MXPA97006639A - Composition of dyeing by oxidation for fibrasqueratinicas, that comprises an anififiloanion polymer - Google Patents

Abstract

The present invention relates to oxidation dyeing composition for keratin fibers, in particular for human keratin fibers such as hair, of the type comprising, in a medium suitable for dyeing, at least one dye precursor by oxidation and arriving at the case, one or more couplers, characterized in that it also contains at least one amphiphilic anionic polymer comprising at least one hydrophilic unit of the carboxylic acid, olefinic unsaturated and at least one hydrophobic unit of the alkyl ester type (C10-C30) of unsaturated carboxylic acid

Description

ATINICAS THAT COMPRISES AN ANIONIC ANIFYLIL POLYMER " FIELD OF THE INVENTION The present invention relates to a composition for oxidation dyeing of keratin fibers and in particular human keratin fibers such as hair, which comprises at least one dye precursor by oxidation and optionally one or more couplers and at least one amphiphilic polymer anionic which includes at least one hydrophilic unit of olefin-unsaturated carboxylic acid type and at least one hydrophobic unit exclusively of thi ?; It is known to dye keratin fibers and in particular human hair, with dyeing compositions containing dye precursors by oxidation, generally referred to as "alkyl ester" (C ?0 ~ 30 ^ unsaturated carboxylic acid). oxidation bases ", in particular ortho- or para-phenylenediamines, ortho- or para-a-phenols, and heterocyclic bases.The oxidation dye precursors are initially little or no colored compounds that develop their dyeing power in the hair in the presence of oxidizing agents leading to the formation of colored compounds.The formation of colored compounds -result either of an oxidative condensation of the REF: 25517"oxidation bases" on itself, or of an oxidative condensation of the "oxidation bases" on coloration modifying compounds, or "couplers", which are generally present in the dyeing compositions used in dyeing by oxidation and are more particularly represented by metaphenylenediamines, meta-amine-phenols and meta-diphenols, and certain heterocyclic compounds. The variety of molecules used, which are made up on the one hand by the "oxidation bases" and "on the other hand by the" copulators ", allows obtaining * a palette very rich in colors. oxidation in the application on the hair so as not to flow on the face or outside the areas that it is proposed to dye, it has been had until now to resort to the use of traditional thickeners such as polyacrylic acid crosslinked, the hydroxyethylcelluloses, the waxes or also mixtures of nonionic surfactants of HLB (Hydrophilic Lipophilic Balance), which, properly chosen, produce the gelling effect when diluted by means of water and / or surfactants. the applicant has observed that traditional thickener-type ingredients, surfactants and solvents, generally slow down the rise of dye on the fibers, which is translated by a tender tone and also by a more important use of dye, solvent and / or surfactants to solubilize the dye, if desired not to obtain a strong tonality. On the other hand, it has also observed - after mixing with the oxidant, the dyeing compositions containing the dye precursor (s) by oxidation and optionally the coupler (s), and also the indicated ingredients, lost a part of their character. gelled and consequently produced undesirable flows. Now, after important investigations carried out for this purpose, the applicant now finishes discovering that it is possible to obtain dyeing compositions -by oxidation (after mixing with the oxidant) -they do not flow and therefore remain better located at the point of application, and which also allow to obtain more chromatic (brighter) and more powerful shades, if (i) is introduced either in the composition containing the colorant precursor (s) by oxidation and, eventually, the copulator (s) [or composition ( A)], either (ii) in the oxidizing composition [or composition (B)], or (iii) in the two compositions at the same time, an effective amount of an anionic amphiphilic polymer that includes at least one hydrophilic unit of type of unsaturated carboxylic acid olofinic acid, and at least one hydrophobic unit exclusively of the alkyl ester type (C1_3_3_3_ unsaturated carboxylic acid) In the sense of the present invention, the Aticidad (luminosidad) is defined by the value c * in the -system of colorimetric indication L *, a *, b *, of the - Commission Internationale de l'Eclairage (C.I.E.). This value is equal to the square root of the sum to 2 + b2 (+ a is red, -a is green, + b is yellow, -b is blue). The hue is brighter than the greater of c *. In this indication system, L * defines the power of the -tonality. The tonality is so much more powerful, the lower the value of L * (0 = black, 100 = white). These discoveries constitute the basis of the present invention.

DESCRIPTION OF THE INVENTION The subject of the present invention is therefore an oxidation dyeing composition for keratin fibers, in particular for human keratin fibers, such as hair, of the type comprising, in a medium suitable for dyeing, at least one color precursor. by oxidation (oxidation base) and, where appropriate, one or more copulators, characterized in that it also contains at least one amphiphilic-anionic polymer comprising at least one hydrophilic motif of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic motif exclusively of the alkyl (- C 1 -C 30) alkyl ester type of unsaturated carboxylic acid. Thanks to the present invention, it is also possible, and this advantageously, to reduce the consumption of a-surfactants, even to suppress them. The invention also makes it possible to reduce the quantity of coloring active substances used in the dyeing compositions, in relation to the conventional techniques known from the prior art. Another object of the present invention relates to a ready-to-use composition for the dyeing of keratin fibers, which contain at least one dye precursor by oxidation and optionally at least one copulator, and at least one anionic amphiphilic pilimer comprising at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the unsaturated carboxylic acid (C 10 -C C) alkyl ester type, and an oxidizing agent. The invention also relates to a process for dyeing keratin fibers, and in particular human keratin fibers such as hair, which consists in applying to these fibers at least one composition (Al) containing, in an appropriate medium. for the dyeing, at least one dye precursor by oxidation and - optionally at least one populant, in association with at least one anionic amphiphilic polymer comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of ester type of alkyl (C.sub.30 ~ C.sub.30 ^ ^ and carboxylic unsaturated acid, the color being revealed to an alkaline, neutral or acidic p with the aid of an oxidizing agent which is mixed just at the time of use of the composition - (Al) or that is present in a composition (Bl) sequentially applied without intermediate rinse The invention also relates to a variant of this invention. This process consists of applying to the fibers at least one composition (A2) which contains in an appropriate medium for the dyeing, at least one dye precursor by oxidation and optionally at least one copulator, and this in presence or absence of anionic amphiphilic polymer including at least one hydrophilic unit of the oleopinic unsaturated carboxylic acid type, and at least one hydrophobic unit - exclusively of the alkyl ester type (C --- C3Q) of unsaturated carboxylic acid, being revealed the color to a p-alkaline, neutral or acid with the aid of a composition-oxidant (B2) containing an oxidizing agent and an effective amount of at least one anionic amphiphilic polymer including at least one acid-type hydrophilic motif olefinic unsaturated carboxylic acid, and at least one hydrophobic unit exclusively of the (C10-C30) alkyl ester type of unsaturated carboxylic acid, and which is mixed just at the time of use of the position? A2) or that is applied sequentially without intermediary clarification. The invention also relates to dyeing devices or "kits" of several compartments, of which the first compartment contains at least one dye precursor by oxidation, optionally at least one copulator, and at least one anionic amphiphilic polymer comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the alkyl ester type. { C-o-C30) of unsaturated carboxylic acid, and the second compartment an oxidizing agent. According to another variant, the invention also has as object dyeing devices or "kits" of several compartments, of which the first compartment contains at least one dye precursor by oxidation, optionally at least one copulator, and this in the presence or absence of anionic amphiphilic polymer including at least one hydrophilic unit of the olefinic unsaturated carbolylic acid type, and at least one hydrophobic unit exclusively of the unsaturated carboxylic acid (C? 0-C30) alkyl ester type, and the second compartment an oxidizing agent and an effective cation of at least one anionic amphiphilic polymer comprising at least one hydrophilic unit of olefinic unsaturated carbonylic acid type, and at least one hydrophobic unit exclusively of the unsaturated carboxylic acid (C? 0-C30) alkyl ester type. The invention also relates to the use of the above-mentioned oxidation dyeing composition or of a dyeing device or multi-compartment "kits" as defined above for dyeing human keratin fibers such as hair. But other characteristics, aspects, objects and advantages of the invention will appear even more clearly on reading the description and the examples that follow. The anionic amphiphilic polymers including at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the unsaturated carboxylic acid (C 10 -C 30) alkyl ester type, used according to the invention, are preferably selected from among those whose hydrophilic unit of the olefinic unsaturated carboxylic acid type corresponds to the following monomer of formula (I): CH, = C - C - OH (I) R- 0 formula wherein, Rx designates H 'CH3 or CH5, that is to say of the units of acrylic acid, methacrylic acid or ethacrylic acid, and of which the hydrophobic unit of the ester type of alkyl (C? o-C3o) carboxylic acid unsaturated corresponds to the onometer of formula (II) below: CH2 = C - C - OR2 | || (ID R? O formula in which, i designates H or CH3 or C2H5 (ie acrylate units, meta-acrylates or etaacrylates) and preferably H (acrylate units) or CH3 (methacrylate units), designated R2 an alkyl radical of C? o-C30, and preferably C ?2-C22- The alkyl (C ?O-C30) esters of unsaturated carboxylic acids according to the invention comprise, for example, lauryl acrylate, stearyl acrylate, acrylate say, isodecyl acrylate, dodecyl acrylate, and corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate. for example, described and prepared according to US Patents 3,915,921 and 4,509,949 The anionic amphiphilic polymers which can be used in the context of the present invention can more particularly designate polymers formed from a monomer mixture. mers comprising: (i) essentially acrylic acid, an ester of formula (II): CH-, = C - C OR- (II) R- O in which Rx designates H or CH3, designated R2 an alkyl radical having from 12 to 22 carbon atoms, and a crosslinking agent, such as for example those constituted by 95 to 60% by weight of acrylic acid (hydrophilic unit) , from 4 to 40% a weight of C 10 -C 3 alkyl acrylate (hydrophobic unit), and from 0 to 6% by weight of crosslinked polymerizable monomer, 5} and 98 to 96% by weight of acrylic acid (hydrophilic unit), from 1 to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and from 0.1 to 0.6% by weight of polymerizable monomer crosslinker, (ii) essentially acrylic acid and lauryl methacrylate such as that formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacrylate. The cross-linked one is a monomer containing a CH2 = C ^ group with at least one other polymerizable group whose unsaturated bonds are non-conjugated with respect to each other. Particular mention may be made of polyallyl ethers, such as, in particular, polyallyl ethers, such as, in particular, polyallyl sucrose and polyallyl pentaerythritol.

Among the aforesaid polymers mentioned above, the products coming from the GOODRICH Company under the relevant designations PEMULEN TR1, PEMULEN TR2, CARBOPOL 1382, and even more preferably PEMULEN TR1, and the product sold by the company are particularly preferred according to the present invention. SEPC society under the name COATEX SX. Anionic amphiphilic polymers including at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the unsaturated carboxylic acid (C? 0-C30) alkyl ester type, are preferably used in accordance with the invention in an amount which may vary from about 0.05 to 10% by weight of the total weight of the dyeing composition applied on the fibers. More preferably, this amount ranges from about 0.2 to 55 by weight. The oxidation dye precursors which can be used in the context of the present invention are chosen from those conventionally known in oxidation dyeing, and among which may be mentioned in particular: • the para-phenylenediamines of formula (III) below and their addition salts. acid: in which: R? represents a hydrogen atom, an alkyl radical of dC, monohydroxyalkyl of C1-C4, polyhydroxyalkynyl of C2-C4 or 4'-aminophenyl, R2 represents a hydrogen atom, an alkyl radical of Ci-C monohydroxyalkyl of C? -C4, or C2-C4 polyhydroxyalkyl f R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, an alkyl radical of C? -C, sulfo, carboxy, monohydroxyalkyl of C? -C4 or hydroxyalkoxy of 1-C, R4 represents a hydrogen atom or an alkyl radical of Cx-C4, Among the para-phenylenediamines of formula (III) indicated above, para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediammine, 2,6 can be more particularly mentioned. - dimethyl paraphenylenyl, 2,6-dimethyl-paraphenylenediamine, 2,5-dimethyl-paraphenylenediamine, N, N-dimethyl-paraphenylenediamine, N, N-diethyl-paraphenylenediamine, N, N dipropyl-paraphenylenediamine, -amino-diethyl-3-methyl-aniline, N, N-bis- (β-hydroxyethyl) -paraphenylenediamine, 4-amino-N, N-bis- (β-hydroxyethyl) -3-methyl-aniline, 4-amino-3-chloro-N, N-bis- (β-hydroxyethyl) -aniline, 2-β-hydroxyethyl-paraphenylenedia ina, 2-fluoro-paraphenylenediamine, 2-isopropyl-paraphenylenediamine, N- (β-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-paraphenylene diamine, N, N-dimethyl-3-methyl-paraphenylenediamine, N, N- (ethyl, β-hydroxyethyl) -paraphenylenediamine, N- (β ,? - dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) -paraphenylenediamine, N-phenyl-paraphenylenediamine, 2-β-hydroxyethyl-oxy-paraphenylenediamine, and their addition salts with an acid. Among the paphenylenediamines of formula (III) indicated above, para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyl-oxy-para-phenylenediamine and 2,6-dimethyl are very particularly preferred. -para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (β-hydroxyethyl) -paraphenylenediamine, 2-chloro-paraphenylenediamine and its addition salts with a acid. bis-phenylalkylenediamines corresponding to formula (IV) below, and their addition salts with an acid: in which: Qi and Q2 identical or different, represent a radical. hydroxyl or NHR8 in which R8 represents a hydrogen atom or a C1-C alkyl radical, R5 represents a hydrogen atom, an alkyl radical of Ci- C4, monohydroxyalkyl of C1-C4, polyhydroxyalkyl of C2-C4 or aminoalkyl of C1-C4 whose amino moiety can be substituted, R6 and R7, identical or different, represent a hydrogen or halogen atom or a C1-C4 alkyl radical, represents a radical taken from the group consisting of the following radicals: ~ ( CH2) n- '- (CH2) m "° - < H2)"? - (CH2 > m "CHOH- (CH2) m- and in which n is an integer between 0 and 8 inclusive and m is an integer between 0 and 4 inclusive.

Among the bis-phenylalkylenediamines of formula (IV) indicated above, N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3- can be more particularly mentioned. diamino-2-propanol, N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4'-aminophenyl) - tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4-methylenediamine, N, N'-bis- (β-hydroxyethyl) -N, N'-bis- ( 4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) -tetramethylenediamine, N, N'-bis- (ethyl) -N, N'-bis- (4'-amino, 3'- methylphenyl) -ethienediamine, and its addition salts with an acid: Among these bis-phenylalkylenediamines of formula (IV), N, N '-bis- (β-hydroxyethyl) -N, N' -bis- (4 '- aminophenyl) -1,3-diamino-2-propanol or an addition salt thereof with an acid are particularly preferred: para-aminophenols corresponding to formula (V) below, and their addition salts with an acid : (V) in which: R9 represents a hydrogen atom, an alkyl radical of Ci- C4, monohydroxyalkyl of C? -C4, alkoxy (C1-C4) alkyl (C? -C4) or aminoalkyl of C1-C4, or hydroxyalkyl (C1-C4) aminoalkyl of C1-C4, Rio represents a hydrogen or fluorine atom, a C1-C4 alkyl radical, C1-C4 monohydroxyalkyl, "C2-C4 polyhydroxyalkyl, C1-C4 aminoalkyl, Ci-C4 cyanoalkyl or (C1-C4) alkoxy) C) -C), it being understood that at least one of the radicals R9 or RIO represents a hydrogen atom. Among the para-aminophenols of formula (V) indicated above, para-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluoro-phenol, 4-amino-phenol, 3-hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino-2-hydroxymethyl-phenol, 4-amino-2-methoxy-methyl-phenol, 4-amino-2-aminomethyl- phenol, 4-amino-2 (β-hydroxyethyl-aminomethyl) -phenol, and its addition salts with an acid. The ortho-aminophenols which can be used as oxidation bases in the context of the present invention are particularly chosen from 2-amino-phenol, 2-amino-1-hydroxy-5-methyl-benzene, 2-amino l-hydroxy-6-methyl-benzene, 5-acetamido-2-amino-f-nol, and their addition salts with an acid. -heterocyclic bases as oxidation bases within the framework of the present invention are particularly chosen from pyridine derivatives, pyridine derivatives, pyrazole derivatives, and their addition salts with an acid. Among the pyridine derivatives, mention may be made more particularly of the compounds described, for example, in GB-1 026 978 and GB-1,153,196, such as 2,5-diaminopyridine, and their addition salts with an acid. Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in German Patents DE-2,359,399 or Japanese JP-88-169,571 and JP-91-333,495, such as 2, 4, 5, 6, -tetra -aminopyrimidine, 4-hydroxy-2, 5,6-triaminopyrimidine, and its addition salts with an acid. Among the pyrimidine derivatives, mention may be made more particularly of the compounds described in DE-3,843,892, DE-4,133,957 and patent applications WO-94/08969 and O-94/08970 such as 4,5-diamino- 1-methyl-pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, and their addition salts with an acid.

According to the invention, the oxidation base (s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the composition (A) and even more preferably from 0.005 to 6% by weight approximately. The copulators which can be used in the dyeing process according to the invention are those conventionally used in oxidation dyeing compositions, namely meta-phenylenediamines, meta-aminophenols and meta-diphenols, mono- or poly-hydroxylated derivatives of naphthalene, sesamol and their derivatives and heterocyclic compounds such as, for example, indole couplers, indoline couplers, pyridine builders and their addition salts with an acid. These couplers can be chosen in particular from 2-methyl-5-amino-phenol, 5-N- (β-hydroxyethyl) -amino-2-methyl-phenol, 3-amino-phenol, 1,3-dihydroxy -benzene, 1,3-dihydroxy-2-methyl-benzene, 4-chloro-1,3-dihydroxy-benzene, 2,4-diamino-1- (β-hydroxyethyl-oxy) -benzene, 2-amino -4- (β-hydroxyethylamino) -1-methoxy-benzene, sesamol, α-naphthol, 6-hydroxy-indole, 4-hydroxy-indole, 4-hydroxy-N-methyl-indole, -hydroxy-indoline, 2,6-dihydroxy-4-methyl-pyridine, lh-3-methyl-pyrazol-5-one, l-phenyl-3-methyl-pyrazol-5-one, and their salts addition with an acid.

When present, these couplers preferably represent from 100% to 10% by weight approximately of the total weight of the composition (A), and even more preferably from 0.005 to 5% by weight approximately. In a general manner, the addition salts with an acid of the oxidation bases and couplers are particularly chosen from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates. The composition (A) may also contain, in addition to the oxidation dye precursors defined above and any associated coupling agents, direct dyes for enriching the tones in reflections. These direct dyes can then be chosen in particular from nitro, azo or anthraquinone dyes. The composition (A) and / or the composition (B) can also more particularly contain at least one cationic or amphoteric substantive polymer as defined on pages 3 and 4 of the patent application EP-0-0673.641 Al, and of which it is advantageously preferred to use: the polyammonium quaternary polymers prepared and described in French patent 2,270,846, constituted by recurring motifs corresponding to the following formula (VI): CHCH¬ and whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900; • the polyammonium quaternary polymers prepared and described in French patent 2,270,846, consisting of recurring units corresponding to the following formula (VII): CH- C2H5 N + _ (CH2) 3_N_ (CH2) 3 _] _ (V. {J) Br "I Rr-CH3 C2H5 and whose molecular weight, determined by gel permeation chromatography, is approximately 1200. The medium of the composition (A) suitable for the dye is preferably an aqueous medium constituted by water and may optionally contain organic solvents which are acceptable on the cosmetic plane, of which more particularly, alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol, and phenylethyl alcohol, or glycols or glycol ethers such as, for example, the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, propylene glycol or their ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol as well as diethylene glycol alkyl esters such as, for example, the monoethylether or the monobutylether of diethylene glycol, in concentrations of between about 0.5 and 20% and, preferably, between and about 2 and 10% by weight relative to the total weight of the composition. The composition (A) may also contain an effective amount of other agents, on the other hand previously known in oxidation dyeing, such as various adjuvants used as sequestering agents, hair conditioning agents and in particular silicones, preservatives, opacifiers, etc., and optionally anionic, non-anionic, amphoteric surfactants or their mixtures . The said composition may also contain antioxidant agents. These may be chosen in particular from sodium sulfite, thioglycolic acid, thiolactic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2-methyl-hydroquinone, tert-butyl-hydroquinone and homogentisic acid, and are then generally present in amounts ranging from about 0.05 to 1.5% by weight relative to the total weight of the composition. Of course, the person skilled in the art will try to choose the one or any additional compounds mentioned above, in such a way that the advantageous properties intrinsically related to the dyeing composition according to the invention are not, or substantially, altered by the addition (s) considered. In composition (B), the oxidizing agent is preferably chosen from urea peroxide, alkali metal bromates or ferricyanides, persalts such as perborates, percarbonates and persulfates. The use of hydrogen peroxide is particularly preferred. The composition (B) is advantageously constituted by a solution of hydrogen peroxide whose titre can vary, more particularly, from about 2.5 to 40 volumes, and even more preferably from about 5 to 20. The p of the composition ready for use and applied on the keratin fibers [composition resulting from the mixture of the dyeing composition (A) and the oxidizing composition (B)], is generally between the values of 4 and 11. It is preferably comprised between 6 and 10, and it can be adjusted to the desired value by means of acidifying agents or alkylating agents well known from the state of the art in the dyeing of keratin fibers. Among alkalizing agents, mention may be made, by way of example, of ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and compounds of formula ( VIII) following: N-R-N (VIII R12 R14 wherein R is a propylene moiety optionally substituted by a hydroxyl group or an alkyl radical of C? -C4; RU / 12 R-a- and u / identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or Ci-C4 hydroxyalkyl. Acidifying agents are conventionally, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, or sulfonic acids. The dyeing process according to the invention preferably involves applying a mixture, made extemporaneously at the time of use, from the compositions (A) and (B) described above, to the dry or wet keratin fibers, and leave to act during a resting time that preferably vary from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately, in lightening the fibers, then eventually in shampooing them, then in lightening them again and in drying them. Concrete examples that illustrate the invention will be given now, without presenting therefore a limiting character.

EXAMPLE 1 : The dyeing composition was prepared according to the following invention: Crosslinked anionic amphiphilic acid acrylic acid / C10-C3o alkyl acrylate (PEMULEN TR1 DE Gocdri ch).-.- .-. 1.0 g Oleic acid ._. ._. 3.0 g Aqueous solution of sodium bisulfite at 35% of MA *.-._. 0.45 g MA * Paraphenylenediamine ._. 0, 162 g Resoreina .-. ._. »._. 0.165 g Ammonia (20% NH3) 11.5 g Sequestrant agent q.s. Water.. ._ .-. .-. c. s. p 100 g MA * = Active Material At the time of use, this composition was mixed weight by weight with a solution of oxygenated water in 20 volumes, then the mixture obtained was applied on natural hair wicks with 90% of white. After 10 minutes of rest, the wicks were rinsed, then washed with a shampoo, rinsed again, then dried. With the help of a I: C: S: spectrocolorimeter, the chromaticity c * of the hue was measured from the values of a * and b * in the international color indication system L *, a *, b * , from C: I: E. The result was the following: c * = 14.36.

The value L * of the tonality was also measured. The result was the following: L * = 48.09.

COMPARATIVE EXAMPLE 2: Example 1 was reproduced, substituting 1 gram of anionic amphiphile polymer crosslinked acrylic acid / C1-C30 alkyl acrylate (PEMULEN TR1 of Goodrich) by mixing the following two non-ionic surfactants (which make it possible to obtain the same viscosity): 18 grams of decyl alcohol (C? 0-C? 2-C? 4 / 85-8.5-6, 5) oxie. in 3.5 moles of ethylene oxide sold under the name Mergital BL 309 by the Henkel Company, and 12 grams of decyl alcohol (C? 0-C? 2-C?) / 85-8.5-6, 5 ) oxyethylenated to 5.5 moles of ethylene oxide sold under the name Mergital BL 589 by the Henkel Company. The same protocol was followed as in Example 1. The results were the following: c * = 12.86 L * = 49.72 CONCLUSION The shade obtained according to the invention is brighter (c * larger) than that obtained according to the prior art; it is also more powerful (L * smaller).

Claims (17)

1. Oxidising dyeing composition for keratinous fibers, in particular for human keratin fibers, such as hair, of the type comprising, in a medium suitable for dyeing, at least one dye precursor by oxidation and, after case, one or more couplers, characterized in that it also contains at least one anionic amphiphilic polymer comprising at least one hydrophilic unit of the carboxylic acid type »unsaturated olefinic, and at least one hydrophobic unit of -type alkyl ester (C1Q) -C30) of unsaturated carboxylic acid.

2. The composition according to claim 1, characterized in that the hydrophilic unit corresponds to the monomer of formula (I) below:

CH-, = C - C - OH (I R- 0

in which, R designates H Ro CH3 or C2H5.

3. The composition according to claim 2, characterized by the fact that it is acrylic acid, methacrylic acid or mixtures thereof.

4. The composition according to any of the preceding claims, characterized by the fact that the hydrophobic unit is an ester corresponding to the following monomer of formula (II):

CH-, = C - C 0R- II) fi¬

in which it designates H & CH3 or C2H5, R2 denoting a C1-C3O alkyl radical; The composition according to claim 4, characterized in that in formula (II) Rj designates H or CH3. The composition according to claims 4 or 5, characterized in that the formula (II) R denotes a C 2 -C 22 alkyl radical

7. The composition according to any of the preceding claims, characterized by the fact that the anionic amphiphilic polymer is recycled.

8. - The composition according to any of the preceding claims, characterized in that the anionic amphiphilic polymer is a polymer formed from a mixture of monomers comprising essentially acrylic acid, an ester of formula (II) below:

(II)

wherein R: designates H or CH3, designated R2 an alkyl radical having from 12 to 22 carbon atoms, and a crosslinking agent.

9. The composition according to any of the preceding claims, characterized in that the anionic amphiphilic polymer is a polymer of acrylic acid and lauryl methacrylate.

10. The composition according to any of the preceding claims, characterized in that the oxidation dye precursors are chosen from ortho- or para-phenylenediamines, bis-phenylalkylenediamines, ortho- or para-aminophenols, and the heterocycline bases, as well as the addition salts of these compounds with an acid.

11. The composition according to any of the preceding claims, characterized in that the oxidation dye precursors are present in concentrations ranging between 0.0005 and 12% by weight with respect to the total weight of the composition.

12. The composition according to any of the preceding claims, characterized in that the couplers are chosen from metaphenylenediamines, meta-aminophenols, meta-diphenols, heterocyclic couplers, and addition salts of these compounds with an acid.

13. The composition according to any of the preceding claims, characterized in that the copulators are present in concentrations ranging between 0.0001 and 10% by weight with respect to the total weight of the composition.

14. The composition according to any of the preceding claims, characterized in that the addition salts with an acid of oxidation dye precursors and couplers are chosen from hydrochlorides, hydrobromides, sulfates, tartrates , lactates and acetates.

15. - The composition according to any of the preceding claims, characterized in that they also contain direct dyes.

16. The composition according to any of the preceding claims, characterized in that they also contain at least one cationic or amphoteric substantive polymer.

17. The composition according to claim 16, characterized in that the polymer is a polyammonium quaternary polymer constituted by recurring units that respond to the following formula (VI): CH3 CH3

L N + _ (CH2) 3_N! _ (CH2) 64- (VI) | cr | cr JHo CH3 18.- The composition according to claim 16, characterized in that the polymer is a quaternary polyammonium polymer constituted by recurring motifs corresponding to the following formula (VII): CH3 C2H5 _N + _ (CH2) 3_N_ (CH2) 3J_ (VII)

CH3 C2H5 19. The composition according to any of the preceding claims, characterized in that it also contains at least one reducing agent, present in amounts ranging between 0.05 and 3% by weight with respect to the total weight of the composition. 20. The composition according to any of the preceding claims, ready for use, characterized in that it also contains an oxidizing agent. 21. The composition according to claim 20, characterized in that it has a pH ranging between 4 and 11. 22. The composition according to claim 20, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, bromates and alkali metal ferricyanides, and persalts. 23. The composition according to claim 20 or 22, characterized in that the oxidizing agent is a solution of hydrogen peroxide whose titre varies from 2.5 to 40 volumes. 24. The composition according to any of the preceding claims, characterized in that the amphiphilic anicic polymers include at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the alkyl ester type (C10) -C30) of unsaturated carboxylic acid are used in an amount ranging between 0.05 and 10% by weight of the total weight of the composition applied on the fibers and even more preferably between 0.2 and 5%. 25. Process for dyeing keratin fibers and in particular human keratin fibers such as hair, characterized in that it consists of applying a dye composition (Al) on the fibers as defined in any one of the fibers. claims 1 to 19, and in disclosing the color in neutral alkyl or acid medium with the aid of an oxidizing agent that is added just at the time of use in this composition (Al) or that is present in the composition (Bl) applied sequentially without intermediate clarification. 26.- Method of dyeing keratin fibers and in particular of human keratin fibers, such as hair, characterized in that it consists of applying a dyeing composition (A2) on the fibers that it contains in an appropriate medium for dyeing, at least one dye precursor by oxidation, optionally one or more couplers, in the presence or absence of an anionic amphiphilic polymer including at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit exclusively of the alkyl ester type (C? 0-C30) of unsaturated carboxylic acid, and in disclosing the color in an alkaline, neutral or acidic medium with the aid of an oxidizing composition (B2) containing an oxidizing agent and an effective amount of at least one amphiphilic ammonium polymer which includes at least one hydrophilic unit of the olefinic hydrated carboxylic acid type, and at least one hydrophobic unit exclusively of the ester type of alkyl (C? 0-C30) of msaturado carboxylic acid, and that is mixed just at the time of use of the composition (A2) or that is applied sequentially without clarifying it intermediary. 27.- Device of several compartments or "Kit" for the dyeing of the keratin fibers and in particular of the human keratim fibers such as the hair, characterized by the fact that it comprises at least two compartments, including one of them a composition ( Al) as defined in any one of claims 1 to 19, and another a composition (Bl) comprising an oxidizing agent in a medium suitable for dyeing. 28.- Device of several compartments or "it" for the dyeing of the keratim fibers and in particular of the human keratim fibers such as the hair, characterized in that it includes at least two compartments, of which one of them includes a composition (A2) and another one a composition (B2) as defined in claim 26. 29.- Use of a composition of oxidation dye as defined in any one of claims 1 to 24 or of a multi-compartment dyeing or "kit" as defined in claim 27 or 28, for dyeing by oxidation of the fibers human keratin such as the hair.