Composition for dying keratine fibres including 2,3-diamino-6, 7-dihydro-1h, 5h-pyrazolo[1,2-a]pyrazol-1-on, 6-chlor-2-methyl-5-aminophenol and substituted m-aminophenol

FIELD: chemistry.

SUBSTANCE: invention relates to composition for dying keratin fibres, including 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1on as first oxidised base, 6-chlor-2-methyl-5-aminophenol as first component of condensation and substituted m-aminophenol as second component of condensation. Molar ratio of first oxidised base and first component of condensation is lower than 1.5, molar ratio of first oxidised base and second component of condensation is higher than 1, and molar amount of first oxidised base is higher or equals 2.5·10-3 mole per 100 g of composition.

EFFECT: claimed composition ensures obtaining intensive, chromatic, esthetically attractive low-selective and stable with respect to different aggressive impacts dying of keratin fibres with copper-red shades and, in addition, with neutral pH value.

16 cl, 2 tbl, 1 ex

 

The object of the present invention is a composition for dyeing Martinovich fibers and in particular human keratin fibres such as the hair, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole-1-first oxidized bases, 6-chloro-2-methyl-5-aminophenol as the first component condensation of substituted m-aminophenol as the second component condensation.

Known dyeing keratin fibers and in particular human keratin fibres such as the hair, with dye compositions comprising predecessors fixed in the oxidation dyes, such as, in particular, o - or p-phenylenediamine, o - or p-aminophenols, heterocyclic compounds such as derivatives of diaminophenol, derivatives of pyrazolo[1,5-a]pyrimidine, pyrimidine derivatives, derivatives of pyridine, indole derivatives, derivatives indoline, usually referred to as oxidized bases. Predecessors fixed in the oxidation dyes, or oxidized bases, are colorless or slightly colored compounds that are assosiated with oxidizing agents, can give rise to a process of oxidative condensation with painted or coloured compounds. Thus achieve long-lasting colors.

It is also known that it is possible to vary Ott the NCI, produced with these oxidized bases by combining them with the components of condensation or color modifiers, and these last chosen, in particular, among the m-phenylenediamines, m-aminophenols, m-hydroxyphenol and certain heterocyclic compounds.

The variety of molecules used at the level of oxidized bases and components condensation, allows to obtain a rich palette of colors.

The use of oxidized bases, such as derivatives of p-phenylenediamine and p-aminophenol, can get pretty wide range of colors at an alkaline pH value, however, without reaching shades good chromaticity, in General, giving hair excellent properties in relation to the intensity of tone, evenness of tone and resistance to external factors.

The use of these bases at neutral pH does not allow to achieve a range of different shades, in particular warm shades, such as red and orange.

The aim of the present invention to provide new compositions for dyeing keratin fibers, which allow to achieve intense, chromatic, aesthetically attractive color with copper-red shades, moselectro and possessing good resistance to various aggressive actions, which may have subjected the sterile hair, such as shampoos, light, sweat and permanent deformation.

The object of the present invention, therefore, is a composition for dyeing keratin fibers, comprising, in an appropriate environment:

• at least the first oxidizing the basis chosen among the 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole-1-it is of the following formula (I) and additive salts:

• at least the first component condensation, choose among 6-chloro-2-methyl-5-aminophenol and its additive salts; and

• at least the second component condensation, choose among the replaced m-aminophenols the following formula (II) and their additive salts:

in which

R1and R2identical or different, denote a hydrogen atom; an alkyl radical; monohydrocalcite radical; polyhydroxyalkane radical; monolingually radical; or

R1and R2with each other and with the nitrogen atom to which they are attached, form a cyclic group containing one or more heteroatoms, with 5-7 members in the loop, saturated or unsaturated, unsubstituted or substituted by one or more radicals selected among carboxyl, carboxamido, hydroxyl, amino, mono - or dialkylamino, alkyl, possibly substituted by one or a few is Kimi hydroxyl radicals, amino groups, mono - or dialkylaminoalkyl;

R3signify, independently from each other, a hydrogen atom; an alkyl radical; CNS radical; monohydrocalcite radical; polyhydroxyalkane radical; monohydroxylation radical; polyhydroxyalkanoates radical;

n means an integer from 0 to 4;

provided that:

when n is 0, then at least one of the radicals R1and R2is different from a hydrogen atom;

when n is 2, and the radicals R3denote methyl or a chlorine atom, respectively, in positions 2 and 6, then R1and R2at the same time do not represent a hydrogen atom;

having in mind that the molar ratio of the first oxidizing the base/first component condensation is below 1.5, the molar ratio of the first oxidizing the base/the second component condensation is above 1 and the molar quantity of the first oxidizing the base above or equal to 2.5 .10-3mol per 100 g of composition.

According to the present invention can be obtained coloring keratin fibers with copper-red shades, in particular, coloring grey hair with 90% natural or subjected to a permanent colouring grey hair with according to the rating system CIELab value L*, less than or equal to 50, the value of a*above or equal to 20, preferably higher than or equal to 25, still valueproposition, comprising from 25 to 50, the value of b*, is higher or equal to 20, preferably higher than or equal to 25, even more preferably comprising from 25 to 50, and the ratio b*/a*comprising from 0.5 to 1.5, preferably from 0.7 to 1.2.

According to the present invention can also be intense, very chromatic, aesthetically appealing color, moselectro and with good resistance to various aggressive actions, which can be subjected to hair, such as shampoos, light, sweat and permanent deformation. According to the invention, moreover, it is possible to achieve intense staining with neutral pH value.

Another object of the invention is a method of coloring keratin fibers, in which case use of the composition according to the present invention, and the use of this composition for dyeing keratin fibers.

Finally, the object of the invention is a kit for dyeing, comprising, on the one hand, a composition for dyeing containing 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole-1-first oxidized bases, 6-chloro-2-methyl-5-aminophenol as the first component condensation of substituted m-aminophenol as the second component condensation, and, on the other hand, the composition containing the oxidizing agent.

The rating system CIELAB used within the infusion is his invention, defines colorimetric interval in which each color is defined by three parameters (L*, a*, b*). The parameter L* represents the lightness of the color, and the value of L* is equal to 0 for black and 100 for absolute white. The higher the value of L*, the less intense is the colour. The parameter a* corresponds to the axis of the antagonistic pair of colors green/red. Option b* corresponds to the axis of the antagonistic pair of colors blue/yellow.

Unless there are other indications, limits of gamma values, which are given in the framework of the present invention, included in these scales.

In the framework of the present invention under an alkyl radical realize a linear or branched alkyl radical with 1-10 carbon atoms, except in opposite directions, preferably with 1-6 carbon atoms, even more preferably from 1-4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, pentyl, hexyl.

In the framework of the present invention, the heteroatom or heteroatoms can be selected from among oxygen atom, nitrogen atom, sulfur atom, phosphorus atom.

In the framework of the present invention, the halogen atom may be selected from among chlorine atom, bromine atom, iodine atom and fluorine atom.

According to one variant of the particular embodiment of the invention R1and R2mean, regardless what about from each other, a hydrogen atom; an alkyl radical such as methyl or ethyl; monohydrocalcite radical such as β-hydroxyethyl or γ-hydroxypropyl; or R1and R2with each other and with the nitrogen atom to which they are bound, form a cycle selected among pyrolidine, piperidino, homopiperazine, pieperazinove, homopiperazine, morpholino heterocycles; and the above cycles may be substituted by one or more hydroxyl radicals, amino groups, mono - or di-(C1-C2-alkylaminocarbonyl, carboxyl radicals, carboxamidotryptamine, (C1-C4)-alkyl radical, possibly substituted by one or more hydroxyl radicals, amino groups, mono - or di-(C1-C2-alkylaminocarbonyl; and, more preferably, selected among pyrrolidine, 2,5-dimethyl-pyrrolidine, pyrrolidin-2-carboxylic acid, 3-hydroxy-pyrrolidin-2-carboxylic acid, 4-hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyridine, 3-hydroxy-2-hydroxyethylpyrrolidine, 2-carboxyethylidene, 3-hydroxy-2-carboxymethylamino, 2-hydroxymethyl-pyrrolidine, 3,4-dihydroxy-2-hydroxyethylpyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxypyrrolidine, 3-aminopyrrolidine, 3-methylaminopropane, 3-dimethylamino-pyrrolidine, 4-amino-3-hydroxyprop Edina, 3-hydroxy-4-(β-hydroxyethyl)aminopyrrolidine, piperidine, 2,6-dimethyl-piperidine, 2-carboxypeptidase, 2-carboxamidotryptamine, 2-hydroxyethylpiperazine, 3-hydroxy-2-hydroxyethylpiperazine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethyl-piperidine, homopiperazine, 2-carboxyaniline, 2-carboxamidotryptamine, homopiperazine, N-methyl-homopiperazine, N-(2-hydroxyethyl)homopiperazine, piperazine, 4-methylpiperazine, 4-ethylpiperazine, 4-(β-hydroxyethyl)-piperazine, of the research; and, more specifically, they form pyrrolidin-1-yl; piperidine-1-yl; piperazine-1-yl; 4-methylpiperazin-1-yl; 4-ethylpiperazin-1-yl; 4-(β-hydroxyethyl)piperazine-1-yl; morpholine-4-yl.

According to the variant of a particular embodiment of the invention R3choose among a halogen atom, alkyl radical, CNS radical, monohydroxylation radical. As an example, R3chosen among chlorine atom, methyl, metoxygroup, β-hydroxyethyloxy.

According to the variant of a particular embodiment of the invention n is 0 to 2. As an example, n is 1 or 2. When n is 1, R3may be in position 2, and when n is 2, R3can be in positions 2 and 4.

Of the substituted m-aminophenol of the formula (II)usable in the framework of the invention, more specifically, can be called 5-amino-2-methoxy who enol; 5-amino-2-(β-hydroxyethyloxy)phenol; 5-amino-2-METHYLPHENOL; 5-N-(β-hydroxyethyl)amino-2-METHYLPHENOL; 5-N-(β-hydroxyethyl)amino-4-methoxy-2-METHYLPHENOL; 5-amino-4-methoxy-2-METHYLPHENOL; 5-amino-4-chloro-2-METHYLPHENOL; 5-amino-2,4-dimethoxyphenol; 5-(γ-hydroxypropylamino)-2-METHYLPHENOL; 3-dimethylaminophenol; 2-methyl-5-dimethylaminophenol; 2-ethyl-5-dimethylaminophenol; 2-methoxy-5-dimethylaminophenol; 2 ethoxy-5-dimethylaminophenol; 2-(β-hydroxyethyl)-5-dimethylaminophenol; 3-diethylaminophenol; 2-methyl-5-diethylaminophenol; 2-ethyl-5-diethylaminophenol; 2-methoxy-5-diethylaminophenol; 2 ethoxy-5-diethylaminophenol; 2-(β-hydroxyethyl)-5-diethylaminophenol; 3-di-(β-hydroxyethyl)aminophenol; 2-methyl-5-di(β-hydroxyethyl)amino-phenol; 2-ethyl-5-di(β-hydroxyethyl)aminophenol; 2-methoxy-5-di-(β-hydroxyethyl)aminophenol; 2-ethoxy-5-di(β-hydroxyethyl)-aminophenol; 2-(β-hydroxyethyl)-5-di(β-hydroxyethyl)aminophenol; 3-pyrrolidin-1-infenal; 2-methyl-5-pyrrolidin-1-infenal; 2-ethyl-5-pyrrolidin-1-infenal; 2-methoxy-5-pyrrolidin-1-infenal; 2 ethoxy-5-pyrrolidin-1-infenal; 2-(β-hydroxyethyl)-5-pyrrolidin-1-infenal; 3-piperidine-1-infenal; 2-methyl-5-piperidine-1-infenal; 2-ethyl-5-piperidine-1-infenal; 2-methoxy-5-piperidine-1-infenal; 2 ethoxy-5-piperidine-1-infenal; 2-(β-hydroxyethyl)-5-piperidine-1-infenal; 3-piperazine-1-infenal; 2-methyl-5-piperazine-1-infenal; 2-ethyl-5-piperazine-1-infenal; 2-methoxy-5-piperazine-1-infenal; 2 ethoxy-5-p is perazin-1-infenal; 2-(β-hydroxyethyl)-5-piperazine-1-infenal; 3-(4-methylpiperazin-1-yl)phenol; 2-methyl-5-(4-methylpiperazin-1-yl)phenol; 2-ethyl-5-(4-methylpiperazin-1-yl)phenol; 2-methoxy-5-(4-methylpiperazin-1-yl)phenol; 2-ethoxy-5-(4-methylpiperazin-1-yl)phenol; 2-(β-hydroxyethyl)-5-(4-methylpiperazin-1-yl)phenol; 3-(4-ethyl-piperazine-1-yl)phenol; 2-methyl-5-(4-ethylpiperazin-1-yl)phenol; 2-ethyl-5-(4-ethylpiperazin-1-yl)phenol; 2-methoxy-5-(4-ethyl-piperazine-1-yl)phenol; 2-ethoxy-5-(4-ethylpiperazin-1-yl)phenol; 2-(β-hydroxyethyl)-5-(4-ethylpiperazin-1-yl)phenol; 3-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-methyl-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-ethyl-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-methoxy-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-ethoxy-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-(β-hydroxyethyl)-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 3-morpholine-4-infenal; 2-methyl-5-morpholine-4-infenal; 2-ethyl-5-morpholine-4-infenal; 2-methoxy-5-morpholine-4-infenal; 2 ethoxy-5-morpholine-4-infenal; 2-(β-hydroxyethyl)-5-morpholine-4-infenal.

Of the substituted m-aminophenol of the formula (II)above, particularly preferred are 5-N-(β-hydroxyethylamino)-2-METHYLPHENOL and 5-amino-2-METHYLPHENOL.

In the composition according to the present invention the molar ratio of the first oxidizing the base/first component condensation is below 1.5. Preferably, the molar ratio of the first oxidizing osnovaniya component condensation is from 0.5 to 1.2.

In the composition according to the present invention the molar ratio of the first oxidizing the base/the second component condensation is above 1. Preferably the molar ratio of the first oxidizing the base/the second component condensation is from 2 to 5.

The ink composition according to the invention may contain at least the second oxidizable base selected among the para-aminophenols.

From p-aminophenol used as oxidized bases in the dye compositions according to the invention, in particular, include compounds corresponding to the following formula (III), and their additive salt:

in which

R4means a hydrogen atom; a halogen atom; an alkyl radical; monohydrocalcite radical; alkoxyalkyl radical; aminoalkyl radical; hydroxyethylaminomethyl radical;

R5means a hydrogen atom; a halogen atom; an alkyl radical; monohydrocalcite radical; polyhydroxyalkane radical; aminoalkyl radical; cyanoaniline radical; alkoxyalkyl radical;

having in mind that at least one of the radicals R4or R5means a hydrogen atom.

Of p-aminophenols the above formula (III) more specifically can be called p-aminophenol, 4-amino-3-METHYLPHENOL, 4-amino-3-terfenol, amino-3-hydroxymethylene, 4-amino-2-METHYLPHENOL, 4-amino-2-hydroxymethylene, 4-amino-2-methoxymethanol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol, 4-amino-2-terfenol. Particularly preferred is p-aminophenol.

The ink composition according to the invention may contain other oxidized bases that are different from those that are suitable according to the present invention, and is usually used for dyeing keratin fibers.

The composition according to the present invention may, for example, include at least one additional oxidizing base selected among p-phenylendiamine, biphenylmethanol, bis-para-aminophenols, o-aminophenols, o-phenylendiamine, heterocyclic bases other than 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole-1-it and its additive salts.

From p-phenylenediamines can be called, as an example, p-phenylenediamine, p-toluidine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)-amino-2-Chloroaniline, 2-(β-hydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenedi the min, 2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylene-diamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N,N-(ethyl-β-hydroxyethyl)-p-phenylenediamine, N-(β,γ-dihydroxypropyl)-p-phenylenediamine, N-(4'-AMINOPHENYL)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-(β-hydroxyethyloxy)-p-phenylenediamine, 2-(β-acetylaminobenzoic)-p-phenylenediamine, N-(β-methoxyethyl)-p-phenylenediamine, 4-aminophenylalanine, 2-thienyl-p-phenylene-diamine, 2-β-hydroxyethylamino-5-aminotoluene, 3-hydroxy-1-(4'-AMINOPHENYL)pyrrolidine, and their additive salt.

From the above p-phenylendiamine especially preferred are 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-p-phenylenediamine, 2-β-hydroxyethyloxy-p-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, N,N-bis(β-hydroxyethyl)-p-phenylene-diamine, 2-chloro-p-phenylenediamine, 2-β-acetamidoacrylate-p-phenylenediamine, and their additive salt.

From biphenylmethanol can be called, as an example, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-AMINOPHENYL)-1,3-diaminopropanol, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-AMINOPHENYL)Ethylenediamine, N,N'-bis(4-AMINOPHENYL)tetramethylene diamine, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-AMINOPHENYL)-tetramethylaniline, N,N'-bis(4-methylaminophenol)tetramethylene diamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-were)ethylene-diamine, 1,8-bis(2,5-dia is noproxy)-3,6-dioxaoctyl, and their additive salt.

From o-aminophenols include, as an example, 2-aminophenol, 2-amino-5-METHYLPHENOL, 2-amino-6-METHYLPHENOL, 5-acetamido-2-aminophenol and their additive salt.

Of the heterocyclic bases include, as an example, pyridine derivatives, pyrimidine derivatives and pyrazole nucleus derived.

Of pyridine derivatives include the compounds described, for example, in patents in the UK 1026978 and 1153196 as 2.5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(β-methoxyethyl)-amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their additive salt.

Other oxidizing the pyridine bases which are suitable according to the present invention are oxidized bases 3-aminopyrazole[1,5-a]pyridine and their additive salts described, for example, in the patent application France 2801308. As example can be mentioned pyrazolo[1,5-a]pyridine-3-ylamine; 2-acetylaminophenol[1,5-a]pyridine-3-ylamine; 2-morpholine-4-yl - pyrazolo[1,5-a]pyridine-3-ylamine; 3-aminopyrazole[1,5-a]-pyridine-2-carboxylic acid; 2-methoxypyrazine[1,5-a]pyridine-3-ylamine; (3-aminopyrazole[1,5-a]pyridin-7-yl)methanol; 2-(3-aminopyrazole[1,5-a]pyridin-5-yl)ethanol; 2-(3-aminopyrazole-[1,5-a]pyridin-7-yl)ethanol; (3-aminopyrazole[1,5-a]pyridine-2-yl)methanol; 3,6-diaminopyridine[1,5-a]pyridine; 3,4-diamino-pyrazolo[1,5-a]feast the Dean; pyrazolo[1,5-a]pyridine-3,7-diamine; 7-morpholine-4-alprazola[1,5-a]pyridine-3-ylamine; pyrazolo[1,5-a]-pyridine-3,5-diamine; 5-morpholine-4-alprazola[1,5-a]pyridine-3-yl-amine; 2-[(3-aminopyrazole[1,5-a]pyridin-5-yl)-(2-hydroxyethyl)amino]ethanol; 2-[(3-aminopyrazole[1,5-a]pyridin-7-yl)-(2-hydroxyethyl)amino]ethanol; 3-aminopyrazole[1,5-a]-pyridine-5-ol; 3-aminopyrazole[1,5-a]pyridine-4-ol; 3-amino-pyrazolo[1,5-a]pyridine-6-ol; 3-aminopyrazole[1,5-a]pyridine-7-ol; as well as their additive salt.

Of pyrimidine derivatives include compounds described, for example, in the patent Germany 2359399, the Japan patent 88-169571 and 05-63124, European patent 0770375 or International patent application WO-96/15765 as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diamino-pyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives, such as those described in the application for French patent A-2750048, and of which can be called 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-aminopyrazole[1,5-a]-pyrimidine-7-ol; 3-aminopyrazole[1,5-a]pyrimidine-5-ol; 2-(3-aminopyrazole[1,5-a]pyrimidine-7-ylamino)ethanol; 2-(7-amino-pyrazolo[1,5-a]pyrimidine-3-ylamino)ethanol; 2-[(3-amino-pyrazolo[1,5-a]pyrimidine-7-yl)-(2-hydroxyethyl)amino]ethanol; 2-[(7-aminopyrazole[1,5-a]pyrimid the n-3-yl)-(2-hydroxyethyl)-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-tetramethylpyrazine[1,5-a]pyrimidine-3,7-diamine; 3-amino-5-methyl-7-imidazolidinylideneamino[1,5-a]pyrimidine; and their additive salts and their tautomeric forms, when there is a tautomeric equilibrium.

From pyrazol derivatives include compounds described in patents Germany 3843892 and 4133957, International patent applications WO-94/08969 and WO-94/08970, the application for French patent A-733749 and the patent application Germany 19543988 as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 3,4-diaminophenol, 4,5-diamino-1-(4'-Chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazol, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinophenyl, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyluracil, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'-amino-ethyl)amino-1,3-dimethylpyrazole, 3,4,5-diaminophenol, 1-methyl-3,4,5-diaminophenol, 3,5-diamino-1-methyl-4-methylaminophenol, 3,5-diamino-4-(β-hydroxyethyl)-amino-1-methylpyrazole, and dditive salt.

The ink composition according to the invention may contain additional components condensation that are different from those that are suitable according to the present invention, and is usually used for dyeing keratin fibers.

The composition according to the present invention may include, for example, at least one additional component condensation, chosen among the m-phenylenediamines, m-aminophenols, non-6-chloro-2-methyl-5-aminophenol, m-aminophenol of the formula (II) and their additive salts, m-diphenols, naphthalene component condensation of heterocyclic components of condensation.

As examples can be called 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzoyl, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzoyl, 1,3-diamino-benzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-origanily, 3 ureido-1-dimethylaminobenzene, sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(β-hydroxyethyl)amino-3,4-methylene-dioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, and their additive salt.

Preferably the composition according to the invention includes at least one d the additional component condensation, choose among 2-amino-3-hydroxypyridine, 1,3-hydroxy-2-methylbenzoyl and their additive salts.

Oxidizing the base or oxidizing the base present in the composition according to the invention, usually are, each in the amount of approximately from 0.001 to 10 wt.%, calculated on the total mass of the ink composition, preferably, 0.005 to 6 wt.%

Component condensation or components of condensation present in the compositions according to the invention, each are in the amount of approximately from 0.001 to 10 wt.%, calculated on the total mass of the ink composition, preferably, 0.005 to 6 wt.%.

Typically, the additive salts of oxidized bases and components of condensation used in the present invention, are selected, in particular, among the additive salts with an acid, such as hydrochloride, hydrobromide, sulphates, citrates, succinate, tartratami, lactates, (C1-C4)-alkyl sulphonates, tozilaty, bansilalpet, phosphates and acetates, and additive salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

Appropriate for dyeing medium, also called the media of paint, is a cosmetic medium generally formed by water or mixture of water and at least one organic solvent to solubilize the compounds which s, which are sufficiently soluble in water. As the organic solvent include, for example, lower alkanols with 1 to 4 carbon atoms, such as ethanol and isopropanol; polyols and ethers of polyols such as 2-butoxyethanol, propylene glycol, simple onomatology ether of propylene glycol, a simple monotropy ether and simple onomatology ether of diethylene glycol, and aromatic alcohols like benzyl alcohol or Phenoxyethanol, and mixtures thereof.

The solvents are preferably in quantities of components, preferably, from about 1 to 40 wt.%, with respect to the total mass of the ink composition, and more preferably, from about 5 to 30 wt.%.

The ink composition according to the invention may also include various additives commonly used in compositions for dyeing hair, such as anionic, cationogenic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof; anionic, cationic, nonionic, amphoteric, zwitterionic polymers or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners; antioxidants; penetration agents; complexing agents; fragrances; buffers; dispersing components; components with a conditioning effect, so is e, as, for example, volatile or non-volatile, modified or unmodified silicones; film-forming components; ceramides; preservatives; opalescent components.

The above additives are usually present in amount comprising for each of them, from 0.01 to 20 wt.%, in relation to the mass of the ink composition.

Of course, the specialist must choose the optional additional compound or these possible additional compounds so that not deteriorated, or not significantly deteriorated due to foreseen or provided for additives useful properties inherent in the composition for oxidative dyeing according to the present invention.

The pH value of the ink composition according to the invention is usually from about 3 to 12 and preferably from about 5 to 11. It can be brought to the desired value using acidifying or alkalizing agents normally used in the dyeing of keratin fibers, or else using a classic buffer systems.

Of acidifying agents include, as an example, inorganic or organic acids as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids, as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

From Podlachia the x agents can be called, as an example, ammonia, carbonates of alkali metals, alkanolamines, such as mono-, di - and triethanolamines and derivatives thereof, sodium hydroxide or potassium hydroxide and the compounds of following formula (IV):

in which W stands for propylene residue, possibly substituted by a hydroxyl group or an alkyl radical with 1-4 carbon atoms; Ra, Rb, Rcand Rdidentical or different, denote a hydrogen atom, an alkyl radical with 1-4 carbon atoms or hydroxyalkyl with 1-4 carbon atoms.

The ink composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other appropriate form for the implementation of colouring keratin fibres and in particular human hair.

Proposed in the present invention the method is a method whereby the fibers cause the composition according to the present invention, such as the above, and show the component condensation using an oxidizer. Component condensation can be revealed at acidic, neutral or alkaline pH and the oxidizing agent may be added to compositions according to the invention just at the time of use or it can be used from the containing oxidizing composition applied simultaneously, the sludge is in series with the composition according to the invention. Preferably the color seen at a neutral pH value.

According to a special variant of the implementation of the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in an appropriate for dyeing medium, at least one oxidizing agent, this oxidizing agent is sufficient for the manifestation of color. The resulting mixture is then applied to the keratin fibers. After keeping for a time from about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.

Oxidizing agents typically used for the oxidative dyeing of keratin fibers, are, for example, hydrogen peroxide, urea peroxide, bromates, alkali metal, Persol, such as perborates and persulfates, nagkalat and oxidase enzymes, which can be called peroxidase, oxidoreductase with 2 electrons, such as uricase, and oxygenate with 4 electrons, as laccase. Especially preferred is hydrogen peroxide.

The oxidizing composition may also include various additives commonly used in compositions for dyeing hair, and such as mentioned above.

The pH of the oxidizing composition comprising the oxidizing agent is such that after the messenia with the ink composition, the pH of the resulting composition, applied to the keratin fibers preferably varies in the range of about 3 to 12, and more preferably, from 5 to 11. The pH value can be increased to the desired value using acidifying or alkalizing agents commonly used in dyeing keratin fibers such as the above.

Ready-to-use composition that is ultimately applied to the keratin fibers may be in various forms, such as in the form of liquids, creams, gels, or in any other appropriate form for the implementation of colouring keratin fibres and in particular human hair.

The object of the present invention is also a device with multiple branches, or "kit" for dyeing, in which the first part includes the ink composition according to the present invention, the above, with the exception of the oxidant, and the second compartment comprises an oxidizing composition. This device can be equipped with a device that allows you to apply to the hair the desired mixture, such as the devices described in French patent 2586913 on the applicant's name.

The object of the present invention is also used for the oxidation dyeing of keratin fibres, and in particular human keratin fibres such as the hair, of a composition such as that indicated the data above.

According to a special variant of implementation, the use of compositions according to the invention in the case of grey hair with 90% natural or subjected to a permanent colouring grey hair allows you to achieve a painting which, according to the rating system CIELab, the value of L*, less than or equal to 50, the value of a*above or equal to 20, preferably higher than or equal to 25, even more preferably comprising from 25 to 50, the value of b*, is higher or equal to 20, preferably higher than or equal to 25, even more preferably comprising from 25 to 50, and the ratio b*/a*constituting from 0.5 to 1.5, preferably from 0.7 to 1.2.

The following examples serve to illustrate the invention but are not restrictive.

EXAMPLES

Example 1

Get the following composition 1:

intenationa salt diethylenetriaminepentaacetic acid, in the form of an aqueous 40%solution2 g
20%aqueous solution of ammonia12 g
metabisulphite sodium in powder form0.71 g
monoethanolamine, net2,02 g
pyrogenic silica with a hydrophobic what harakterom 1.2 g
2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]-pyrazole-1-it, 2 CH3SO3H1.9 grams
5-amino-2-METHYLPHENOL0.2 g

titanium dioxide (raw anatase), coated from dimethylsiloxane (98:2)0.15 g
6-chloro-2-methyl-5-aminophenol, peeled0.8 g
p-aminophenol0.1 g
picoliter2 g
mica with titanium dioxide and ferrous brown (58:37,5:4,5)0.5 g
perfume0.5 g
polycondensate of tetramethylethylenediamine and 1,3-dichloropropylene in aqueous solution3 g
polydimethyldiallylammonium, in the form of a 40%aqueous solution, unstabilized5 g
carboxyvinyl polymer synthesized in a mixture of ethyl acetate and hexane 0.6 g
deionized watera 24.57 g
propylene glycol7 g
natural lauric acid3 g
acetyltyrosine (12 ethyleneoxide units) lauric alcohol7 g
acetyltyrosine (3 ethyleneoxide units) decroly alcohol10 g
cetylstearyl alcohol (C16-18 50/50) (synthetic origin)11.5g
acetyltyrosine (30 ethyleneoxide units) ileocecectomy alcohol4 g
vitamin C: L-ascorbic acid in the form of fine powder0.25 g

At the time of use 1 wt. part of the composition 1 is mixed with 1.5 wt. parts of hydrogen peroxide solution with a concentration of 25 volumes at pH of 2.2. Get the final value of pH of 9.6.

The resulting mixture was applied to locks of grey hair with 90% natural or subjected to a permanent colouring grey hair. After incubation for 20 minutes at room temperature, the strands are rinsed, washed with a standard is on shampoo, again, rinsed, then dried.

The hair coloring is assessed visually. Get bright blond copper hue.

Hair color is determined with the aid of spectrocolorimeter MINOLTA CM 2002®(light source D65-10oCSI) in the CIELab system. In this system, L* denotes brightness, a* means the tone and b* indicates saturation.

The obtained results are presented in the following table.

Hair typeL*a*b*
Natural gray hair44,831,334,1
Subjected to a permanent coloring gray hair38,135,529,4

1. Composition for dyeing keratin fibers, comprising, in an appropriate environment:
at least a first oxidizing the basis chosen among the 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole-1-it and its additive salts;
at least the first component condensation, choose among 6-chloro-2-methyl-5-aminophenol and its additive salts; and
at least the second component condensation, choose among the replaced m-Amini is NOlow the following formula (II) and their additive salts:

in which R1and R2identical or different, denote a hydrogen atom; an alkyl radical; monohydrocalcite radical; polyhydroxyalkane radical; monolingually radical; or
R1and R2with each other and with the nitrogen atom to which they are attached, form a cyclic group containing one or more heteroatoms, with 5-7 members in the loop, saturated or unsaturated, unsubstituted or substituted by one or more radicals selected among carboxyl, carboxamido, hydroxyl, amino, mono - or dialkylamino, alkyl, possibly substituted by one or more hydroxyl radicals, amino groups, mono - or dialkylaminoalkyl;
R3denote, independently of each other a halogen atom; an alkyl radical; CNS radical; monohydrocalcite radical; polyhydroxyalkane radical; monohydroxylation radical; polyhydroxyalkanoates radical;
n means an integer from 0 to 4;
provided that:
when n is 0, then at least one of the radicals R1and R2is different from a hydrogen atom;
when n is 2, and the radicals R3denote methyl or a chlorine atom, respectively, in positions 2 and 6, then R1and R2at the same time do not represent a hydrogen atom;
having in mind that modernisaton first oxidizing the base/first component condensation is below 1.5, the molar ratio of the first oxidizing the base/the second component of condensation is greater than 1, and the molar quantity of the first oxidizing the base above or equal to 2.5·10-3mol per 100 g of composition.

2. The composition according to claim 1, in which R1and R2signify, independently from each other, a hydrogen atom; an alkyl radical such as methyl or ethyl; monohydrocalcite radical such as β-hydroxyethyl or γ-hydroxypropyl; or R1and R2with each other and with the nitrogen atom to which they are bound, form a cycle selected among pyrolidine, piperidino, homopiperazine, pieperazinove, homopiperazine, morpholino heterocycles; and the above cycles may be substituted by one or more hydroxyl radicals, amino groups, mono - or di-(C1-C2-alkylaminocarbonyl, carboxyl radicals, carboxamidotryptamine, (C1-C4)-alkyl radical, possibly substituted by one or more hydroxyl radicals, amino groups, mono - or di-(C1-C2-alkylaminocarbonyl.

3. The composition according to claim 1, in which R3choose among a halogen atom, alkyl radical, CNS radical, monohydroxylation radical.

4. Composition according to any one of claims 1 to 3, in which n denotes 0 to 2.

5. Composition according to any one of the claim 1 to 3, in which the substituted m-aminophenol or substituted m-aminophenol of the formula (II) choose among 5-amino-2-methoxyphenol; 5-amino-2-(β-hydroxyethyloxy)phenol; 5-amino-2-METHYLPHENOL; 5-N-(β-hydroxyethyl)amino-2-METHYLPHENOL; 5-N-(β-hydroxyethyl)amino-4-methoxy-2-METHYLPHENOL; 5-amino-4-methoxy-2-METHYLPHENOL; 5-amino-4-chloro-2-METHYLPHENOL; 5-amino-2,4-dimethoxyphenol; 5-(γ-hydroxypropylamino)-2-METHYLPHENOL; 3-dimethylaminophenol; 2-methyl-5-dimethylaminophenol; 2-ethyl-5-dimethylaminophenol; 2-methoxy-5-dimethylaminophenol; 2 ethoxy-5-dimethylaminophenol; 2-(β-hydroxyethyl)-5-dimethylaminophenol; 3-diethylaminophenol; 2-methyl-5-diethylaminophenol; 2-ethyl-5-diethylaminophenol; 2-methoxy-5-diethylaminophenol; 2 ethoxy-5-diethylaminophenol; 2-(β-hydroxyethyl)-5-diethylaminophenol; 3-di-(β-hydroxyethyl)aminophenol; 2-methyl-5-di-(β-hydroxyethyl)aminophenol; 2-ethyl-5-di(β-hydroxyethyl)aminophenol; 2-methoxy-5-di-(β-hydroxyethyl)aminophenol; 2-ethoxy-5-di-(β-hydroxyethyl)aminophenol; 2-(β-hydroxyethyl)-5-di(β-hydroxyethyl)aminophenol; 3-pyrrolidin-1-kilfenora; 2-methyl-5-pyrrolidin-1-kilfenora; 2-ethyl-5-pyrrolidin-1-kilfenora; 2-methoxy-5-pyrrolidin-1-kilfenora; 2 ethoxy-5-pyrrolidin-1-kilfenora; 2-(β-hydroxyethyl)-5-pyrrolidin-1-kilfenora; 3-piperidine-1-kilfenora; 2-methyl-5-piperidine-1-kilfenora; 2-ethyl-5-piperidine-1-kilfenora; 2-methoxy-5-piperidine-1-kilfenora; 2 ethoxy-5-piperidine-1-kilfenora; 2-(β-is hydroxyethyl)-5-piperidine-1-kilfenora; 3-piperazine-1-kilfenora; 2-methyl-5-piperazine-1-kilfenora; 2-ethyl-5-piperazine-1-kilfenora; 2-methoxy-5-piperazine-1-kilfenora; 2 ethoxy-5-piperazine-1-kilfenora; 2-(β-hydroxyethyl)-5-piperazine-1-kilfenora; 3-(4-methylpiperazin-1-yl)phenol; 2-methyl-5-(4-methylpiperazin-1-yl)phenol; 2-ethyl-5-(4-methylpiperazin-1-yl)phenol; 2-methoxy-5-(4-methylpiperazin-1-yl)phenol; 2-ethoxy-5-(4-methylpiperazin-1-yl)phenol; 2-(β-hydroxyethyl)-5-(4-methylpiperazin-1-yl)phenol; 3-(4-ethylpiperazin-1-yl)phenol; 2-methyl-5-(4-ethylpiperazin-1-yl)phenol; 2-ethyl-5-(4-ethylpiperazin-1-yl)phenol; 2-methoxy-5-(4-ethylpiperazin-1-yl)phenol; 2-ethoxy-5-(4-ethylpiperazin-1-yl)phenol; 2-(β-hydroxyethyl)-5-(4-ethylpiperazin-1-yl)phenol; 3-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-methyl-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-ethyl-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-methoxy-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-ethoxy-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 2-(β-hydroxyethyl)-5-(4-(β-hydroxyethyl)piperazine-1-yl)phenol; 3-morpholine-4-kilfenora; 2-methyl-5-morpholine-4-kilfenora; 2-ethyl-5-morpholine-4-kilfenora; 2-methoxy-5-morpholine-4-kilfenora; 2 ethoxy-5-morpholine-4-kilfenora; 2-(β-hydroxyethyl)-5-morpholine-4-kilfenora.

6. The composition according to claim 5, in which the substituted m-aminophenol or substituted m-aminophenol of the formula (II) choose among 5-N-(β-hydroxyethylamino)-2-METHYLPHENOL and 5-amino-2-METHYLPHENOL.

7. Composition according to any one of claims 1 to 3, the sludge is 6, in which the molar ratio of the first oxidizing the base/first component condensation is from 0.5 to 1.2.

8. Composition according to any one of claims 1 to 3 or 6, in which the molar ratio of the first oxidizing the base/the second component condensation is from 2 to 5.

9. Composition according to any one of claims 1 to 3 or 6, comprising at least a second oxidizing basis, choose among the para-aminophenols.

10. The composition according to claim 9, in which p-aminophenol or p-aminophenols is chosen among the compounds corresponding to the following formula (III), and their additive salts:

in which R4means a hydrogen atom; a halogen atom; an alkyl radical; monohydrocalcite radical; alkoxyalkyl radical; aminoalkyl radical; hydroxyethylaminomethyl radical;
R5means a hydrogen atom; a halogen atom; an alkyl radical; monohydrocalcite radical; polyhydroxyalkane radical; aminoalkyl radical; cyanoaniline radical; alkoxyalkyl radical;
having in mind that at least one of the radicals R4or R5means a hydrogen atom.

11. The composition according to claim 10, in which p-aminophenol or p-aminophenols of formula (III) is selected among p-aminophenol, 4-amino-3-METHYLPHENOL, 4-amino-3-terfenol; 4-amino-3-hydroxymethylene, 4-amino-2-METHYLPHENOL, 4-amino-2-hydroxymethyl who Enola, 4-amino-2-methoxymethanol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethylaminomethyl)phenol, 4-amino-2-terfenol.

12. Composition according to any one of claims 1 to 3, 6, 10 or 11 comprising, in addition, the oxidizer.

13. Method of coloring keratin fibers, characterized in that a composition, such as shown in any one of claims 1-11, applied to the keratin fibers in the presence of an oxidizing agent for a time sufficient for the manifestation of the desired color.

14. A device with several compartments, in which a first compartment contains the ink composition, such as shown in any one of claims 1 to 11, and the second compartment contains the oxidizing agent.

15. Use for oxidation dyeing keratin fibers a composition, such as shown in any one of claims 1 to 12.

16. Use 15 to achieve the colouring grey hair with 90% natural or subjected to a permanent colouring grey hair which, according to the rating system CIELAB, the value of L*, less than or equal to 50, the value of a*above or equal to 20, the value of b*, is higher or equal to 20, and the ratio b*/a*comprising from 0.5 to 1.5.



 

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SUBSTANCE: invention concerns a composition for ceratic fibre colouring, including colouring of human hair. The composition includes at least one diamino-N,N-dihydropyrizolone derivative as an oxidised base. Also the invention describes a method of keratic fibre colouring with application of the said composition, amino-N,N-dihydropyrizolone derivatives or one of its additive salts, diamino-N,N-dihydropyrizolone derivatives or one of its additive salts, and a method of thir obtaining.

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