FR2838337A1 - Dyeing composition used for oxidation dyeing of human keratinous fibers, e.g. hair, includes alkalinizing agent comprising sodium metasilicate and aqueous ammonia - Google Patents

Abstract

A dyeing composition comprises an oxidation dye(s) and an alkalinizing agent, based on water and at a basic pH. The alkalinizing agent is a combination of sodium metasilicate and aqueous ammonia.

Description

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COMPOSITION FOR OXIDATION DYE
The invention relates to a composition for the oxidation dyeing of human keratinous fibers and in particular to the hair comprising, in a cosmetically acceptable medium based on water and at basic pH, at least one dye of oxidation and an alkalizing agent consisting of sodium metasilicate and ammonia, and the dyeing process using this composition.

It is known to dye human keratin fibers and in particular the hair with dye compositions containing oxidation dyes. Oxidation dyes include oxidation dye precursors and couplers.

Oxidation dye precursors, generally known as oxidation bases, are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds and dyes by a process of oxidative condensation. These are in particular ortho or para-phenylenediamines, ortho or para-aminophenols, or heterocyclic bases.

The grades obtained with these oxidation bases may be modified by combining said bases with couplers or color modifiers, the couplers being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds.

The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors.

The oxidation dyeing process consists in applying to the fibers, oxidation bases or a mixture of oxidation bases and couplers with an oxidizing agent, most often hydrogen peroxide, to be allowed to pause, then to rinse the fibers. The application generally carried out at basic pH makes it possible to obtain a dyeing and at the same time a lightening of the fiber which, in practice, results in the possibility of obtaining a final coloration that is lighter than the original color. In addition, the lightening of the fiber has the advantageous effect of generating a solid color in the case of gray hair, and in the case of naturally pigmented hair, to bring out the color, that is to say to make it more visible.

The lightening of the hair is evaluated by the pitch that characterizes the degree or level of lightening. The notion of tone is based on the classification of

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 natural nuances, a tone separating each nuance from that which follows it or immediately precedes it. This definition and the classification of natural shades is well known to professionals in the hair and published in the book Sciences capillary treatments Charles ZVIAK 1988, Ed Masson, pp. 215 and 278.

The pitch ranges from 1 (black) to 10 (light light blond), a unit corresponding to a tone; the higher the number, the clearer the nuance.

The current technology of lightening oxidation dye to achieve a lightening of the fiber from 2 tones to 2 and a half shades and coverage of 100% white hair, it has so far involved using ammonia as an alkalinizing agent at high levels.

As everyone knows, ammonia has the major disadvantage of giving off a very irritating and unpleasant odor during the application of the dye.

It also sometimes causes, in high concentrations, irritations of the scalp in the form of tingling.

Here now that after extensive research conducted on the issue, the Applicant has discovered that it is possible to reduce the irritating odor and the risk of irritation of the scalp of said dyes while obtaining acceptable levels of lightening and intense coloring in various shades, using as a basifying agent a mixture of sodium metasilicate and ammonia.

This discovery is the basis of the present invention.

The invention therefore firstly relates to a composition for the oxidation dyeing of human keratinous fibers and more particularly to hair comprising, in a cosmetically acceptable water-based medium, and at basic pH, at least one oxidation dye. and an alkalinizing agent, characterized in that the basifying agent is a combination of sodium metasilicate and ammonia.

The dye composition in accordance with the invention makes it possible to reduce the ammonia content conventionally used with a perfect maintenance of the dyeing properties and makes it possible to formulate less odorous and less irritating products.

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The subject of the invention is also a process for the oxidation dyeing of human keratinous fibers and more particularly hair using said composition.

Another object of the invention is a ready-to-use composition for the oxidation dyeing of human keratinous fibers and more particularly hair comprising the mixture of a composition described above and an oxidizing composition.

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 compositions.

Basifying agent The combination according to the invention of sodium metasilicate and ammonia used as basifying agent must make it possible to adjust the pH of the dyeing composition of the present invention from 7.5 to 13 and preferably from 8 to , 5 to 11.5.

According to the present invention, said combination comprises, in active material, from 0.1 to 6% by weight of sodium metasilicate, preferably from 0.5 to 5% and more particularly from 0.1 to 3%, and from 0 to From 1 to 1.6% by weight of ammonia, preferably from 0.4 to 1.2 and more particularly from 0.6 to 1% relative to the total weight of the composition.

According to the present invention, the sodium metasilicate [Na2SiO3] is an anhydrous compound but it can also be in its hydrated forms with 5 or 9 water molecules. Ammonia is introduced into the formulas in the form of ammonia, which is an aqueous solution of ammonia. Ammonia generally used as 20 to 25% by weight of ammonia.

 The present invention makes it possible to reduce the level of ammonia on the basis of an aqueous solution containing 20.5% of ammonia, of 20 to 80% and more particularly of 30 to 60%.

Middle
The cosmetically acceptable medium for dyeing according to the invention consists of water or a mixture of water and at least one organic solvent to solubilize compounds that are not sufficiently soluble in water. As an organic solvent, mention may be made, for example, of C1-C4 alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and

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 monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, the like and mixtures thereof.

The solvents may be present in proportions ranging preferably from 1 to 40% by weight approximately relative to the total weight of the dyeing composition, and even more preferably from 5 to 30% by weight approximately.

Oxidation dyes The oxidation dyes that can be used according to the invention are chosen from oxidation bases and / or couplers.

Preferably the compositions according to the invention contain at least one oxidation base.

The oxidation bases are chosen from those conventionally known in oxidation dyeing, and among which mention may especially be made of ortho- and para-phenylenediamines, double bases, ortho- and para-aminophenols, the following heterocyclic bases and their salts. addition with an acid.

dans laquelle : R1 représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxyalkyle en
C1-C4, polyhydroxyalkyle en C2-C4 , alcoxy(C1-C4)alkyle(C1-C4), alkyle en C1-C4 substitué par un groupement azoté, phényle ou 4'-aminophényle ; R2 représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxyalkyle en

C,-C4 ou polyhydroxyalkyle en C2-C4, alcoxy(CrC4)alkyle(CrC4) ou alkyle en Ci-C4 substitué par un groupement azoté ; R1 et R2 peuvent également former avec l'atome d'azote qui les porte un hétérocycle azoté à 5 ou 6 chaînons éventuellement substitué par un ou plusieurs groupements alkyle, hydroxy ou uréido; There may be mentioned in particular: - (1) the paraphenylenediamines of formula (I) below and their addition salts with an acid:

in which: R1 represents a hydrogen atom, a C1-C4 alkyl radical, monohydroxyalkyl radical;
C1-C4, C2-C4 polyhydroxyalkyl, (C1-C4) alkoxy (C1-C4) alkyl, C1-C4 alkyl substituted by nitrogen, phenyl or 4'-aminophenyl; R2 represents a hydrogen atom, a C1-C4 alkyl radical, monohydroxyalkyl radical,

C 1 -C 4, or C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl or C 1 -C 4 alkyl substituted with a nitrogen moiety; R 1 and R 2 may also form, with the nitrogen atom carrying them, a 5- or 6-membered nitrogenous heterocycle optionally substituted by one or more alkyl, hydroxyl or ureido groups;

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 R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, a C1-C4 alkyl, sulfo, carboxy, C1-C4 monohydroxyalkyl or C1-C4 hydroxyalkoxy, C1-C4 acetylaminoalkoxy radical; , C 1 -C 4 mesylaminoalkoxy or C 1 -C 4 carbamoylaminoalkoxy, R 4 represents a hydrogen atom, a halogen atom or a C 1 -C 4 alkyl radical.

radicaux amino, monoalkyl(CrC4)amino, dialkyl(Cl-C4)amino, trialkyl(Cl-C4)amino, monohydroxyalkyl(C1-C4)amino, imidazolinium et ammonium. Among the nitrogen groups of the formula (I) above, mention may in particular be made of

amino, monoalkyl (CrC4) amino, dialkyl (C1-C4) amino, trialkyl (C1-C4) amino, monohydroxy (C1-C4) alkylamino, imidazolinium and ammonium radicals.

paraphénylènediamine, la 2-méthyl-1 -N-p-hydroxyéthyl-paraphénylèned i amine, la N-(4- aminophényl)-3-hydroxy-pyrrolidine, et leurs sels d'addition avec un acide. Among the paraphenylenediamines of formula (I) above, mention may be made more particularly of para-phenylenediamine, paratoluylenediamine, 2-chloroparaphenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethylparapenylenediamine and 2,6-diethyl para-phenylenediamine, 2,5-dimethylparapenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methyl-aniline, N, N-bis - ((3-hydroxyethyl) -paraphenylenediamine, 4-N, N-bis- (p-hydroxyethyl) amino-2-methyl-aniline, 4-N, N-bis- (ss); hydroxyethyl) -amino-2-chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine N, N-dimethyl-3-methylparaphenylenediamine, N, N- (ethyl, p-hydroxyethyl) -paraphenylenediamine, N- (p, N- (4'-aminophenyl) -paraphenylenediamine, N-phenyl-para-phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2-s-acetylaminoethyloxy-para-phenylenediamine, N- (ss-methoxyethyl) -

paraphenylenediamine, 2-methyl-1-N-hydroxyethyl paraphenyl amine, N- (4-aminophenyl) -3-hydroxy-pyrrolidine, and their addition salts with an acid.

Among the paraphenylenediamines of formula (I) above, paraphenylenediamine, paratoluylenediamine, 2-isopropylparapenylenediamine, 2-p-hydroxyethyl-para-phenylenediamine, 2- [3-hydroxyethyloxy-para-phenylenediamine, 2,6 dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (hydroxyethyl) -paraphenylenediamine, 2-chloro-para-phenylenediamine, and their salts; addition with an acid.

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 (II) According to the invention, the term "double bases" is intended to mean compounds containing at least two aromatic rings bearing amino and / or hydroxyl groups.

dans laquelle : - Z1 et Z2, identiques ou différents, représentent un radical hydroxyle ou-NH2 pouvant être substitué par un radical alkyle en C1-C4 ou par un bras de liaison Y , - le bras de liaison Y représente une chaîne alkylène comportant de 1 à 14 atomes de carbone, linéaire ou ramifiée pouvant être interrompue ou terminée par un ou plusieurs groupements azotés et/ou par un ou plusieurs hétéroatomes tels que des atomes d'oxygène, de soufre ou d'azote, et éventuellement substituée par un ou plusieurs radicaux hydroxyle ou alcoxy en Ci-Ce ; - R5 et R6 représentent un atome d'hydrogène ou d'halogène, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, polyhydroxyalkyle en C2-C4, aminoalkyle en C1-C4 ou un bras de liaison Y ; - R7, R8, Rg, Rio, R11 et R12, identiques ou différents, représentent un atome d'hydrogène, un bras de liaison Y ou un radical alkyle en C1-C4 ; étant entendu que les composés de formule (II) ne comportent qu'un seul bras de liaison
Y par molécule. Among the double bases which can be used as oxidation bases in the dyeing compositions in accordance with the invention, mention may in particular be made of the compounds corresponding to the following formula (II), and their addition salts with an acid:

in which: Z1 and Z2, which may be identical or different, represent a hydroxyl or -NH2 radical which may be substituted by a C1-C4 alkyl radical or by a Y linker; the Y linker represents an alkylene chain containing 1 to 14 carbon atoms, linear or branched may be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms such as oxygen, sulfur or nitrogen, and optionally substituted with one or several hydroxyl or C1-C6 alkoxy radicals; R5 and R6 represent a hydrogen or halogen atom, a C1-C4 alkyl, C1-C4 monohydroxyalkyl, C2-C4 polyhydroxyalkyl, C1-C4 aminoalkyl radical or a Y linkage arm; - R7, R8, Rg, Rio, R11 and R12, which are identical or different, represent a hydrogen atom, a linker Y or a C1-C4 alkyl radical; it being understood that the compounds of formula (II) have only one linking arm
Y per molecule.

radicaux amino, monoalkyl(C1-C4)amino, dialkyl(CrC4)amino, trialkyl(Cl-C4)amino, monohydroxyalkyl(C1-C4)amino, imidazolinium et ammonium. Parmi les bases doubles de formules (II) ci-dessus, on peut plus particulièrement citer le

N,N'-bis-(a-hydroxyéthyl)-N,N'-bis-(4'-aminophényl)-1,3-diamino-propanol, la N,N'-bis-(p- Among the nitrogen groups of formula (II) above, mention may be made in particular of

amino, monoalkyl (C 1 -C 4) amino, dialkyl (C 1 -C 4) amino, trialkyl (C 1 -C 4) amino, monohydroxy (C 1 -C 4) alkylamino, imidazolinium and ammonium radicals. Among the double bases of formulas (II) above, mention may be made more particularly of

N, N'-bis- (α-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diaminopropanol, N, N'-bis- (p-);

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tétraméthylènediamine, la N,N'-bis-(i-hydroxyéthyl)-N,N'-bis-(4-aminophényl)- tétraméthylènediamine, la N,N'-bis-(4-méthyl-aminophényl)-tétraméthylènediamine, la N,N'-bis-(éthyl)-N,N'-bis-(4'-amino-3'-méthylphényl)-éthylènediamine, le 1,8-bis-(2,5diaminophénoxy)-3,5-dioxaoctane, et leurs sels d'addition avec un acide.

hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -ethylenediamine, N, N'-bis- (4-aminophenyl) -

tetramethylenediamine, N, N'-bis (i-hydroxyethyl) -N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) -N, N'-bis- (4'-amino-3'-methylphenyl) -ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane and their addition salts with an acid.

Among these double bases of formula (II), N, N'-bis ((3-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, 1 , 8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane or an acid addition salt thereof are particularly preferred.

dans laquelle : R13 représente un atome d'hydrogène, un atome d'halogène tel que le fluor, un radical

alkyle en C,-C4, monohydroxyalkyle en Croc4, alcoxy(C1-C4)alkyle(C1-C4) ou aminoalkyle en Ci-C4, ou hydroxyalkyl(C,-C4)aminoalkyle en C1-C4. (III) para-aminophenols corresponding to the following formula (III), and their addition salts with an acid:

in which: R13 represents a hydrogen atom, a halogen atom such as fluorine, a radical

C 1 -C 4 alkyl, Croc 4 monohydroxyalkyl, C 1 -C 4 alkoxy (C 1 -C 4) alkyl or C 1 -C 4 aminoalkyl, or C 1 -C 4 hydroxyalkyl (C 1 -C 4) aminoalkyl.

R 14 represents a hydrogen atom or a halogen atom such as fluorine, a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 aminoalkyl, C 1 -C 4 cyanoalkyl or alkoxy (C1-C4) alkyl (C1-C4).

Among the para-aminophenols of formula (III) above, mention may be made more particularly of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol and 4-amino. 3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol 4-amino-2- (ss-hydroxyethylaminomethyl) phenol and their addition salts with an acid.

- (IV) ortho-aminophenols used as oxidation bases in the context of the present invention, are chosen in particular from 2-amino-phenol, 2-amino-1-

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 hydroxy-5-methyl-benzene, 2-amino-1-hydroxy-6-methyl-benzene, 5-acetamido-2-aminophenol, and their addition salts with an acid.

- (V) among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions in accordance with the invention, mention may be made more particularly of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

pyridine, la 2-(p-méthoxyéthyt)amino-3-amino-6-méthoxy pyridine, la 3,4-diamino-pyridine, et leurs sels d'addition avec un acide. Among the pyridine derivatives, mention may be made more particularly of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2,3-diamino-6-methoxy-

pyridine, 2- (p-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino-pyridine, 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 Patent DE 2,359,399 or Japanese JP 88-169,571 and JP 91-10659 or patent applications WO 96/15765, such as 2,4, 5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4dihydroxy-5,6-diaminopyrimidine, 2,5 6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2,750,048 and among which mention may be made of pyrazolo [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino-pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino-pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-Amino-pyrazolo [1,5-a] pyrimidin-7-ylamino) -ethanol; 2- (7-amino-pyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) amino] ethanol; 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) amino] ethanol; 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5-N7-N7-tetramethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-5-methyl-7-imidazolylpropylamino-pyrazolo [1,5-a] pyrimidine; and their addition salts and tautomeric forms, when there is a tautomeric equilibrium and their acid addition salts.

Among the pyrazole derivatives, mention may be made more particularly of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43. 988 such as 4,5-diamino-1-methyl-

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pyrazole, le 4,5-diamino-1-([i-hydroxyéthyl)-pyrazole, le 4,5-diamino-1-éthyl-3-méthyl- pyrazole, le 4,5-diamino-1-éthyl-3-(4'-méthoxyphényl)-pyrazole, le 4,5-diamino-1-éthyl-3hydroxyméthyl-pyrazole, le 4,5-diamino-3-hydroxyméthyl-1-méthyl-pyrazole, le 4,5- diamino-3-hydroxyméthyl-1-isopropyl-pyrazole, le 4,5-diamino-3-méthyl-1-isopropylpyrazole, le 4-amino-5-(2'-aminoéthyl)amino-1,3-diméthyl-pyrazole, le 3,4,5-triaminopyrazole, le 1-méthyl-3,4,5-triamino-pyrazole, le 3,5-diamino-1-méthyl-4-méthylamino-

pyrazole, le 3,5-diamino-4-(p-hydroxyéthyl)amino-1-méthyl-pyrazole, et leurs sels d'addition avec un acide. pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethyl-pyrazole, 4,5-diamino-3- methyl-1-phenyl-pyrazole, 4,5-diamino-1-methyl-3-phenyl-pyrazole, 4-amino-1,3-dimethyl-5-hydrazino-pyrazole, 1-benzyl-4,5- diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5 diamino-1 - ([3-hydroxyethyl) -3-methyl

pyrazole, 4,5-diamino-1- (β-hydroxyethyl) -pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4,5-diamino-3- hydroxymethyl-1-isopropyl-pyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl-pyrazole, 3,4 , 5-triaminopyrazole, 1-methyl-3,4,5-triamino-pyrazole, 3,5-diamino-1-methyl-4-methylamino-

pyrazole, 3,5-diamino-4- (p-hydroxyethyl) amino-1-methyl-pyrazole, and their addition salts with an acid.

According to the present invention, the oxidation bases preferably represent from 0.0005 to 12% by weight approximately of the total weight of the composition and still more preferably from 0.005 to 8% by weight approximately of this weight.

The couplers that can be used in the dyeing composition according to the invention are those conventionally used in oxidation dyeing compositions, that is to say meta-aminophenols, meta-phenylenediamines, meta-diphenols, naphthols and couplers. heterocyclic compounds such as, for example, indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles, quinolines and their addition salts with an acid.

benzène, le 2-méthyl-5-amino-phénol, le 5-N-([i-hydroxyéthyl)amino-2-méthyl-phénol, le 3- amino-phénol, le 2-chloro-3-amino-6-méthyl-phénol, le 1,3-dihydroxy-benzène, le 1,3dihydroxy-2-méthyl-benzène, le 4-chloro-1,3-dihydroxy-benzène, le 2-amino4-(p- hydroxyéthylamino)-1-méthoxy-benzène, le 1,3-diamino-benzène, le 1,3-bis-(2,4diaminophénoxy) -propane, le sésamol, le 1-amino-2-méthoxy-4,5-méthylènedioxy benzène, l'a-naphtol, le 6-hydroxy-indole, le 4-hydroxy-indole, le 4-hydroxy-N-méthyl indole, la 6-hydroxy-indoline, la 2,6-dihydroxy-4-méthyl-pyridine, le 1-H-3-méthyl-pyrazole-5-one, le 1phényl-3-méthyl-pyrazole-5-one, la 2-amino-3-hydroxypyridine, le 3,6-diméthyl-pyrazolo-[3,2- These couplers are more particularly chosen from 2,4-diamino-1- (ss-hydroxyethyloxy) -

benzene, 2-methyl-5-amino-phenol, 5-N - ([i-hydroxyethyl) amino-2-methyl-phenol, 3-amino-phenol, 2-chloro-3-amino-6- methylphenol, 1,3-dihydroxybenzene, 1,3dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2-amino4- (p-hydroxyethylamino) -1- methoxybenzene, 1,3-diamino-benzene, 1,3-bis- (2,4-diaminophenoxy) -propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1- H-3-methyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethyl-pyrazolo-

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 c] -1,2,4-triazole, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole and their addition salts with an acid.

When present, these couplers preferably represent from 0.0001 to 10% by weight approximately of the total weight of the composition, and still more preferably from 0.005 to 5% by weight approximately.

In general, the acid addition salts of the oxidation bases and couplers are chosen in particular from hydrochlorides, hydrobromides, sulphates and tartrates, lactates and acetates.

The composition according to the invention may also contain, in addition to the oxidation dyes defined above, direct dyes to enrich the shades in reflections. These direct dyes may especially be chosen from nitro, azo or anthraquinone, neutral, cationic or anionic dyes in the weight proportion of about 0.001 to 20% and preferably from 0.01 to 10% of the total weight of the composition.

Adjuvants The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, fatty alcohols fatty acids, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners or thickening polymers such as, for example, nonionic guar gums, associative polymers comprising at least a hydrophilic unit and at least one fatty chain of nonionic, anionic, cationic or amphoteric nature, antioxidants or reducing agents, penetration agents, sequestering agents such as EDTA and etidronic acid, UV filters, waxes, perfumes, buffers, dispersing agents, conditioning agents such as, for example volatile or non-volatile silicones, modified or unmodified, film-forming agents, pearlescent agents, preserving agents, ceramides, pseudoceramides, vegetable, mineral or synthetic oils, vitamins or provitamines such as panthenol, opacifiers , etc ....

Preferably, the dyeing composition of the invention contains at least one cationic polymer in a proportion of approximately 0.05 to 10% by weight and at least one preferably nonionic surfactant in the proportion of 0.1 to 20% by weight. weight.

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Preferably it also contains at least one thickening polymer preferably selected from associative polymers in the proportion of about 0.05 to 10% by weight.

The reducing agents or antioxidants may be chosen in particular from sodium sulphite, thioglycolic acid and thiolactic acid as well as their ammonium salts, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2- methylhydroquinone, tert-butyl-hydroquinone and homogentisic acid, and they are then generally present in amounts ranging from about 0.05 to 3% by weight relative to the total weight of the composition.

Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially, impaired by the one or more proposed additions.

The dyeing process according to the invention comprises the following steps: at the moment of use, a dyeing composition as described above is mixed and therefore comprising a cosmetically acceptable medium based on water and at basic pH. ranging from 7.5 to 13, at least one oxidation dye and a combination of sodium metasilicate and ammonia, with an oxidizing composition, the mixture obtained is then applied to the keratinous fibers, allowed to set for 3 to 50 minutes. minutes, preferably about 5 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried.

The coloring composition before mixing with the oxidant may be in various forms, such as liquid, cream, gel, possibly pressurized or in any other form suitable for carrying out after mixing a dyeing of human keratinous fibers and in particular hair.

Oxidant In the oxidizing composition, the oxidizing agent is chosen from hydrogen peroxide and compounds capable of releasing hydrogen peroxide in situ, oxidation-reduction enzymes such as laccases, peroxidases and 2-electron oxidoreductases. (such as uricase), if appropriate in the presence of their respective donor or cofactor.

<Desc / Clms Page number 12>

The use of hydrogen peroxide is particularly preferred. This oxidizing agent is advantageously constituted by a solution of hydrogen peroxide whose content may vary, more particularly, from about 1 to 40 volumes, and even more preferably from about 5 to 40.

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

EXAMPLES 1 - 3 The following dyeing compositions were prepared: (contents expressed in grams of active ingredient)

<Tb>
<tb> Example <SEP> 1 <SEP> Example <SEP> 2 <SEP> Example <SEP> 3
<Tb>

Paraphénytènediamine.................................... 0,24 0,24 0,24 Para-aminophénol............................................ 0,44 0,44 0,44

Paraphenytenediamine .................................... 0.24 0.24 0.24 Para-aminophenol. ........................................... 0.44 0.44 0 , 44

<Tb>
<tb> 2-amino-phenol .......................................... ....... <SEP> 0.028 <SEP> 0.028 <SEP> 0.028
<tb> 1,3-dihydroxybenzene ........................................ <SEP> 0.192 <SEP> 0.192 <SEP> 0.192
<tb> 3-amino-phenol .......................................... ....... <SEP> 0.019 <SEP> 0.019 <SEP> 0.019
<Tb>

5-N-(p-hydroxyéthyt)-amino-2-méthyt-phénot............ 0,021 0,021 0,021

5-N- (p-hydroxyethyl) -amino-2-methylphenol ............ 0.021 0.021 0.021

<Tb>
<tb> 1,3-dihydroxy-2-methyl-benzene ........................... <SEP> 0.055 <SEP> 0.055 <SEP> 0.055
<tb> Metasilicate <SEP> of <SEP> Sodium <SEP> Anhydrous ............................ <SEP> 2 <SEP > 2 <SEP> 2 <SEP>
<tb> Ammonia <SEP> to <SEP> 20.5% <SEP> of <SEP> NH3 ........................... .... <SEP> 1.23 <SEP> 1.23 <SEP> 1.23
<tb> Reducer, <SEP> antioxidant, <SEP> sequestering, <SEP> perfume ......... <SEP> qs <SEP> qs <SEP> qs
<Tb>

Propylene <SEP> glycol ............................................. ... <SEP> 10 <SEP> 10 <SEP> 10
<tb> Polymer <SEP> anionic <SEP>: <SEP> polyacrylic acid <SEP> polyacrylic <SEP> crosslinked <SEP> 0,4 <SEP> 0,4 <SEP> 0,4
<tb> Polymer <SEP> amphoteric: <SEP> Polyquaternium <SEP> 22 <SEP> (Name <SEP> 1,5 <SEP> 1,5
<tb> C. <SEP> TFA) <SEP> Merquat <SEP> 280 <SEP> sold <SEP> by <SEP> the <SEP> company <SEP> CALGON
<tb> Polymer <SEP> cationic <SEP>: <SEP> Polyquaternium <SEP> 6 <SEP> (Name <SEP> 2,8
<tb> C. <SEP> TFA) <SEP> Merquat <SEP> 100 <SEP> sold <SEP> by <SEP> the <SEP> company <SEP> MERCK
<tb> Cationic <SEP> Polymer <SEP>: <SEP> Hexadimethrin <SEP> Chloride <SEP> (Name <SEP> 3 <SEP> 3
<tb> C. <SEP> TFA) <SEP> Mexomer <SEP> PO <SEP> sold <SEP> by <SEP> the <SEP> company
<tb> CHIMEX <SEP> ........................................... ............... <SEP>
<Tb>

<SEP> anionic surfactant <SEP>: <SEP> laurylsulfate <SEP> from <SEP> sodium <SEP> in <SEP> 3
<Tb>

<Desc / Clms Page number 13>

<Tb>
<tb> powder <SEP> ........................................... ................ <SEP>
<Tb>

Surfactant <SEP> no <SEP> ionic <SEP>: <SEP> alcohol <SEP> lauric <SEP> oxyethylenated <SEP> 7.5 <SEP> 7.5
<tb> to <SEP> 12 <SEP> moles <SEP> oxide <SEP> of ethylene .......................... ..
<Tb>

Surfactant <SEP> no <SEP> ionic <SEP>: <SEP> alcohol <SEP> oleocetyl alcohol <SEP> 4 <SEP> 4
<tb> oxyethylenated <SEP> at <SEP> 30 <SEP> moles <SEP> oxide <SEP> of ethylene ............
<Tb>

Surfactant <SEP> no <SEP> ionic <SEP>: <SEP> alcohol <SEP> decylate <SEP> 10 <SEP> 10 <SEP> 10
<tb> oxyethylenated <SEP> at <SEP> 3 <SEP> moles <SEP> oxide <SEP> of ethylene ............
<Tb>

Surfactant <SEP> no <SEP> ionic <SEP>: <SEP> alcohol <SEP> decylate <SEP> 8
<tb> oxyethylenated <SEP> to <SEP> 5 <SEP> moles <SEP> oxide <SEP> of ethylene ............
<Tb>

<SEP> lauric acid ............................................. ...... <SEP> 2.5 <SEP> 2.5
<tb> Alcohol <SEP> cetylstearyl alcohol <SEP> 50/50 ................................ <SEP> 11 , 5 <SEP> 11.5
<tb> Agent <SEP> nacrant <SEP>: <SEP><SEP> pyrogenous silica <SEP> hydrophobic ......... <SEP> 1,2 <SEP> 1,2
<tb> Agent <SEP> nacrant <SEP>: <SEP> Monostearate <SEP> of <SEP> glycerol <SEP> .............. <SEP> 2 <SEP> 2
<tb> Demineralized water <SEP> ................................ qsp ...... <SEP> 100 <SEP> 100
<Tb>
At the time of use, weight for weight, each dye composition described above, was mixed with a solution of hydrogen peroxide at 20 volumes (6% by weight).

The mixtures thus produced were applied for 30 minutes to locks of natural gray hair or permed with 90% of whites. The locks were then rinsed, washed with a standard shampoo, rinsed again and then dried.

It has been found that these mixtures are much less odorous than those of the prior art with satisfactory application qualities.

The hair was dyed in a deep golden golden shade for each of Examples 1 to 3.

Compared to identical compositions of the prior art except that they do not contain sodium metasilicate and have a much higher ammonia content of about 2% of active material, the dyeing performance of compositions 1 to 3 were retained.

Claims (22)

 1. A composition for the oxidation dyeing of human keratin fibers and more particularly the hair, comprising, in a cosmetically acceptable water-based medium, and at basic pH, at least one oxidation dye and an alkalinizing agent, characterized in that the basifying agent is a combination of sodium metasilicate and ammonia. 2. Composition according to claim 1, characterized in that the basifying agent comprises active material, from 0.1 to 6% by weight of sodium metasilicate relative to the total weight of the composition. 3. Composition according to claim 2, characterized in that the basifying agent comprises active material, from 0.5 to 5% by weight of sodium metasilicate relative to the total weight of the composition. 4. Composition according to claim 3, characterized in that the basifying agent comprises active material, from 1 to 3% by weight of sodium metasilicate relative to the total weight of the composition. 5. Composition according to any one of the preceding claims, characterized in that the basifying agent comprises active material, from 0.1 to 1.6% by weight of ammonia, relative to the total weight of the composition. 6. Composition according to claim 5, characterized in that the alkalizing agent comprises active material, 0.4 to 1.2% by weight of ammonia, relative to the total weight of the composition. 7. Composition according to claim 6, characterized in that the basifying agent comprises active material, from 0.6 to 1% by weight of ammonia, relative to the total weight of the composition. 8. Composition according to any one of the preceding claims, characterized in that its pH is 7.5 to 13. 9. Composition according to claim 8, characterized in that its pH is 8.5 to 11.5. <Desc / Clms Page number 15> 10. Composition according to any one of the preceding claims, characterized in that the oxidation dye (s) are chosen from oxidation bases and couplers. 11. Composition according to claim 10, characterized in that it comprises at least one oxidation base. 12. The composition as claimed in claim 11, characterized in that the oxidation bases are chosen from the group formed by ortho- and para-phenylenediamines, double bases, ortho- and para-aminophenols, heterocyclic bases and their addition salts with an acid. 13. Composition according to Claim 10, characterized in that the couplers are chosen from the group formed by meta-aminophenols, meta-phenylenediamines, meta-diphenols, naphthols, indole derivatives, indoline derivatives, sesamol and its derivatives. derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles, quinolines, and their addition salts with an acid. 14. Composition according to any one of Claims 10 to 13, characterized in that the acid addition salts of the oxidation bases and couplers are chosen from hydrochlorides, hydrobromides, sulphates and tartrates. lactates and acetates. 15. Composition according to any one of the preceding claims, characterized in that the oxidation base (s) are present at a concentration ranging from 0.0005% to 12% by weight relative to the total weight of the composition. 16. Composition according to any one of the preceding claims, characterized in that the coupler or couplers are present at a concentration of between 0.0001 and 10% by weight relative to the total weight of the composition. 17. Composition according to any one of the preceding claims, characterized in that the cosmetically acceptable water-based medium comprises at least one organic solvent. <Desc / Clms Page number 16> 18. Composition according to Claim 17, characterized in that the organic solvent or solvents are present in proportions ranging from 1 to 40% by weight relative to the total weight of the composition. 19. Composition according to any one of the preceding claims, characterized in that it contains at least one cationic polymer in the proportion of 0.05 to 10% by weight and at least one nonionic surfactant in the proportion of 0, 1 to 20% by weight relative to the total weight of the composition. 20. A process for dyeing human keratin fibers, and in particular hair, characterized in that, at the time of use, a dye composition as described in any one of Claims 1 to 19 is mixed with an oxidizing composition. the resulting mixture is applied to the fibers, allowed to set for 3 to 50 minutes, preferably 5 to 30 minutes, after which it is rinsed, washed with shampoo, rinsed again and dried, said oxidizing composition comprising hydrogen peroxide or a compound capable of releasing hydrogen peroxide in situ, or a redox enzyme. 21. Ready-to-use composition for the oxidation dyeing of human keratinous fibers and in particular the hair, characterized in that it comprises the mixing of a composition defined in any one of Claims 1 to 19 with an oxidizing composition. 22. Composition according to Claim 21, characterized in that the oxidizing composition comprises hydrogen peroxide.