primary, secondary, tertiary and quaternary amine substituent esters of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butyl-acrylamide and N-tert-octyl-acrylamide. N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.

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

The copolymers whose CTFA (4th Ed., 1991) name is octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer, such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company National Starch, are particularly used.

dérivant de polyaminoamide de formule générale :

+CO-R19-CO-Z-± (X)

dans laquelle Ri 9 représente un radical divalent dérivé d'un acide dicarboxylique saturé, d'un acide aliphatique mono ou dicarboxylique à double liaison éthylénique, d'un ester d'un alcanol inférieur ayant 1 à 6 atomes de carbone de ces acides ou d'un radical dérivant de l'addition de l'un quelconque desdits acides avec une amine bis primaire ou bis secondaire, et Z désigne un radical d'une polyalkylène-polyamine bis-primaire, mono

ou bis-secondaire et de préférence représente : a) dans les proportions de 60 à 100 moles %, le radical

- N --t- (CH2) x - N + (XI) H H P

où x=2 et p=2 ou 3, ou bien x=3 et p=2 (3) The crosslinked polyaminoamides and alkylated partially or totally

derived from polyaminoamide of the general formula:

+ CO-R19-CO-Z- ± (X)

wherein R 9 represents a divalent radical derived from a saturated dicarboxylic acid, an ethylenically double-bonded mono or dicarboxylic aliphatic acid, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or a radical derived from the addition of any of said acids with a primary bis or secondary bis amine, and Z denotes a radical of a bis-primary polyalkylene-polyamine, mono

or bis-secondary and preferably represents: a) in the proportions of 60 to 100 mol%, the radical

- N --t- (CH2) x - N + (XI) HHP

where x = 2 and p = 2 or 3, or x = 3 and p = 2

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ce radical dérivant de la diéthylène triamine, de la triéthylène tétraamine ou de la dipropylène triamine ; b) dans les proportions de 0 à 40 moles % le radical (XI) ci-dessus, dans lequel x=2 et p=1 et qui dérive de l'éthylènediamine, ou le radical dérivant de la pipérazine :

c) dans les proportions de 0 à 20 moles % le radical-NH- (CH2) 6-NH- dérivant de l'hexaméthylènediamine, ces polyaminoamines étant réticulées par addition d'un agent réticulant bifonctionnel choisi parmi les épihalohydrines, les diépoxydes, les dianhydrides, les dérivés bis insaturés, au moyen de 0,025 à 0,35 mole d'agent réticulant par groupement amine du polyaminoamide et alcoylés par action d'acide acrylique, d'acide chloracétique ou d'une alcane sultone ou de leurs sels.

this radical derived 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 is derived from ethylenediamine, or the radical derived from piperazine:

c) in the proportions of 0 to 20 mole%, the radical-NH- (CH 2) 6 -NH- derived from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis unsaturated derivatives, by means of 0.025 to 0.35 mole of crosslinking agent per amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloroacetic acid or an alkane sultone or their salts.

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

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

dans laquelle R20 désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou méthacrylamide, y et z représentent un nombre entier de 1 à 3, R21 et R22 représentent un atome d'hydrogène, méthyle, éthyle ou propyl, R23 et R24 représentent un atome d'hydrogène ou un radical alkyle de telle façon que la somme des atomes de carbone dans R23 et R24 ne dépasse pas 10. (4) polymers having zwitterionic units of formula:

in which R 20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer of 1 to 3, R 21 and R 22 represent a hydrogen, methyl, ethyl or propyl atom, R 23 and R24 represents a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.

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

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A titre d'exemple, on peut citer le copolymère de méthacrylate de méthyle/diméthylcarboxyméthylammonio-éthylméthacrylate de méthyle tel que le produit vendu sous la dénomination DIAFORMER Z301 par la société SANDOZ.

By way of example, mention may be made of the copolymer of methyl methacrylate / methyl dimethylcarboxymethylammonioethyl methacrylate, such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.

le motif (Xi))) étant présent dans des proportions comprises entre 0 et 30%, le motif (XIV) dans des proportions comprises entre 5 et 50% et le motif F dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif (XV), R25 représente un radical de formule :

dans laquelle si q=0, R26, R27 et R28, identiques ou différents, représentent chacun un atome d'hydrogène, un reste méthyle, hydroxyle, acétoxy ou amino, un reste monoalcoylamine ou un reste dialcoylamine éventuellement interrompus par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes amine, hydroxyle, carboxyle, alcoylthio, sulfonique, un reste alcoylthio dont le groupe alcoyle porte un reste amino, l'un au moins des radicaux R26, R27 et R28 étant dans ce cas un atome d'hydrogène ; ou si q=1, R26, R27 et R28 représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides. (5) polymers derived from chitosan having monomeric units corresponding to the following formulas (XIII), (XIV), (XV):

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

in which if q = 0, R26, R27 and R28, which are identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or more carbon atoms. nitrogen and / or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio, sulphonic groups, an alkylthio radical whose alkyl group carries an amino residue, at least one of the radicals R26, R27 and R28 being in this case a hydrogen atom; or if q = 1, R26, R27 and R28 each represents a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

 (6) The polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under the name "Evalsan" by the company Jan Dekker.

<Desc / Clms Page number 27>

dans laquelle R29 représente un atome d'hydrogène, un radical CH30, CH3CH20, phényle, R30 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R31désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R32 désigne un radical alkyle inférieur tel que méthyle, éthyle ou un radical répondant à la formule :-R33-N (R31) 2, R33 représentant un groupement-CH2-CH2-,-CH2-CH2-CH2- ,-CH2-CH (CH3)-, R31 ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces radicaux et contenant jusqu'à 6 atomes de carbone, r est tel que le poids moléculaire est compris entre 500 et 6000000 et de préférence entre 1000 et 1000000. (7) The polymers corresponding to the general formula (XI) such as those described for example in the French patent 1,400,366:

in which R29 represents a hydrogen atom, a radical CH30, CH3CH20, 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 (R31) 2, R33 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH ( CH3) -, R31 having the meanings mentioned above, as well as the higher homologues of these radicals and containing up to 6 carbon atoms, r is such that the molecular weight is between 500 and 6000000 and preferably between 1000 and 1000000.

(8) Amphoteric polymers of the -DXDX-type chosen from: a) the polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula: -DXDXD- (XVII) where D designates a radical

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et X désigne le symbole E ou E'et au moins une fois E' ; E ayant la signification indiquée ci-dessus et E'est un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs radicaux hydroxyle et comportant un ou plusieurs atomes d'azote, l'atome d'azote étant substitué par une chaîne alkyle interrompue éventuellement par un atome d'oxygène et comportant obligatoirement une ou plusieurs fonctions carboxyle ou une ou plusieurs fonctions hydroxyle et bétaïnisées par réaction avec l'acide chloracétique ou du chloracétate de soude. and X denotes the symbol E or E ', E or E' the same or different denotes a divalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the unsubstituted or group-substituted main chain hydroxyl and may further comprise oxygen, nitrogen, sulfur, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide groups, alcohol, ester and / or urethane; b) polymers of formula: -DXDX- (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 divalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or unsubstituted by one or more hydroxyl radicals and having a or a plurality of nitrogen atoms, the nitrogen atom being substituted by an optionally interrupted alkyl chain by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betaineized by reaction with chloroacetic acid or chloroacetate of soda.

Ces copolymères peuvent également comporter d'autres comonomères vinyliques tels que le vinylcaprolactame. (9) (C1-C5) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with an N, N-dialkanolamine.

These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam.

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

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

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The compositions of the invention preferably comprise one or more surfactants. The surfactant or surfactants can be indifferently chosen, alone or in mixtures, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.

d'aminoalcools ou sels de magnésium) des composés suivants : les alkylsulfates, les alkyléthersulfates, alkylamidoéthersulfates, alkylarylpolyéthersulfates, monoglycérides sulfates ; les alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, a-oléfine-sulfonates, paraffine-sulfonates ; les alkyl (C6-C24) sulfosuccinates, les alkyl (C6- C24) éthersulfosuccinates, les alkyl (C6-C24) amidesulfosuccinates, les alkyl (C6-C24) sulfoacétates ; les acyl (C6-C24) sarcosinates et les acyl (C6-C24) glutamates. On peut également utiliser les esters d'alkyl (C6-C24) polyglycosides carboxyliques tels que les alkylglucoside citrates, les alkylpolyglycoside tartrate et les alkylpolyglycoside

sulfosuccinates., les alkylsulfosuccinamates ; les acyliséthionates et les N-acyltaurates, le radical alkyle ou acyle de tous ces différents composés comportant de préférence de 12 à 20 atomes de carbone, et le radical aryl désignant de préférence un groupement phényle ou benzyl. Parmi les tensioactifs anioniques encore utilisables, on peut également citer les sels d'acides gras tels que les sels des acides oléique, ricinoléique, palmitique, stéarique, les acides d'huile de coprah ou d'huile de coprah hydrogénée ; les acyl-lactylates dont le radical acyle comporte 8 à 20 atomes de carbone. On peut également utiliser les acides d'alkyl D galactoside uroniques et leurs sels, les acides alkyl (Ce-C24) éther carboxyliques polyoxyalkylénés, les acides alkyl (C6-C24) aryl éther carboxyliques polyoxyalkylénés, les acides alkyl (C6-C24) amido éther carboxyliques polyoxyalkylénés et leurs sels, en particulier ceux comportant de 2 à 50 groupements oxyde d'alkylène en particulier d'éthylène, et leurs mélanges. The surfactants that are suitable for carrying out the present invention are, in particular: (i) Anionic surfactant (s): As an example of anionic surfactants that can be used, alone or as mixtures, in the context of the According to the present invention, mention may be made especially of (non-limiting list) salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, salts,

aminoalcohols or magnesium salts) of the following compounds: alkyl sulphates, alkyl ether sulphates, alkyl amido ether sulphates, alkyl aryl polyether sulphates, monoglyceride sulphates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin-sulfonates, paraffin-sulfonates; (C6-C24) alkylsulfosuccinates, (C6-C24) alkylsulfosuccinates, (C6-C24) alkylamidesulfosuccinates, (C6-C24) alkylsulfoacetates; acyl (C6-C24) sarcosinates and acyl (C6-C24) glutamates. It is also possible to use (C6-C24) alkyl polyglycoside carboxylic esters such as alkylglucoside citrates, alkylpolyglycoside tartrate and alkylpolyglycoside

sulfosuccinates., alkylsulfosuccinamates; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably comprising from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants that can still be used, mention may also be made of fatty acid salts such as the salts of oleic, ricinoleic, palmitic and stearic acids, coconut oil acid or hydrogenated coconut oil acid; acyl lactylates whose acyl radical has 8 to 20 carbon atoms. It is also possible to use alkyl D-galactoside uronic acids and their salts, polyoxyalkylenated alkyl (C6-C24) ether carboxylic acids, polyoxyalkylenated (C6-C24) aryl ether carboxylic acids, (C6-C24) alkyl amido acids. polyoxyalkylenated carboxylic ether and their salts, in particular those containing from 2 to 50 alkylene oxide groups, in particular ethylene, and mixtures thereof.

 (ii) Nonionic surfactant (s):

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Les agents tensioactifs non-ioniques sont, eux aussi, des composés bien connus en soi (voir notamment à cet égard"Handbook of Surfactants"par M. R. PORTER, éditions Blackie & Son (Glasgow and London), 1991, pp 116-178) et leur nature ne revet pas, dans le cadre de la présente invention, de caractère critique. Ainsi, ils peuvent être notamment choisis parmi (liste non limitative) les alcools, les alpha-diols, les alkylphénols polyéthoxylés, polypropoxylés, ayant une chaîne grasse comportant par exemple 8 à 18 atomes de carbone, le nombre de groupements oxyde d'éthylène ou oxyde de propylène pouvant aller notamment de 2 à 50. On peut également citer les copolymères d'oxyde d'éthylène et de propylène, les condensats d'oxyde d'éthylène et de propylène sur des alcools gras ; les amides gras polyéthoxylés ayant de préférence de 2 à 30 moles d'oxyde d'éthylène, les amides gras polyglycérolés comportant en moyenne 1 à 5 groupements glycérol et en particulier 1,5 à 4 ; les amines grasses polyéthoxylées ayant de préférence 2 à 30 moles d'oxyde d'éthylène ; les esters d'acides gras du sorbitan oxyéthylénés ayant de 2 à 30 moles d'oxyde d'éthylène ; les esters d'acides gras du sucrose, les esters d'acides gras du polyéthylèneglycol, les alkylpolyglycosides, les

dérivés de N-alkyl glucamine, les oxydes d'amines tels que les oxydes d'alkyl (C0-C14) amines ou les oxydes de N-acylaminopropylmorpholine. On notera que les alkylpolyglycosides constituent des tensio-actifs non-ioniques rentrant particulièrement bien dans le cadre de la présente invention.

Nonionic 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 does not, in the context of the present invention, be critical. Thus, they may be chosen in particular from (non-limiting list) alcohols, alpha-diols, polyethoxylated alkylphenols, polypropoxylated, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of ethylene oxide groups or propylene oxide which may range from 2 to 50. Mention may also be made of copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and of propylene oxide 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; polyethoxylated fatty amines preferably having 2 to 30 moles of ethylene oxide; oxyethylenated sorbitan fatty acid esters 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 (C0-C14) alkyl oxides or N-acylaminopropylmorpholine oxides. It will be noted that the alkylpolyglycosides constitute nonionic surfactants that fall particularly well within the scope of the present invention.

 (iii) amphoteric (s) or zwitterionic (s) surfactant (s): Amphoteric or zwitterionic surfactants, the nature of which does not fall within the scope of the present invention of a critical nature, may especially be (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulphonate, sulphate, phosphate or phosphonate); mention may also be made of (C8-C20) alkyl betaines, sulphobetaines, (C8-C20) alkylamido (C1-C6) alkyl betaine or (C8-C20) alkylamido (C1-C6) alkyl sulphobetaines.

Among the amine derivatives, mention may be made of the products sold under the name MIRANOL, as described in US Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates of respective structures: R2-CONHCH2CH2-N (R3) (R4) (CH2COO-)

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dans laquelle : R2 désigne un radical alkyle d'un acide R2-COOH présent dans l'huile de coprah hydrolysée, un radical heptyl, nonyle ou undécyle, R3 désigne un groupement bêta-hydroxyéthyle et R4 un groupement carboxyméthyle ; et R2'-CONHCH2CH2-N (B) (C) dans laquelle :

B représente-CHCHOX', C représente- (CH2) z-Y', avec z = 1 ou 2, X'désigne le groupement-CH2CH2-COOH ou un atome d'hydrogène Y'désigne-COOH ou le radical-CH2-CHOH-SCH R2'désigne un radical alkyle d'un acide Rg-COOH présent dans l'huile de coprah ou dans l'huile de lin hydrolysée, un radical alkyle, notamment en C7, Cg, Cl ou C13, un radical alkyle en C17 et sa forme iso, un radical C17 insaturé.

in which: R2 denotes an alkyl radical of a R2-COOH acid present in the hydrolysed coconut oil, a heptyl, nonyl or undecyl radical, R3 denotes a beta-hydroxyethyl group and R4 a carboxymethyl group; and R2'-CONHCH2CH2-N (B) (C) wherein:

B represents-CHCHOX ', C represents- (CH2) z-Y', with z = 1 or 2, X'disigne the group -CH2CH2-COOH or a hydrogen atom Y'digne-COOH or the radical-CH2- CHOH-SCH R2 'denotes an alkyl radical of an Rg-COOH acid present in coconut oil or in hydrolysed linseed oil, an alkyl radical, in particular a C7, Cg, Cl or C13 alkyl radical, C17 and its iso form, an unsaturated C17 radical.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium Caprylamphodipropionate, Disodium Capryloamphodipropionate, Lauroamphodipropionic Acid, Cocoamphodipropionic Acid.

By way of example, mention may be made of cocoamphodiacetate sold under the trade name MIRANOLO C2M concentrated by the company Rhodia Chimie.

 (iv) Cationic surfactants: Among the cationic surfactants, mention may be made in particular (non-limiting list): primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated; quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides; imidazoline derivatives; or oxides of amines with a cationic character.

The amounts of surfactants present in the composition according to the invention may vary from 0.01 to 40% and preferably from 0.5 to 30% of the total weight of the composition.

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Le pH de la composition prête à l'emploi est généralement compris entre environ 1, 5 et 12. Plus préférentiellement, le pH des compositions de l'invention prêtes à l'emploi destinées à la décoloration est compris entre environ 1,5 et 10, et encore plus préférentiellement entre environ 1,5 et 7.

The pH of the ready-to-use composition is generally between about 1.5 and 12. More preferably, the pH of the ready-to-use compositions of the invention for bleaching is between about 1.5 and 10. and even more preferably between about 1.5 and 7.

More preferably, the pH of the compositions of the invention ready for use for permanent deformation is between about 6 and 12 and even more preferably between about 7 and 11.

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

dans laquelle R est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en Ci-C4 ; R38, R39, R4o et R4,, identique ou différents, représentent un atome d'hydrogène, un radical alkyle en Ci-C4 ou hydroxyalkyl en Ci-C4 Les agents acidifiants sont classiquement, à titre d'exemple, des acides minéraux ou organiques comme l'acide chlorhydrique, l'acide orthophosphorique, des acides carboxyliques comme l'acide tartrique, l'acide citrique, l'acide lactique, ou des acides sulfoniques. Among the alkalinizing agents, mention may be made, for example, of ammonia, alkali or ammonium carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, hydroxyalkylamines and ethylene-diamines ethoxylated and or oxypropylenes, the hydroxides of sodium or of potassium and the compounds of formula (XIX) below:

wherein R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R38, R39, R4o and R4, identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl acidifying agents are conventionally, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, or sulfonic acids.

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

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

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When the compositions containing the reducing agent and the polymer according to the invention are in anhydrous form (powder or cream), they contain the main agents and additives mentioned above in the form of solids or essentially anhydrous liquids.

monométhyléther de propylèneglycol, le butylèneglycol, le dipropylèneglycol ainsi que les alkyléthers de diéthylèneglycol comme par exemple, le monoéthyléther ou le monobutyléther du diéthylèneglycol. Les solvants peuvent alors être présents dans des concentrations comprises entre environ 0,5 et 20% et, de préférence, entre environ 2 et 10% en poids par rapport au poids total de la composition. When the medium containing the reducing agent is an aqueous medium, it may optionally contain cosmetically acceptable organic solvents, more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or polyols or polyol ethers such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example,

propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers, for example diethylene glycol monoethyl ether or monobutyl ether. The solvents can then be present 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, moreover previously known in discoloration or in permanent deformation of the keratinous fibers. Of course, those skilled in the art will take care to choose the or the optional additional compounds mentioned above, in such a way that the advantageous properties intrinsically attached to the permanent fading or deformation composition of the keratinous fibers according to the invention are not, or not substantially, impaired by the addition or additions envisaged. .

Preferably, the bleaching process according to the invention consists in applying the ready-to-use reducing composition to the dry or moist keratinous fibers and in letting it act for a rest period, preferably varying from 1 to 60 hours. minutes, and more preferably from 10 to 45 minutes, rinsing the fibers, then possibly washing them with shampoo, then rinsing again, and drying.

Preferably, the permanent deformation process according to the invention consists in applying the ready-to-use reducing composition to the dry or moist keratinous fibers, allowing it to act for a pause time varying, preferably from 1 to 60 minutes. approximately, and more preferably from 10 to 45 minutes, to possibly rinse the fibers, then to apply an oxidizing composition and to let act

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pendant un temps de pause compris entre 1 et 20 minutes et de préférence entre 1 et 10 minutes, puis éventuellement à les laver au shampooing, puis à les rincer à nouveau, et à les sécher.

during a pause of between 1 and 20 minutes and preferably between 1 and 10 minutes, then optionally washing them with shampoo, then rinsing them again, and drying them.

Mechanical means for tensioning the keratinous fibers may 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 given below, without being limiting in nature.

PREPARATION EXAMPLES Preparation of ethoxylated (meth) acrylic esters

They may especially be obtained by the action of glycidyl (meth) acrylate, or (meth) acrylic acid, or of an alkyl (meth) acrylate, or of a (meth) acryloyl halide on a fatty alcohol. ethoxylated. By way of non-limiting examples, mention may be made of the following preparations: a) from glycidyl methacrylate and from GENAPOL T-250 b) from (meth) acrylic acid and from GENAPOL UD-070 c) from methyl (meth) acrylate and GENAPOL LA-090 d) from (meth) acryloyl chloride and GENAPOL UD-070. a) In a one-liter one-liter reactor equipped with a stirrer, a thermometer and a reflux condenser, 500 g of Genapol T-250 and 75 g of glycidyl methacrylate are introduced. The reaction mixture was heated at 100 ° C. for 2 hours, and the excess glycidyl methacrylate was distilled off under reduced pressure. The monomer obtained can be used for the polymerization without further purification. b) In a one-liter one-liter reactor equipped with a stirrer, a thermometer and a reflux condenser, 500 g of Genapol UD-070,100 g of (meth) acrylic acid and p-acid are introduced. -toluenesulphonic as catalyst. The reaction mixture was refluxed for 2 hours, and excess acid and water formed during the reaction were distilled off under reduced pressure. The monomer obtained can be used for the polymerization without further purification.

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c) Dans un réacteur tricol d'un litre équipé d'un agitateur, d'un thermomètre et d'un condensateur à reflux, on introduit 500g de Genapol LA-090, 100g de (méth) acrylate de méthyle et 20g de tétraisopropoxyde de titane. On chauffe le mélange réactionnel au reflux pendant 2 heures, et après séparation par distillation de l'alcool formé, on distille l'ester qui reste sous pression réduite.

c) In a one-liter one-liter reactor equipped with a stirrer, a thermometer and a reflux condenser, 500 g of Genapol LA-090, 100 g of methyl (meth) acrylate and 20 g of tetraisopropoxide are introduced. titanium. The reaction mixture is heated at reflux for 2 hours, and after separation of the alcohol formed by distillation, the ester which remains under reduced pressure is distilled off.

The monomer obtained can be used for the polymerization without further purification. d) In a one-liter one-liter reactor equipped with a stirrer, a thermometer and a reflux condenser, 500 g of Genapol UD-O70, 110 g of (meth) acryloyl chloride and 50 g of sodium carbonate are introduced. sodium. The reaction mixture was refluxed for 2 hours, and the excess acid chloride was distilled off under reduced pressure. The monomer obtained can be used for the polymerization without further purification.

Polymerization according to the precipitation method in tert-butanol In a 2-liter reactor equipped with a reflux condenser, a gas inlet, a thermometer and a stirrer, 500 ml of tert-butanol are introduced. and the calculated amount of AMPS. The mixture is neutralized by introducing NH 3, and the monomer prepared above is added to the reaction mixture. The reaction mixture is made inert by passing nitrogen or argon and when the internal temperature has reached 60oC, the initiator (AIBN) is introduced to initiate the polymerization.

After a few minutes, the polymer thus prepared precipitates. The mixture is refluxed for 2 hours, and the polymer is separated from the solvent by suction filtration and then dried under reduced pressure.

As described above, the following polymers were prepared: (from the following reactants in amounts expressed in grams)

<Tb>
<tb> Methacrylate <SEP> from <SEP> Genapol <SEP> T-250 .......... <SEP> 10 <SEP> 20 <SEP> 30 <SEP> 97
<tb> AMPS <SEP> neutralized <SEP> with <SEP> NH3 .................. <SEP> 90 <SEP> 80 <SEP> 90 <SEP> 3
<tb> Methylene-bis-acrylamide <SEP> (crosslinker) .. <SEP> 1.5
<tb> Methacrylate <SEP> of allyl <SEP> (crosslinker) ......... <SEP> 1, <SEP> 7
<tb> TMPTA <SEP> (crosslinker) <SEP> 1, <SEP> 8 <SEP> 1, <SEP> 8
<tb> Azobisisobutyronitrile <SEP> (initiator) ...... <SEP> 1
<tb> Peroxide <SEP> dilauryl <SEP> (initiator) ......... <SEP> 1 <SEP> 1 <SEP> 1
<tb> Tert-butanol <SEP> 300 <SEP> 300 <SEP> 300 <SEP> 300
<Tb>

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EXEMPLES D'UTILISATION EXEMPLE 1 : Composition de décoloration On a préparé la composition de décoloration aqueuse prête à l'emploi suivante (exprimée en grammes) :

EXAMPLES OF USE EXAMPLE 1: Bleaching composition The following ready-to-use aqueous bleaching composition (expressed in grams) was prepared:

<Tb>
<tb> Copolymer <SEP> acid <SEP> acrylamido-2-methyl-2-propanesulfonic acid /
<tb> n-dodecylacrylamide <SEP> (3, <SEP> 5% / 96, <SEP> 5%) <SEP> neutralized <SEP> to <SEP> 100% <SEP> by
<tb> the <SEP> soda <SEP> 1
<tb> Alcohol <SEP> isostearyl <SEP> (TEGO <SEP> ALKANOL <SEP> 66 <SEP> sold <SEP> by <SEP>
<tb> company <SEP> GOLDSCHMIDT) <SEP> 12
<tb> Benzyl <SEP> alcohol <SEP> 10
<tb> Hydroxymethane <SEP> sulfinate <SEP> of <SEP> sodium .......... 7
<tb> Adjusted <SEP> to <SEP> pH ...................................... .................. <SEP> 3
<tb> Demineralized <SEP> Water <SEP> q. <SEP> s. <SEP> p <SEP> 100
<Tb>
The fading composition above was applied to natural gray hair with 90% of whites, previously colored by the shade 20 (coppery) of L'OREAL MOVIDA range with a bath ratio of 10 g per 1 g of hair .

After 30 minutes of installation, the locks were rinsed and dried.

The coppery reflection disappeared, revealing the hair as it was before the application of the dye.

EXAMPLE 2: Composition of permanent deformation The following reducing composition (expressed in grams) was prepared:

<Tb>
<tb><SEP> thioglycolic acid <SEP> 9.2
<tb> Arginine <SEP> 15
<tb> Ammonia <SEP> to <SEP> 20% <SEP> of NH3 ....... <SEP> 9.3
<tb> Ammonium carbonate <SEP> ........................................ .......... 4.5
<tb> Cocoylamidopropylbetaine / monolaurate <SEP> of <SEP> glycerol <SEP> (25/5) <SEP> en
<tb> aqueous <SEP> solution <SEP> to <SEP> 30% <SEP> 1,3
<tb> Peptisant <SEP> 0.8
<tb> Copolymer <SEP> acid <SEP> acrylamido-2-methyl-2-propanesulfonic acid /
<Tb>

<Desc / Clms Page number 37>

<Tb>
<tb> n-dodecylacrylamide <SEP> (3.5% / 96, <SEP> 5%) <SEP> neutralized <SEP> to <SEP> 100% <SEP> by <SEP>
<tb> soda <SEP> 1
<tb> Alcohol <SEP> isostearyl <SEP> (TEGO <SEP> ALKANOL <SEP> 66 <SEP> sold <SEP> by <SEP>
<tb> company <SEP> GOLDSCHMIDT) <SEP> 12
<tb> Agent <SEP> sequestering <SEP> 0, <SEP> 4
<tb> Perfume <SEP> 0.4
<tb> Demineralized <SEP> Water <SEP> q. <SEP> s. <SEP> p <SEP> 100
<Tb>
This reducing composition was applied to a lock of damp hair, previously wound on a curler 9 mm in diameter.

After 10 minutes of break time, it was thoroughly rinsed with water.

An oxidizing composition (oxygenated water 8 volumes of pH = 3) was then applied.

After 10 minutes of break time, the wick was rinsed again abundantly.

Then we unrolled the curler's hair and dried it.

The wick was wavy.

Similar results were obtained by replacing the acrylamido-2-methyl-2-propanesulfonic acid / n-dodecylacrylamide acid copolymer neutralized with sodium hydroxide of Examples 1 and 2 above by a methylene-bis-acrylamide crosslinked copolymer constituted by of 75% by weight of NH3 neutralized AMPS units and 25% by weight of units of formula (III) in which R1 = H, R4 = C16-C18 and x = 25.

Similar results were obtained by replacing the above-neutralized 2-acrylamido-2-methyl-propane-sulfonic acid / n-dodecylacrylamide acid copolymer with the sodium hydroxide of Examples 1 and 2 above with a copolymer crosslinked with allyl methacrylate consisting of 90% by weight of NH3 neutralized AMPS units and 10% by weight of GENAPOL T-250 methacrylate units [units of formula (here) in which R1 = CH3, R4 = C16-C18 and x = 25], or by a copolymer crosslinked with allyl methacrylate consisting of 80% by weight of NH3 neutralized AMPS units and 20% by weight of GENAPOL T-250 methacrylate units [units of formula (III) in which R1 = CH3, R4 = C16-C18 and x = 25].

Claims (61)

1. cosmetic and / or dermatological composition for the treatment of keratin materials, characterized in that it comprises in a suitable carrier for keratin materials: (a) at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer to sulfonic group, in free or partially or completely neutralized form and in addition at least one hydrophobic part and (b) at least one reducing agent. 2. Composition according to Claim 1, characterized in that the hydrophobic part of the amphiphilic polymer comprises from 6 to 50 carbon atoms. 3. Composition according to claim 2, characterized in that the hydrophobic portion of the amphiphilic polymer has from 6 to 22 carbon atoms. 4. Composition according to claim 3, characterized in that the hydrophobic part of the amphiphilic polymer comprises from 6 to 18 carbon atoms. 5. Composition according to claim 4, characterized in that the hydrophobic portion of the amphiphilic polymer comprises from 12 to 18 carbon atoms. 6. Composition according to any one of claims 1 to 5, characterized in that the amphiphilic polymers are partially or completely neutralized with a mineral or organic base. 7. Composition according to any one of claims 1 to 6, characterized in that the amphiphilic polymers have a number average molecular weight ranging from 1000 to 20 000 000 g / mol. 8. Composition according to claim 7, characterized in that the number average molecular weight ranges from 20,000 to 5,000,000 g / mol. <Desc / Clms Page number 39>

 9. Composition according to claim 8, characterized in that the number average molecular weight ranges from 100,000 to 1,500,000 g / mol. 10. Composition according to any one of the preceding claims, characterized in that an aqueous solution at 1% by weight of said polymers has at 25 C a viscosity measured Brookfield viscometer, needle 7, ranging from 20,000 mPas at 100,000 mPas. 11. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymers are prepared by radical polymerization by precipitation in tert-butanol. 12. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymers are crosslinked or non-crosslinked. 13. Composition according to claim 12, characterized in that the amphiphilic polymers are crosslinked. 14. Composition according to Claim 13, characterized in that the one or more crosslinking agents are chosen from olefinically polyunsaturated compounds. 15. Composition according to Claim 14, characterized in that the crosslinking agent (s) is (are) chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). 16. Composition according to any one of claims 13 to 15, characterized in that the degree of crosslinking preferably ranges from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer. 17. Composition according to any one of the preceding claims, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is chosen. <Desc / Clms Page number 40>  among vinylsulfonic acid, styrene sulphonic acid, (meth) acrylamido (CiC22) alkylsulphonic acids, N- (Ci-C22) alkyl (meth) acrylamido (Ci-C22) alkylsulphonic acids and their partially or totally neutralized.

18. Composition according to Claim 17, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is chosen from acrylamido acid.

 methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-acid -butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid as well as their partially or completely neutralized forms. 19. Composition according to any one of claims 17 or 18, characterized in that the ethylenically unsaturated monomer containing sulfonic group is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and its forms partially or completely neutralized. 20. Composition according to Claim 19, characterized in that the amphiphilic polymers are chosen from the random polymers of AMPS modified by reaction with a n-mono (C6-C22) alkylamine or a di-n- (Ce-C22). a) ky) amine. 21. Composition according to any one of claims 19 or 20, characterized in that the AMPS amphiphilic polymers additionally contain at least one ethylenically unsaturated monomer having no fatty chain. 22. The composition as claimed in claim 20, characterized in that the ethylenically unsaturated monomer not comprising a fatty chain is chosen from (meth) acrylic acids and their ss-substituted alkyl derivatives, and their esters obtained with monoalcohols or mono- or polyalkylene glycols, or from (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds. 23. Composition according to any one of claims 1 to 19, characterized in that the AMPS amphiphilic polymers are chosen from copolymers <Desc / Clms Page number 41>  amphiphiles of AMPS and at least one ethylenically unsaturated hydrophobic monomer having at least one hydrophobic portion having from 6 to 50 carbon atoms.

24. Composition according to Claim 23, characterized in that the hydrophobic part contains from 6 to 22 carbon atoms. 25. Composition according to Claim 24, characterized in that the hydrophobic part contains from 6 to 18 carbon atoms. 26. Composition according to claim 25, characterized in that the hydrophobic portion comprises from 12 to 18 carbon atoms. 27. Composition according to any one of claims 23 to 26, characterized in that the hydrophobic monomer ethylenically unsaturated is selected from acrylates or acrylamides of formula (1) below:

 in which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y is 0 or NH; R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms and more preferably 6 to 22 carbon atoms and even more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100. 28. Composition according to Claim 27, characterized in that the hydrophobic radical R2 is chosen from linear, branched or C 6 -C 18 alkyl radicals. <Desc / Clms Page number 42>  cyclical; C 6 -C 18 perfluorinated alkyl radicals; the cholesteryl radical or a cholesterol ester; polycyclic aromatic groups.

29. Composition according to any one of claims 27 or 28, characterized in that the monomer of formula (1) additionally comprises at least one alkylene oxide unit (x 1). 30. Composition according to any one of claims 27 to 29, characterized in that the monomer of formula (1) further comprises at least one polyoxyalkylene chain. 31. The composition as claimed in claim 30, characterized in that the polyoxyalkylene chain consists of ethylene oxide units and / or propylene oxide units. 32. Composition according to Claim 31, characterized in that the polyoxyalkylenated chain consists solely of ethylene oxide units. 33. Composition according to any one of claims 27 to 32, characterized in that the number of oxyalkylenated units ranges from 3 to 100. 34. Composition according to claim 33, characterized in that the number of oxyalkylenated units ranges from 3 to 50. 35. Composition according to claim 34, characterized in that the number of oxyalkylenated units ranges from 7 to 25. 36. Composition according to any one of claims 23 to 28, characterized in that the amphiphilic AMPS polymer is chosen from: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS patterns and from 40 to 85% by weight of patterns <Desc / Clms Page number 43>  (C8-C, alkyl (meth) acrylamide or (C8-C16) alkyl (meth) acrylate units, with respect to the polymer; terpolymers having from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mole percent of AMPS units and from 5 to 80 mole percent of n- (C-18) alkylacrylamide units, based on the polymer. 37. Composition according to any one of claims 23 to 28, characterized in that the AMPS amphiphilic polymer is chosen from: - uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecyl methacrylate.  crosslinked or uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecylmethacrylamide. 38. Composition according to claims 23 to 35, characterized in that the amphiphilic AMPS polymer is chosen from copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of the following formula (11):

 in which X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion, and units of the following formula (here):

<Desc / Clms Page number 44>  in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; Ri has the same meaning as that indicated above in the formula (!) And? 4 denotes a linear or branched C6-C22 alkyl and more preferentially C, O-C22.

39. Composition according to claim 38, characterized in that x = 25, Ri is methyl and R4 is n-dodecyl. 40. A composition according to claim 27 or 38, characterized in that the molar proportion in% of the units of formula (1) or units of formula (here) in the polymers ranges from 50.1 to 99.9%. 41. A composition according to claim 27 or 38, characterized in that the molar proportion in% of units of formula (1) or units of formula (here) in the polymers ranges from 0.1 to 50%. 42. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymers are present in concentrations ranging from 0.01 to 30% by weight, more preferably from 0.1 to 10% by weight, and even more preferably from 0.1 to 5% by weight, and more particularly from 0.5 to 2% by weight relative to the total weight of the composition. 43. Composition according to any one of the preceding claims, characterized in that the reducing agent (s) is (are) chosen from thiols such as cysteine, thioglycolic acid, thiolactic acid, their salts and their esters, and cysteamine. and its salts, sulfites, ascorbic acid, its salts and esters, erythorbic acid, its salts and esters. 44. Composition according to claim 43, characterized in that the concentration of reducing agent may vary from 0.1 to 30% by weight relative to the total weight of the composition. <Desc / Clms Page number 45>

 45. Composition according to claim 44, characterized in that it can vary from 0.5 to 20% by weight relative to the total weight of the composition. 46. Composition according to any one of the preceding claims, characterized in that it also contains at least one amphoteric or cationic polymer. 47. A composition according to claim 46, characterized in that the cationic polymer is a quaternary polyammonium consisting of repeating units corresponding to the following formula (W):

 48. A composition according to claim 46, characterized in that the cationic polymer is a quaternary polyammonium consisting of repeating units corresponding to the following formula (U):

 49. Composition according to claim 46, characterized in that the amphoteric polymer is a copolymer comprising at least as monomers of acrylic acid and a dimethyldiallylammonium salt. 50. Composition according to any one of Claims 46 to 49, 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. <Desc / Clms Page number 46>

 51. 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. 52. Composition according to claim 51, 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. 53. Composition according to any one of the preceding claims, characterized in that it additionally contains at least one basifying or acidifying agent in amounts ranging from 0.01% to 30% by weight relative to the total weight of the composition. 54. A composition according to claim 53, characterized in that the basifying agent is chosen from ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, hydroxyalkylamines and ethylenediamines. oxyethylenated and / or oxypropylenated, hydroxides of sodium or potassium and compounds of formula (XIX) below:

 wherein R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R38, R39, R40 and R41, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. 55. A composition according to claim 54, characterized in that the acidifying agent is selected from inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid or sulphonic acids. 56. Process for the preparation of a composition as defined in any one of claims 1 to 55, characterized in that an anhydrous composition containing at least one reducing agent and at least one reducing agent is mixed extemporaneously at the time of use. an aqueous composition, at least one of the anhydrous or aqueous compositions containing at least one amphiphilic polymer as defined in any one of claims 1 to 42. <Desc / Clms Page number 47>

57. A composition according to any one of claims 1 to 55, characterized in that it is anhydrous and intended for the bleaching or deformation of human keratin fibers and more particularly the hair. 58. Composition according to Claim 57, characterized in that the anhydrous composition is in pulverulent form. 59. A method of bleaching or permanent deformation of human keratinous fibers and more particularly of the hair, consisting in applying to the fibers, dry or wet, a ready-to-use composition containing, in a medium suitable for bleaching, at least one reducing agent and at least one amphiphilic polymer as defined in any one of Claims 1 to 42, and allowing it to act for a rest period ranging from 1 to 60 minutes, and preferably from 10 to 45 minutes, to be rinsed off optionally the fibers, washing them with shampoo, then rinsing them again, and drying them, the application of said composition can be followed, in the case of permanent deformation, by the application, possibly after rinsing, of an oxidizing composition which is allowed to act for a pause time of between 1 and 20 minutes and preferably between 1 and 10 minutes, then it is optionally washed with shampoo, rinsed again, and dried. 60. Device with two compartments or Kit for the decolorization or permanent deformation of human keratinous fibers and more particularly 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 amphiphilic polymer as defined in any one of claims 1 to 42. 61. Use as a thickening and / or gelling agent in a cosmetic and / or dermatological composition comprising at least one reducing agent, of an amphiphilic polymer as defined in any one of Claims 1 to 42.