FR2818540A1 - Oxidizing composition for treating keratinic materials, especially human hair, includes an amphiphilic polymer comprising sulfo-functional ethylenically unsaturated monomer units and a hydrophobic portion - Google Patents

Abstract

Cosmetic or dermatological composition for treating keratinic materials, comprising an oxidizing agent, includes an amphiphilic polymer (I) comprising sulfo-functional ethylenically unsaturated monomer units and a hydrophobic portion.

Description

<Desc / Clms Page number 1>

OXIDIZING COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIALS BASED ON AMPHIPHILIC POLYMERS IN LESS THAN ONE
ETHYLENE UNSATURATED MONOMER WITH SULFONIC GROUPING AND
The present invention relates to a gelled oxidizing composition for the treatment of keratin materials comprising an amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or completely neutralized, and in addition at least one a hydrophobic part and its uses for dyeing, for permanent deformation or for the bleaching of human keratinous fibers and in particular 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.

Said bleaching compositions are mainly in the form of anhydrous products (powders or creams) containing alkaline compounds (amines and alkali silicates), and a peroxygenated reagent such as persulfates, perborates or percarbonates, ammonium or alkali metal, which it is diluted at the time of use with an aqueous composition of hydrogen peroxide.

The bleaching compositions may also result from mixing, at the time of use, the anhydrous powder of peroxygenated reagent with an aqueous composition containing the alkaline compounds and another aqueous composition containing the hydrogen peroxide.

The bleaching compositions are also in the form of thickened aqueous compositions of hydrogen peroxide, ready for use.

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.

<Desc / Clms Page number 2>

 It is also known to dye keratinous fibers and in particular human hair with dyeing compositions containing oxidation dye precursors, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, heterocyclic compounds, generally known as oxidation. The oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored and coloring compounds. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as than indolic compounds.

The oxidizing agent present in the oxidizing composition as defined above may be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide or compounds capable of produce hydrogen peroxide by hydrolysis such as urea peroxide, persalts such as perborates and persulfates. Hydrogen peroxide is particularly preferred.

To locate the product of discoloration or dye on application to the hair so that it does not run on the face or outside the areas that we propose to discolor, so far we have resorted to the use of conventional thickeners such as crosslinked polyacrylic acid, hydroxyethylcelluloses, certain polyurethanes, waxes, and moreover, in the case of aqueous bleaching compositions, mixtures of nonionic surface-active agents of HLB ( Hydrophilic Lipophilic Balance), which, if properly chosen, give the gelling effect when diluted with water and / or surfactants.

However, the Applicant has found that the thickening systems mentioned above do not allow to obtain sufficiently powerful and homogeneous discolorations and leave the hair ripe.

 Moreover, it has also found that the ready-to-use bleaching compositions containing the oxidizing agent (s), and furthermore the thickening systems of the prior art, do not allow a sufficiently precise application without sagging or falling of viscosity in the time.

It is also known that the most usual technique for obtaining a permanent deformation of the hair consists, in a first step, in achieving the opening of the

<Desc / Clms Page number 3>

 disulfide-SS-keratin (cystine) bonds using a composition containing a suitable reducing agent (reduction step) and, after rinsing the hair so treated, to reconstitute in a second time said disulfide bonds by applying , on hair previously put under tension (hair curlers and others), an oxidizing composition (oxidation stage, also called fixation) so as finally to give the hair the desired shape. This technique thus makes it possible to achieve either the waving of the hair, or their straightening or their curing. The new form imposed on the hair by a chemical treatment as above is eminently durable over time and resists particularly the action of washing with water or shampoo, and this as opposed to simple conventional techniques of temporary deformation, such as styling.

The reducing compositions that can be used for carrying out the first step of a permanent operation generally contain, as reducing agents, sulphites, bisulphites, alkylphosphines or, preferably, thiols. Among these, those commonly used are cysteine and its various derivatives, cysteamine and its derivatives, thiolactic acid or thioglycolic acid, their salts and their esters, especially glycerol thioglycolate.

As regards the oxidizing compositions necessary for carrying out the fixing step, in practice hydrogen peroxide-based compositions are most often used.

 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 oxidizing formulations used in hair dyeing, for perms or for hair discoloration. These should spread well and spread evenly along the keratinous fibers and do not run on the forehead, the neck, the face or in the eyes.

 It is generally difficult to obtain peroxide-based gels such as storage-stable hydrogen peroxide using conventional water-soluble thickeners and / or gelling agents, for example those of the cross-linked acrylic polymer type such as those sold under the name CARBOPOL by the company GOODRICH. Peroxides are

<Desc / Clms Page number 4>

 used in cosmetics in the form of acidic aqueous solutions for reasons of stability. They lead most often in the presence of conventional gelling agents to significant variations in the viscosity of the gel during storage.

US Pat. No. 4,804 is known. 705. Hydrogen peroxide-based gels containing a gelling agent formed by reaction of a quaternized hydroxyethylcellulose of the CELQUAT type (product sold by National Starch) with an aqueous solution containing 15% by weight of a poly (acidic) polymer. 2-acrylamido-2-methylpropane sulfonic acid) of the COSMEDIA HSP-1180 type (product sold by HENKEL) and a sodium polystyrene sulfonate of the FLEXAN 3 type (product sold by National Starch), used in particular concentrations.

The Applicant has surprisingly found that it is possible to obtain ready-to-use discoloration compositions which do not flow and therefore remain well localized at the point of application, and which also make it possible to obtain powerful discolorations and homogeneous while leaving the hair less coarse if we introduce into the composition an effective amount of a particular amphiphilic polymer.

The Applicant has also surprisingly discovered a new family of thickening and / or gelling agents making it possible to obtain transparent gels based on oxidants and preferably hydrogen peroxide or an oxidizing compound capable of releasing peroxide. hydrogen, storage stable. It is amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing sulfonic group, in free form or partially or completely neutralized and in addition at least one hydrophobic part. These new gelling agents do not affect the oxidizing properties of hydrogen peroxide or of a compound capable of producing hydrogen peroxide by hydrolysis present in the gel thus formed.

The subject of the present invention is therefore a cosmetic and / or dermatological composition intended for the treatment of keratin materials 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 oxidant.

<Desc / Clms Page number 5>

 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 oxidant.

According to the invention, the oxidizing agent is preferably chosen from the group consisting of hydrogen peroxide and compounds that can produce hydrogen peroxide by hydrolysis, or mixtures thereof.

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 and even more preferably from 12 to 18 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.

They generally have a molecular weight, calculated by weight, ranging from 20,000 to 10,000,000, more preferably from 50,000 to 8,000,000 and even more preferably from 100,000 to 7,000,000.

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

<Desc / Clms Page number 6>

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.

diallyléther, les polyglycol-diallyléthers, le triéthylèneglycol-divinyléther, l'hydroquinone- diallyl-éther, le diacrylate de tétraéthylèneglycol, la triallylamine, le méthylène-bisacrylamide, le triméthylol propane triacrylate, le tétra-allyloxy-éthane, le triméthylolpropane-diallyléther, le méthacrylate d'allyle, les éthers allyliques d'alcools de la série des sucres, ou d'autres allyl-ou vinyi-éthers d'alcools polyfonctionnels, ou les mélanges de ces composés. There may be mentioned, for example, divinylbenzene, diallyl ether, dipropylene glycol,

diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraethylene glycol diacrylate, triallylamine, methylenebisacrylamide, trimethylol propane triacrylate, tetra-allyloxyethane, trimethylolpropane diallyl ether, allyl methacrylate, allyl ethers of alcohols of the series of sugars, or other allyl or vinyi-ethers of polyfunctional alcohols, 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 sulphonic group are chosen in particular from vinylsulfonic acid, styrenesulphonic acid, (meth) acrytamido (C 1 -C 22) alkylsulphonic acids, and N- (C 1 -C 22) alkyl (meth) acrylamido acids ( C₁-C₂₂) alkylsulfonic acids such as undecyl-acrylamido-methanesulfonic acid and their partially or completely neutralized forms.

sulfonique, l'acide acrylamido-propane-sulfonique, t'acide 2-acrylamido-2méthylpropane-sulfonique, l'acide méthacrylamido-2-méthylpropane-sulfonique, l'acide 2acrylamido-n-butane-sulfon ique, l'acide 2-acrylamido-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. Plus particulièrement, on utilisera l'acide 2-acrylamido-2-méthylpropane-sulfonique (AMPS) ainsi que ses formes partiellement ou totalement neutralisées. More preferably, (meth) acrylamido (C 1 -C 22) alkylsulphonic acids such as, for example, acrylamido-methanesulphonic acid, acrylamidoethane acid, are used.

sulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2- acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulphonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and also their partially or completely neutralized forms. More particularly, use 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or completely neutralized forms.

<Desc / Clms Page number 7>

The amphiphilic polymers in accordance with the invention may especially be chosen from AMPS random amphiphilic polymers modified by reaction with a n-cycloalkylamine or a di-n-alkylamine at Ce-C22, and such as those described in the patent application WO00 / 31154 (forming 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 not containing a fatty chain, such as (meth) acrylic acids, their ss-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 micelle networks formed by non-ionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior-Langmuir, 2000,
Flight. 16,? 12, 5324-5332));

<Desc / Clms Page number 8>

   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 R2 is preferably chosen from linear (e.g. n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (e.g. cyclododecane (C12) alkyl radicals. or adamantane (C, O)); perfluorinated C8-C18 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.

<Desc / Clms Page number 9>

 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 is preferably composed of ethylene oxide units and / or propylene oxide units and even more particularly 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 8 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 (Ca-C16) alkyl (meth) units acrylamide or (Ca-C16) alkyl (meth) acrylate units with respect to the polymer, such as those described in application EP-A750 899; terpolymers comprising from 10 to 90% by mole of acrylamide units, from 0.1 to 10% by mole of AMPS units and from 5 to 80% by mole of n- (C 6 -C 18) alkylacrylamide units, such as those described in US Patent 5089578.

Mention may also be made of the uncrosslinked and crosslinked copolymers of partially or totally neutralized AMPS and of dodecyl methacrylate as well as the noncrosslinked and crosslinked copolymers of partially or totally neutralized AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles. mentioned 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 (II) below:

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 10>

dans laquelle x désigne un nombre entier variant de 3 à 100, de préférence de 3 à 50 et plus préférentiellement de 8 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 C12-Ci8.

in which x denotes an integer ranging from 3 to 100, preferably from 3 to 50 and more preferably from 8 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 C12-C18 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 molar concentration in% of the units of formula (tut) and units of formula (tut) will vary depending on the desired cosmetic application and the rheological properties of the desired formulation. It preferably varies from 70 to 99 mol% of AMPS units and from 1 to 30 mol% of units of formula (tet) relative to the copolymer and more particularly from 70 to 90 mol% of AMPS units and from 10 to 30 mol% of units of formula (III).

These copolymers can be obtained by conventional methods of radical copolymerization in the presence of one or more initiators such as, for example, azobisisobutyronitrile (AIBN), azobisdivaleronitrile, ABAH (2,2-azobis- [2-amidinopropane] hydrochloride) or dilauryl peroxide.

The amphiphilic polymers in accordance with the invention are present in the cosmetic or dermatological compositions of the invention in concentrations ranging from 0.01 to

<Desc / Clms Page number 11>

 30% by weight, more preferably from 0.1 to 10% by weight and even more preferably from 0.5 to 2% by weight.

The oxidizing agent of the composition according to the invention is preferably chosen from the group formed by hydrogen peroxide, urea peroxide, persalts such as perborates or persulfates or mixtures thereof.

Preferably, the oxidizing agent is hydrogen peroxide, and more preferably still, the oxidizing agent is hydrogen peroxide.

The concentration of hydrogen peroxide can vary from 0.5 to 40 volumes, preferably from 2 to 30 volumes, and that of a compound capable of forming hydrogen peroxide by hydrolysis of 0.1 to 25% by weight relative to total weight of the oxidizing composition.

The oxidizing compositions according to the invention can be anhydrous or aqueous.

The oxidizing compositions according to the invention are preferably aqueous and the pH of the whole of an aqueous oxidizing composition preferably varies from 1 to 13, and even more preferably from 2 to 12.

The oxidizing composition may also be present, in particular in the case of discoloration, in the form of two parts to be mixed at the time of use, one of these two parts containing alkaline agents and in solid or liquid form. .

For hydrogen peroxide, the pH is preferably less than 7 before mixing.

l'ammoniaque, la monoéthanolamine, la diéthanolamine, la triéthanolamine, l'isopropanolamine, la propanediamine-1,3, un carbonate ou bicarbonate alcalin ou d'ammonium, un carbonate organique tel que le carbonate de guanidine, ou bien encore un hydroxyde alcalin, tous ces composés pouvant bien entendu être pris seuls ou en mélange, soit d'agents acidifiants tels que par exemple l'acide chlorhydrique, l'acide acétique, l'acide lactique ou l'acide borique. The pH of the aqueous oxidizing compositions according to the invention can be obtained and / or adjusted conventionally by adding either basifying agents, such as, for example

ammonia, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, propanediamine-1,3, an alkaline or ammonium carbonate or bicarbonate, an organic carbonate such as guanidine carbonate, or an alkaline hydroxide all these compounds can of course be taken alone or as a mixture, or acidifying agents such as for example hydrochloric acid, acetic acid, lactic acid or boric acid.

<Desc / Clms Page number 12>

 The oxidizing composition may contain additives known for their use in oxidizing compositions for hair dyeing by oxidation, for permanent deformation or bleaching of hair such as basifying or acidifying agents, preservatives, or sequestering agents.

Preferably, when the oxidizing agent is hydrogen peroxide, the oxidizing composition according to the invention contains at least one stabilizing agent for hydrogen peroxide. In the compositions associating oxygenated water and the amphiphilic polymers of the present invention, particularly advantageous results have been obtained by using at least one stabilizing agent chosen from alkaline or alkaline earth metal pyrophosphates, alkali or alkaline earth metal stannates. phenacetin or salts of acids and oxyquinoline, such as oxyquinoline sulfate. More advantageously still, at least one stannate is used in combination or not with at least one pyrophosphate.

In the oxidizing compositions according to the invention, the concentration of stabilizing agents of hydrogen peroxide can vary from 0.0001% to 5% by weight and preferably from 0.01 to 2% by weight relative to the total weight of the compositions oxidising.

In the oxidizing compositions according to the invention with hydrogen peroxide, the ratio of the concentrations of hydrogen peroxide to the stabilizing agents may vary from 0.05 to 1000 and preferably from 0.1 to 500 and even more preferably from 1 to 200. Likewise, the ratio of the concentrations of the amphiphilic polymer (s) according to the invention to the stabilizing agents can vary from 0.05 to 1000 and preferably from 0.1 to 500 and even more preferably from 1 to 500. at 200.

In the oxidizing compositions according to the invention the concentration of oxidizing agents ranges from 0.1 to 25% by weight relative to the total weight of the composition.

Preferably, according to the invention, the ratio of the concentrations of the amphiphilic polymer (s) according to the invention to the oxidizing agents is between 0.001 and 10, the amounts of said polymers and oxidants being expressed as active ingredients (peroxide hydrogen for hydrogen peroxide). More preferably still, this ratio is between 0.01 and 5 and more particularly between 0.02 and 1.

When the compositions according to the invention are generally in the form of a transparent gel, their viscosity preferably varies from 50 mPa. s to 10 Pa. s and more preferably 75 mPa. s at 0.5 Pa. s.

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

<Desc / Clms Page number 13>

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.

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):

<Desc / Clms Page number 14>

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, Rg, R6, identiques ou différents, représentent un groupe alkyle ayant de 1 à 18 atomes de carbone ou un radical benzyle 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 hydroxyalkyl group of 1 to 4 carbon atoms; R4, Rg, 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, acrylamide diacetones, acrylamide and methacrylamides substituted on nitrogen with

<Desc / Clms Page number 15>

alkyles inférieurs (Cl-C4), des acides acryliques ou méthacryliques ou leurs esters, des vinyllactames tels que la vinylpyrrolidone ou le vinylcaprolactame, des esters vinyliques.

lower alkyls (Cl-C4), acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.

- 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/méthacrylamidopropyl dimethylamine commercialisés notamment sous la dénomination STYLEZE CC 10 par ISP, - et les copolymères vinylpyrrolidone/méthacrylamide de diméthylaminopropyle quaternisés tel que le produit vendu sous la dénomination"GAFQUAT HS 100"par la société ISP. 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, the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate sold under the name Reten by the company Hercules, - vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate quaternized or otherwise, such as the products sold under the name "GAFQUAT" by the company ISP, for example "GAFQUAT 734" or "GAFQUAT 755" or the products referred to as "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 / methacrylamidopropyl dimethylamine copolymers sold in particular under the name STYLEZE CC 10 by ISP, and the copolymers quaternized vinylpyrrolidone / 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

<Desc / Clms Page number 16>

décrits notamment dans le brevet US 4 131 576, tels que les hydroxyalkyl celluloses, comme les hydroxyméthyl-, hydroxyéthyl-ou hydroxypropyl celluloses greffées notamment avec un sel de méthacryloyléthyl triméthylammonium, de méthacrylmidopropyl triméthylammonium, de diméthyl-diallylammonium.

especially described 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 methacryloylethyltrimethylammonium, methacrylmidopropyltrimethylammonium, dimethyl-diallylammonium salt.

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

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

<Desc / Clms Page number 17>

bifonctionnels. On peut citer par exemple les polymères acide adipiquediacoylaminohydroxyalcoyldialoylène triamine dans lesquels le radical alcoyle comporte de 1 à 4 atomes de carbone et désigne de préférence méthyle, éthyle, propyle. De tels polymères sont notamment décrits dans le brevet français 1.583. 363.

bifunctional. Mention may be made, for example, of adipiquadioacylaminohydroxyalkyldialoylene 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 reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid is between 0.8: 1 and 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.

(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):

<Desc / Clms Page number 18>

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 R8, 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 morpholinyle ; R7 et Ra indépendamment l'un de l'autre désignent de préférence un groupement alkyle ayant de 1 à 4 atomes de 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.

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 R8, independently of each other, denote an alkyl group having 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 1 to 4 carbon atoms; Y- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are described in particular in French patent 2,080,759 and in its certificate of addition 2.190. 406.

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

formule (VII) dans laquelle : R10. P1. R12 et R13, 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, Ru, 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 (10) The quaternary diammonium polymer containing recurring units having the formula:

formula (VII) in which: R10. P1. R12 and R13, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or R10, Ru, R12 and R13, together or separately, together with the atoms of nitrogen to which they are attached heterocycles optionally containing a second heteroatom other than nitrogen or

<Desc / Clms Page number 19>

Ri Pu. 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 ; Al 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 ; Ai, R10 et R12 peuvent former avec les deux atomes d'azote auxquels ils sont rattachés un cycle pipérazinique ; en outre si Al 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 : 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-.

Ri Pu. R12 and R13 represent a linear or branched C1-C6 alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-O-RD group or -CO-NH-R14-D where R14 is an alkylene and D a grouping quaternary ammonium; Al 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 atoms of oxygen, sulfur or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and X 'denotes an anion derived from a mineral or organic acid; Ai, R10 and R12 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition, if Al denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 can also denote a group - (CH2) n -CO-D-OC- (CH2) n- in which D denotes: a) a radical glycol composition of formula: -O-ZO-, wherein Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: - (CH 2 -CH 2 -O) x-Ch 2 -CH 2 - - [CH 2 - CH (CH 3) -O] y-CH 2 -CH (CH 3) - where x and y denote an integer of 1 to 4, representing a defined and unique degree of polymerization or any number of 1 to 4 representing a degree of polymerization way ; 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 alternatively 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 particular in French Patents 2,320,330, 2,270. 846.2. 316.271, 2.336. 434 and 2.413. 907 and US Patents 2,273. 780.2. 375853, 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.

<Desc / Clms Page number 20>

On peut utiliser plus particulièrement les polymères qui sont constitués de motifs récurrents répondant à la formule (vil) suivante :

dans laquelle RI R11 R12 et R13, identiques ou différents, désignent un radical alkyle ou hydroxyalkyle 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.

Polymers which consist of recurring units corresponding to the following formula (VII) can be used more particularly:

in which RI R11 R12 and R13, which are 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.

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. n 4 157 388, 4 702 906, 4 719 282. Ils sont notamment décrits dans la demande de brevet EP-A-122 324. (11) Quaternary polyammoniums consisting of repeating units of formula (IX):

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", "Mirapot AD1", "Mirapo! AZ1" and "Mirapo! 175" 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.

<Desc / Clms Page number 21>

(14) Les polymères réticulés de sels de méthacryloyloxyalkyl (Cl-c4) trialkyl (Ci- C4) ammonium tels que les polymères obtenus par homopolymérisation du diméthylaminoéthylméthacrylate quaternisé par le chlorure de méthyle, ou par copolymérisation de l'acrylamide avec le diméthylaminoéthylméthacrylate quaternisé par le chlorure de méthyle, l'homo ou la copolymérisation étant suivie d'une réticulation par un composé à insaturation oléfinique, en particulier le méthylène bis acrylamide. On peut plus particulièrement utiliser un copolymère réticulé acrylamide/chlorure de méthacryloyloxyéthyl triméthylammonium (20/80 en poids) sous forme de dispersion contenant 50 % en poids dudit copolymère dans de l'huile minérale. Cette dispersion est commercialisée sous le nom de"SALCARE SC 92"par la Société ALLIED COLLOIDS. On peut également utiliser un homopolymère réticulé du chlorure de méthacryloyloxyéthyl triméthylammonium contenant environ 50 % en poids de l'homopolymère dans de l'huile minérale ou dans un ester liquide. Ces dispersions sont commercialisées sous les noms de"SALCARE SC 95"et"SALCARE SC 96"par la Société ALLIED COLLOIDS.

(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 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 ; 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;

<Desc / Clms Page number 22>

et notamment ceux dont le poids moléculaire, déterminé par chromatographie par perméation de gel, est d'environ 1200.

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 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 denote groups derived from zwitterionic monomers of carboxybetaines or of sulphobetaines; 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.

The amphoteric polymers corresponding to the definition given above, which are more particularly preferred, are chosen from the following polymers: (1) The polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as, more particularly, the 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, the

<Desc / Clms Page number 23>

dialkylaminoalkylméthacrylate et acrylate, les dialkylaminoalkylméthacrylamide et acrylamide. De tels composés sont décrits dans le brevet américain no 3 836 537.

dialkylaminoalkylmethacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in U.S. Patent No. 3,836,537.

Mention may also be made of the sodium acrylate / 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 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.

<Desc / Clms Page number 24>

- f-CO-R19-CO-Z-t- (X)

dans laquelle Rlg 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

H H P H p

où x=2 et p=2 ou 3, ou bien x=3 et p=2 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.

(3) Polyamino amides crosslinked and alkylated partially or totally derived from polyaminoamide of general formula:

- f-CO-R19-CO-Zt- (X)

wherein Rlg 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 one of said acids with a primary bis or secondary bis amine, and Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents:

a) in the proportions of 60 to 100 mol%, the radical

HHPH p

where x = 2 and p = 2 or 3, or x = 3 and p = 2 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) dans les proportions de 0 à 20 mo ! es %) e radica !-NH- (CH) g-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 sulfone ou de leurs sels.

c) in the proportions of 0 to 20 mo! and wherein the polyaminoamines are crosslinked by addition of a bifunctional crosslinking agent selected 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 sulfone or their salts.

The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms, such as adipic acid, trimethyl-2,4,4-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.

<Desc / Clms Page number 25>

(4) Les polymères comportant des motifs zwittérioniques de formule :

(4) polymers having zwitterionic units of formula:

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 propyle, 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.

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.

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

le motif (XIII) 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 : (5) polymers derived from chitosan having monomeric units corresponding to the following formulas (XIII), (XIV), (XV):

the unit (XIII) 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 R25 represents a radical of formula

<Desc / Clms Page number 26>

dans laquelle si q=O, 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, suifonique, 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.

in which if q = O, R26, R27 and R28, which are identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulfonic acid groups, an alkylthio radical whose alkyl group carries an amino residue, at least one of the radicals R 26 R 27 and R 28 being in this case a hydrogen atom. hydrogen; 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.

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, R31 désigne 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 (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

<Desc / Clms Page number 27>

formula: -R33-N (R31) 2, R33 representing a -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH (CH3) -, R31 group 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.

et X désigne le symbole E ou E', E ou E'identiques ou différents désignent un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée comportant jusqu'à 7 atomes de carbone dans la chaîne principale non substituée ou substituée par des groupements hydroxyle et pouvant comporter en outre des atomes d'oxygène, d'azote, de soufre, 1 à 3 cycles aromatiques et/ou hétérocycliques ; les atomes d'oxygène, d'azote et de soufre étant présents sous forme de groupements éther, thioéther, sulfoxyde, sulfone, sulfonium, alkylamine, alkénylamine, des groupements hydroxyle, benzylamine, oxyde d'amine, ammonium quaternaire, amide, imide, alcool, ester et/ou uréthanne ; b) les polymères de formule : - D-X-D-X- (XVIII) où D désigne un radical

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 (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

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 more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by a

<Desc / Clms Page number 28>

 oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betaineized by reaction with chloroacetic acid or sodium chloroacetate.

 (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.

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.

particulier sels alcalins, notamment de sodium, sels d'ammonium, sels d'amines, sels 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 (C6C24) 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 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 the present invention, mention may be made in particular (non-limiting list) of salts (in

especially alkali salts, especially of sodium, ammonium salts, amine salts, aminoalcohol salts 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) alkylsulphosuccinates, (C6C24) alkylsulfosuccinates, (C6-C24) alkylamidesulfosuccinates; (C6-C24) alkyl sulphoacetates; acyl (C6-C24) sarcosinates and acyl (C6-C24) glutamates. It is also possible to use (C6-C24) alkyl polyglycoside carboxylic esters such as

<Desc / Clms Page number 29>

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 (C6-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.

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 (C6-C24) alkyl carboxylic ether 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.

dérivés de N-alkyl glucamin, les oxydes d'amines tels que les oxydes d'alkyl (Cl 0-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. (ii) Nonionic surfactant (s): Nonionic surfactants are also well-known compounds in SOI (see in particular in this regard "Handbook of Surfactants" by MR PORTER, Blackie & Son editions ( Glasgow and London), 1991, pp 116-178) and their nature is not critical in the context of the present invention. 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,

derivatives of N-alkylglucamines, amine oxides such as the oxides of alkyl (Cl 0 -C14) amines or the oxides of N-acylaminopropylmorpholine. It will be noted that the alkylpolyglycosides constitute nonionic surfactants that fall particularly well within the scope of the present invention.

<Desc / Clms Page number 30>

alkyl (C8-C20) bétaïnes, les sulfobétaïnes, les alkyl (C8-C20) amidoalkyl (Cl-C6) betaïnes ou les alkyl (C8-C20) amidoalkyl (Cl-C6) sulfobétaïnes. (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); we can still mention the

alkyl (C8-C20) betaines, sulfobetaines, (C8-C20) alkylamidoalkyl (C1-C6) betaines or (C8-C20) alkylamido (C1-C6) alkylsulfobetaines.

Y'désigne-COOH ou) e radica !-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, C11 ou C13, un radical alkyle en C17 et sa forme iso, un radical Cl insaturé. 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-) in which: R2 denotes an alkyl radical of an R2-COOH acid present in the hydrolysed coconut oil, a heptyl radical, nonyl or undecyl, R3 denotes a beta-hydroxyethyl group and R4 a carboxymethyl group; and R2'-CONHCH2CH2-N (B) (C) wherein: B is -CH2CH2OX ', C is - (CH2) z-Y', where z = 1 or 2, X 'is the group -CH2CH2-COOH or a hydrogen atom

Y'désigne-COOH or) radica! -CH2-CHOH-SCH R2'désigne an alkyl radical of an Rg-COOH acid present in coconut oil or in hydrolysed linseed oil, an alkyl radical, in particular C7, C8, C11 or C13, a C17 alkyl radical and its iso form, an unsaturated Cl 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 Caprylamphosphonate

<Desc / Clms Page number 31>

 dipropionate, 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.

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

28, 33, 44, or 46 by the company ROHM & HAAS and ELFACOS T210 and T212 by the company AKZO.

These auxiliary thickeners may represent from 0.01 to 10% by weight of the total weight of the composition.

Another subject of the invention is a process for the oxidation dyeing of human keratinous fibers and in particular the hair using a coloring composition

<Desc / Clms Page number 32>

composition oxydante selon l'invention qui est appliquée simultanément ou séquentiellement, avec ou sans rinçage intermédiaire. comprising in a support suitable for dyeing said fibers at least one oxidation dye and an oxidizing composition as defined above. According to this process, at least one coloring composition as defined above is applied to the fibers, the color being revealed at acidic, neutral or alkaline pH by means of a

oxidizing composition according to the invention which is applied simultaneously or sequentially, with or without intermediate rinsing.

According to a particularly preferred embodiment of the dyeing process according to the invention, the dyeing composition described above is mixed, at the time of use, with an oxidizing composition according to the invention. The resulting mixture is then applied to the keratin fibers and allowed to stand for about 3 to 50 minutes, preferably about 5 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried.

Another object of the present invention is a method of permanent deformation of human keratinous fibers and in particular hair, using as oxidizing composition the composition defined above.

According to this method, a reducing composition is applied to the keratin fiber to be treated, the keratinous fiber being put under mechanical tension before, during or after said application, the fiber is optionally rinsed, the oxidizing composition of the invention and then rinsing the fiber again.

The first step of this process consists in applying to the hair a reducing composition. This application is wicked by wick or globally.

The reducing composition comprises at least one reducing agent, which may in particular be chosen from thioglycolic acid, cysteine, cysteamine, glycerol thioglycolate, thiolactic acid, or salts of thiolactic or thioglycolic acids.

The usual step of tensioning the hair in a form corresponding to the final shape desired for the latter (loops for example) can be implemented by any means, including mechanical, appropriate and known per se to keep under tension hair , such as for example rollers, curlers and the like.

The hair can also be shaped without the aid of external means, simply with the fingers.

Before proceeding to the optional next step of rinsing, it is advisable, in a conventional manner, to let stand for a few minutes, generally between 5 minutes and one hour, preferably between 10 and 30 minutes, the hair on which has been

<Desc / Clms Page number 33>

 applied the reducing composition, and this so as to allow time for the reducer to act properly on the hair. This waiting phase is preferably carried out at a temperature ranging from 35 ° C. to 45 ° C., preferably also protecting the hair with a cup.

In the optional second stage of the process (step (ii)), the hair impregnated with the reducing composition is then rinsed thoroughly with an aqueous composition.

Then, in a third step (step (iii)), the hair thus rinsed is applied to the oxidizing composition according to the present invention, for the purpose of fixing the new shape imposed on the hair.

As in the case of the application of the reducing composition, the hair on which the oxidizing composition has been applied is then, in a conventional manner, left in a resting or waiting phase which lasts a few minutes, generally between 3 and 30 minutes. minutes, preferably between 5 and 15 minutes.

monométhylique, monoéthylique et monobutylique d'éthylèneglycol, le propylèneglycol ou ses éthers tels que, par exemple, le 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. The vehicle of the reducing and oxidizing compositions used according to the invention is preferably an aqueous medium consisting of water and may advantageously 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, ethers

monomethyl, monoethyl and monobutyl ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers such as, 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.

If the hair tension is maintained by external means, the hair (hair rollers, curlers and the like) can be removed from the hair before or after the fixation step.

<Desc / Clms Page number 34>

Finally, in the last step of the process according to the invention (step (iv)), optional step also, the hair impregnated with the oxidizing composition is rinsed thoroughly, generally with water.

We finally get a hair easy to disentangle, soft. The hair is wavy.

The oxidizing composition according to the invention can also be used in a process for bleaching human keratin fibers and in particular the hair.

The bleaching process according to the invention comprises a step of applying to the keratinous fibers an oxidizing composition according to the invention, this composition preferably comprising oxygenated water in an alkaline medium after extemporaneous mixing. Conventionally, a second step of the bleaching process according to the invention is a step of rinsing the keratinous fibers.

Concrete examples illustrating the invention will now be given.

In what follows or the above, unless otherwise stated, the percentages are expressed by weight.

The following examples illustrate the invention without being limiting in nature.

EXAMPLE 1: Oxidation Dyeing Composition: Coloring Composition: The dark brown shade of the EXCELLENCE CREME range of trade was used.

n-dodécylacrylamide (3, 5%/96, 5%) neutralisé à 100% par la soude...... 1 g - Peroxyde d'hydrogène............ q. s....................................... 20 volumes - Pyrophosphate tétrasodique (0, 02g) et stannate de sodium (0, 04 g) - Agent séquestrant : pentaacétate pentasodique........................... 0, 06 MA* - Eau déminéralisée.............................. q. s. p........................... 100g MA* désigne Matière Active Oxidizing composition: Acrylamido-2-methyl-2-propanesulfonic acid copolymer

n-dodecylacrylamide (3, 5% / 96, 5%) 100% neutralized with sodium hydroxide ...... 1 g - Hydrogen peroxide ............ qs ... ................................... 20 volumes - Tetrasodium pyrophosphate (0.22 g) and sodium stannate ( 0, 04 g) - Sequestering agent: pentasodium pentaacetate ................................. 0, 06 MA * - Demineralised water .... .......................... qsp ....................... ... 100g MA * means Active Matter

<Desc / Clms Page number 35>

 At the time of use, the coloring composition was mixed with the oxidizing composition in a weight ratio 1/1, 5. The mixture obtained was applied to strands of gray hair at 90% white at a rate of 10 g for 1 g of hair, and left for 30 minutes.

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

A uniform dark brown shade was obtained.

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

<Tb>
<tb> Thioglycolic acid <SEP> .......................................... .............. <SEP> 9, <SEP> 2
<tb> Arginine <SEP> 15
<tb> Ammonia <SEP> to <SEP> 20% <SEP> of NH3 ............................... ............... <SEP> 9, <SEP> 3
<tb> Ammonium carbonate <SEP><SEP> 4, <SEP> 5
<tb> Cocoylamidopropylbetaine / monolaurate <SEP> of <SEP> glycerol <SEP> (25/5) <SEP> en
<tb><SEP> aqueous solution <SEP> to <SEP> 30% ................................. .................. <SEP> 1,3
<tb> Peptisant .............................................. ........................ <SEP> 0, <SEP> 8
<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.

The following oxidizing composition was then applied: Oxidizing composition: Acrylamido-2-methyl-2-propanesulfonic acid / n-dodecylacrylamide acid copolymer (3.5% / 96.5%) 100% neutralized with sodium hydroxide. .... 1 g-8-volume oxygenated water - tetrasodium pyrophosphate (0.02 g) and sodium stannate (0.04 g)

<Desc / Clms Page number 36>

- Agent séquestrant : pentaacétate pentasodique.................. 0, 06 MA* - Eau déminéralisée.............................. q. s. p........................... 100g MA* désigne Matière Active Après 10 minutes de temps de pause, on a rincé à nouveau abondamment la mèche.

- Sequestering agent: pentasodium pentaacetate .................. 0, 06 MA * - Demineralized water .................. ............ qsp .......................... 100g MA * means Active Matter After 10 minutes of time pause, we rinsed again abundantly the wick.

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

The wick was wavy.

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

Claims (60)

 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 form or partially or completely neutralized and in addition at least one hydrophobic part and (b) at least one oxidant. 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 molecular weight by weight ranging from 20,000 to 10,000,000. 8. Composition according to claim 7, characterized in that the molecular weight ranges from 50,000 to 8,000,000. <Desc / Clms Page number 38>  9. Composition according to claim 8, characterized in that the molecular weight ranges from 100,000 to 7,000,000. 10. Composition according to any one of claims 1 to 9, characterized in that the amphiphilic polymers are crosslinked or non-crosslinked. 11. Composition according to claim 10, characterized in that the amphiphilic polymers are crosslinked. 12. Composition according to any one of claims 10 or 11, characterized in that the crosslinking agent (s) are chosen from the olefinically polyunsaturated compounds commonly used for the crosslinking of polymers obtained by radical polymerization. 13. Composition according to Claim 12, characterized in that the crosslinking agent (s) is (are) chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). 14. Composition according to any one of claims 11 to 13, 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. 15. Composition according to any one of the preceding claims, characterized in that the ethylenically unsaturated monomer containing sulfonic group is chosen from vinylsulfonic acid, styrene sulfonic acid, (meth) acrylamido (C1-C22) acids. alkylsulphonic acids, N- (C 1 -C 22) alkyl (meth) acryl acids; amido (Ci-C22) atkytsutfoniques and their partially or totally neutralized forms. 16. The composition as claimed in claim 15, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is chosen from acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid and acrylamidopropane. <Desc / Clms Page number 39>  sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentane acid sulfonic acid, 2-methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and their partially or completely neutralized forms.

17. Composition according to any one of claims 15 or 16, characterized in that the ethylenically unsaturated monomer containing sulfonic group is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and its forms partially or completely neutralized. 18. Composition according to Claim 17, 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- (C6-C22) alkylamine. 19. Composition according to any one of claims 17 or 18, characterized in that the AMPS amphiphilic polymers additionally contain at least one ethylenically unsaturated monomer having no fatty chain. 20. A composition according to claim 19, characterized in that the ethylenically unsaturated monomer not comprising a fatty chain is chosen from (meth) acrylic acids and their alkyl derivatives substituted in ss, 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. 21. Composition according to any one of claims 1 to 17, characterized in that the AMPS amphiphilic polymers are chosen from amphiphilic copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation comprising at least a part. hydrophobic having from 6 to 50 carbon atoms. 22. Composition according to Claim 21, characterized in that the hydrophobic part contains from 6 to 22 carbon atoms. <Desc / Clms Page number 40>  23. Composition according to Claim 22, characterized in that the hydrophobic part contains from 6 to 18 carbon atoms. 24. Composition according to Claim 23, characterized in that the hydrophobic part contains from 12 to 18 carbon atoms. 25. Composition according to any one of claims 21 to 24, characterized in that the hydrophobic monomer ethylenically unsaturated is chosen from acrylates or acrylamides of formula (1) below: in which R1 and R3, identical or different, denote a hydrogen atom or a linear or branched C 1 -C 6 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.

 26. Composition according to Claim 25, characterized in that the hydrophobic radical R2 is chosen from linear, branched or cyclic C 6 -C 18 alkyl radicals; perfluorinated C 8 -C 18 alkyl radicals; the cholesteryl radical or a cholesterol ester; polycyclic aromatic groups. 27. Composition according to any one of claims 25 or 26, characterized

 in that the monomer of formula (1) additionally comprises at least one alkylene oxide unit (x1). <Desc / Clms Page number 41>  28. Composition according to any one of claims 25 to 27, characterized in that the monomer of formula (1) further comprises at least one polyoxyalkylene chain. 29. Composition according to Claim 28, characterized in that the polyoxyalkylene chain is composed of ethylene oxide units and / or propylene oxide units. 30. Composition according to Claim 29, characterized in that the polyoxyalkylene chain consists solely of ethylene oxide units. 31. Composition according to any one of claims 25 to 30, characterized in that the number of oxyalkylenated units ranges from 3 to 100. 32. Composition according to claim 31, characterized in that the number of oxyalkylenated units ranges from 3 to 50. 33. Composition according to claim 32, characterized in that the number of oxyalkylenated units ranges from 8 to 25. 34. Composition according to any one of claims 21 to 26, characterized in that the amphiphilic polymer of AMPS is chosen from: - 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 (Cs-C16) alkyl (meth) acrylamide units or (C8-C16) alkyl (meth) acrylate units, based on the polymer; 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- (C6-18) alkylacrylamide units, relative to the polymer . 35. Composition according to any one of claims 21 to 26, characterized in that the amphiphilic AMPS polymer is chosen from: <Desc / Clms Page number 42>  uncrosslinked and crosslinked copolymers of partially or totally neutralized AMPS and of n-dodecyl methacrylate. uncrosslinked or crosslinked copolymers of partially or totally neutralized AMPS and n-dodecylmethacrylamide.

36. Composition according to claims 21 to 33, characterized in that the AMPS amphiphilic polymer is chosen from copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II) below:

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

 in which x denotes an integer ranging from 3 to 100, preferably from 3 to 50 and more preferably from 8 to 25; R 1 has the same meaning as that indicated above in formula (1) and R 4 denotes a linear or branched C 6 -C 22 and more preferably C 12 -C 18 alkyl. 37. Composition according to claim 36, characterized in that x = 25, Ri is methyl and R4 is n-dodecyl. <Desc / Clms Page number 43>  38. Composition according to claim 36 or 37, characterized in that the concentration of AMPS pattern varies from 70 to 99 mol% and the concentration of the unit of formula (here) varies from 1 to 30 mol% relative to the copolymer. . 39. The composition as claimed in claim 38, characterized in that the concentration of AMPS unit varies from 70 to 90 mol% and the concentration of the formula of (hot) varies from 10 to 30 mol% relative to the copolymer. 40. 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 more preferably more preferably from 0.5 to 2% by weight relative to the total weight of the composition. 41. A composition according to any one of claims 1 to 40, characterized in that the oxidizing agent is selected from the group consisting of hydrogen peroxide, urea peroxide, perborates, persulfates, or their mixtures. 42. Composition according to any one of claims 1 to 41, characterized in that the oxidizing agent is hydrogen peroxide. 43. Composition according to claim 42, characterized in that the concentration of hydrogen peroxide ranges from 0.5 to 40 volumes and preferably from 2 to 30 volumes. 44. Composition according to claim 42, characterized in that the oxidizing agent is hydrogen peroxide. 45. Composition according to claim 44, characterized in that the oxygenated water contains a stabilizing agent. 46. Composition according to Claim 45, characterized in that the stabilizing agent is chosen from alkaline or alkaline-earth metal pyrophosphates, alkali metal or alkaline-earth metal stannates, phenacetin, or acid and alkali salts. oxyquinoline. <Desc / Clms Page number 44>  47. A composition according to claim 46, characterized in that the stabilizing agent is a stannate or a stannate associated with a pyrophosphate. 48. Composition according to any one of Claims 44 to 47, characterized in that the concentration of stabilizing agent ranges from 0.0001 to 5% by weight and preferably from 0.01 to 2% by weight relative to the weight. total of the composition. 49. Composition according to any one of Claims 42 to 48, characterized in that the ratio of the concentrations of hydrogen peroxide to the stabilizing agents ranges from 0.05 to 1000, preferably from 0.1 to 500 and more particularly from 1 to 200. 50. Composition according to any one of Claims 42 to 49, characterized in that the ratio of the concentrations of the amphiphilic polymer or polymers defined according to Claims 1 to 40, to the stabilizing agents, varies from 0.05 to 1000, preferably from 0.1 to 500 and more particularly from 1 to 200. 51. Composition according to any one of the preceding claims, characterized in that the ratio of the concentrations of the amphiphilic polymer or polymers defined according to Claims 1 to 40 to the oxidizing agents ranges from 0.001 to 10, preferably from 0.01 to 10. at 5 and more particularly from 0.02 to 1. 52. Composition according to any one of claims 41 to 50, characterized in that the concentration of oxidizing agents ranges from 0.1 to 25% by weight relative to the total weight of the composition. 53. Composition according to any one of claims 1 to 52, characterized in that it is aqueous and that the pH of the entire composition varies from 1 to 13, and preferably from 2 to 12. 54. Composition according to any one of claims 1 to 53, characterized in that it is in the form of a transparent gel with a viscosity of 50 mPa. s to 10 Pa. s and more preferably 75 mPa. s at 0.5 Pa. s. 55. A process for the oxidation dyeing of human keratinous fibers and in particular the hair using a dye composition comprising, in a support suitable for dyeing keratinous fibers, at least one oxidation dye and an oxidizing composition as defined in US Pat. any one of claims 1 to 54. <Desc / Clms Page number 45> 56. The dyeing process as claimed in claim 55, in which the dyeing composition is mixed with the oxidizing composition at the time of use; the resulting mixture is then applied to the keratin fibers and allowed to stand for about 3 to 50 minutes, preferably about 5 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried. 57. The dyeing process as claimed in claim 55, wherein the dyeing composition and the oxidizing composition are applied sequentially, with or without intermediate rinsing. 58. A process for treating human keratinous fibers, and in particular the hair, so as to obtain permanent deformation of the latter, in particular in the form of permed hair, this process comprising the following steps: (i) keratinous material to treat a reducing composition, the keratin fiber being put under mechanical tension before, during, or after said application, (ii) optionally rinsing the keratinous fiber, (iii) an optionally oxidizing composition is applied to the optionally rinsed keratinous fiber as defined in one of claims 1 to 54, (iv) optionally rinsing the keratin fiber again. 59. A process for bleaching human keratinous fibers and in particular the hair, comprising the following steps: i) an oxidizing composition according to any one of claims 1 to 54 is applied to the keratin fiber, ii) the keratinous fiber is rinsed, and treated. 60. Use as a thickening and / or gelling agent in a cosmetic and / or dermatological composition comprising at least one oxidant chosen from the group consisting of hydrogen peroxide and compounds capable of hydrolytically producing hydrogen peroxide or their mixtures , an amphiphilic polymer as defined in any one of claims 1 to 40.