CZ205999A3 - Oxidant and its use for dyeing, permanent modeling or for decoloring of keratin fibers - Google Patents

Abstract

Cosmetic agent for keratin fiber treatment containing in a carrier suitable for keratin fibers (a) at least one enzyme with 2 electrons of an oxidoreductase type v the presence of at least one donor for said enzyme; M at least one aminosilicon; and a method of treating keratin fibers, in particular dyeing processes, permanent modeling or bleaching using this composition.

Description

Oxidizing agent and its use, for permanent modeling or for decolorizing keratin fibers

Technical field

BACKGROUND OF THE INVENTION The present invention relates to an oxidizing agent for the treatment of keratin fibers, comprising at least one oxidizeductase enzyme with two electrons in the presence of at least one donor for said enzyme and at least one aminosilicone, as well as its use for dyeing, permanently modeling or bleaching keratin fibers. . BACKGROUND OF THE INVENTION

It is known to dye keratin fibers, and in particular human hair, with dyeing compositions containing oxidative dye precursors, in particular p-phenylenediamines, o- or p-aminophenols and heterocyclic bases, which are commonly referred to as oxidation bases. Oxidative dye precursors or oxidation bases are weakly colored compounds which, in combination with oxidation products, can increase the color of the compounds and dyes by oxidative condensation.

It is also known that the shades obtained by these oxidation bases can be varied by combining them with coupling agents or modifiers, the modifiers being selected in particular from aromatic m-diamines, m-aminophenols and certain heterocyclic compounds.

The variety of compounds used as oxidizing bases and as coupling agents allows a wide range of colors to be obtained.

In addition, the so-called "permanent" coloration achieved by the use of these oxidative dyes must satisfy some other requirements. It must not have any toxic disadvantages, it must be able to deliver shades of the desired intensity and must be resistant to external influences (light, bad weather, washing, permanent waving, sweating, wiping).

The dyes must also be able to include white hair and, finally, be as selective as possible, in other words they must provide the smallest possible color differences along the length of keratin fibers, which may in fact be of different sensitivity (eg damaged) between root and tail.

The oxidative dyeing of keratin fibers is usually carried out in an alkaline environment in the presence of hydrogen peroxide. However, the use of an alkaline medium in the presence of hydrogen peroxide has the significant disadvantage of considerable damage to the fibers as well as a considerable discoloration of keratin fibers, which is not always desirable.

Oxidative dyeing of keratin fibers can also be performed using oxidation systems other than hydrogen peroxide, such as enzyme systems. Thus, it has already been proposed to dye keratin fibers, particularly in patent application EP-A-0 310 675 with compositions comprising oxidative dye precursors in combination with enzymes such as pyranose oxidase, glucose oxidase or uricase, in the presence of a donor for said enzymes. Although used under conditions which do not lead to degradation of keratin fibers comparable to the degradation caused by the dye used in the presence of hydrogen peroxide, these color formulations result in a coloration which is insufficient both in terms of homogeneity of color distributed along the fiber (harmony) in terms of color (brightness), color intensity and resistance to various aggressive factors to which hair may be exposed.

• 9 • 9 • 9 • 9 • 9 • 9 • 9 • 9 • 9

9 9 99

It is known that most conventional techniques for obtaining permanent modeling consist in the first step of opening keratin -SS-disulfide (cysteine) bonds using a composition comprising a suitable reducing agent (reducing step), followed by rinsing such treated hair by reconstitution in the second step. disulfide bonds, apply an oxidizing agent (an oxidation stage, also known as a fixation stage) to hair that has been previously stretched (curlers, etc.) so that hair of the desired shape is finally obtained. This technique makes it equally either to achieve curled hair or straighten it after curling. The new shape given to the hair by chemical treatment as mentioned above has a considerably longer shelf life and is particularly resistant to shampooing with water, compared to simple standard techniques for temporary modeling, such as water waving.

The reducing agents that can be used to perform the first stage of hair styling permanently comprise, as reducing agents, sulfites, bisulfites, alkylphosphines or preferably thiols. As thiols, cysteine and its various derivatives, cysteamine and its derivatives, thiol acetic acid or thiol glycolic acid, their salts and esters, in particular glyceryl thioglycolate, are usually used.

With regard to the oxidizing agents required to perform the fixation step, in practice compositions based on aqueous hydrogen peroxide, sodium bromate or persalts such as perborate, which have the disadvantages of hair damage, are commonly used.

A problem with permanent waving techniques known to date is that its application to the hair induces long-term adverse changes in hair quality. The underlying causes of these adverse changes in hair quality are a reduction in their cosmetic properties such as shine and their feel and degradation of their mechanical properties, in particular degradation of mechanical strength due to swelling of keratin fibers during rinsing between the reduction stage and the oxidation stage, their porosity. Hair becomes thin and becomes brittle during subsequent treatment, for example, by blow drying.

The same problem of adverse changes in keratin fibers is encountered in hair bleaching processes.

It is known that permanent modeling or bleaching of keratin fibers can also be performed under milder conditions, using oxidation systems other than hydrogen peroxide, such as enzyme systems. Processes for the permanent waving or bleaching of keratin fibers have already been proposed, in particular in patent application EP-A-0 310 675, compositions comprising an enzyme such as pyranose oxidase, glucose oxidase or uricase in the presence of a donor for said enzyme. Although used under conditions which do not lead to degradation of keratin fibers comparable to degradation caused by conventional crimping or bleaching processes, these oxidation formulations nevertheless produce results that are still inadequate as to the compatibility of curly or bleached hair with subsequent treatment, and as regards the degradation of the mechanical properties of the permanent curly hair, in particular the reduction of the porosity of the hair and the reduction of the cosmetic properties, such as the touch, or alternatively in terms of uniformity of discoloration along the keratin fibers.

The present invention is intended to solve the above problems.

• • •

SUMMARY OF THE INVENTION

Surprisingly, the Applicant has discovered novel compositions comprising as oxidation system at least one oxidoreductase enzyme having 2 electrons in the presence of at least one donor for said enzyme and at least one aminosilicone which may form, in the presence of oxidizing bases and optionally coupling agents, a ready-to-use formulation which they lead to more homogeneous, intense and colored dyes without increasing degradation of keratin fibers, these dyes being relatively non-selective and showing good resistance to the various aggressive factors to which the hair may be exposed.

The Applicant has further unexpectedly discovered that the use of an oxidizing agent comprising, as an oxidation system, at least one 2-electron oxidoreductase enzyme in the presence of at least one donor for said enzyme and at least one aminosilicone for permanent modeling of keratin fibers represents a possible solution to the problem. In particular, this type of oxidizer improves the durability of the curl over time, substantially reduces the porosity of the permanently formed hair and improves the compatibility of the permanently waved hair with respect to subsequent treatment.

The Applicant has further unexpectedly discovered that the use of an oxidizing agent comprising, as an oxidation system, at least one 2-electron oxidoreductase enzyme in the presence of at least one donor for said enzyme and at least one aminosilicone to decolorize keratin fibers presents a possible solution to the problem. hair with regard to subsequent treatment. This type of oxidizing agent provides a more uniform bleaching effect on the hair and improves cosmetic properties such as touch.

These findings form the basis of the present invention.

The object of the present invention is firstly a cosmetic and / or dermatological composition intended for the treatment of keratin fibers, in particular human keratin fibers and in particular human hair, comprising on a carrier which is suitable for keratin fibers:

(a) at least one 2-electron oxidoreductase enzyme in the presence of at least one donor for said enzyme, (b) at least one aminosilicon.

The 2-electron oxidoreductases used in the oxidizing compositions of the present invention are particularly selected from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases and uricases.

According to the present invention, the dual electron oxidoreductase is preferably selected from uricases of animal, microbiological or biotechnological origin.

Examples include uricase extracted from male liver, uricase from Arthrobacter globiformis, as well as uricase from Aspergillus flavus.

The 2-electron oxidoreductase may be used in crystalline form or in a form diluted in a diluent which is inert with respect to said 2-electron oxidoreductase.

The 2-electron oxidoreductase according to the invention preferably constitutes 0.01 to 20 wt. % to the total weight of the composition, more preferably 0.1 to 5 wt. to this weight.

The term "donor" according to the invention is to be understood in relation to various substrates also necessary for the function of said 2-electron oxireductases. The nature of the donor (or substrate) for said enzyme varies depending on the nature of the 2 electron oxidoreductase used.

For example, D-glucose, L-sorbose and D-xylose are mentioned as donors for pyranose oxidases; D-glucose is mentioned as a donor for glucose oxidases; glycerol oxidase donors include glycerol and dihydroxyacetone; lactic acid oxidase donors include lactic acid and its salts; pyruvate oxidase donors include pyruvic acid and salts thereof; and finally, uricase donors include uric acid and salts thereof.

The donors (or substrates) used according to the invention preferably represent 0.01 to 20 wt. % to the total weight of the composition according to the invention, more preferably 0.1 to 5 wt. to this weight.

According to the invention, the term "aminosilicone" is to be understood as any silicone containing at least one primary, secondary or tertiary amine or quaternary ammonium group. It is stated:

(a) the polysiloxanes listed in the CTFA dictionary as "amiodimethicone" and corresponding to formula 1:

HIM

Γ ³ OH 1 O JL 1 '0 Si CH ₃ (CH3) ₃ -. X 1

NH (CH _{2) i}

NHj

Jv (1) wherein x and y are integers dependent on molecular weight, usually such that said molecular weight is between 5000 and 500000;

(b) cationic silicone polymers corresponding to the formula:

R _and G ₃ . _and -Si (OSiG ₂ ), _1- (OSiG _b R ₂ , _b ) _m -O-SiG ₃ . _and -R _and (II) wherein:

G is hydrogen or phenyl, OH or C 1 -C 8 alkyl, for example methyl, ethyl, and is 0 or an integer of 1 to 3, especially 0, b is 0 or 1, especially 1, and m are numbers such that the sum (n + m) ranges from 1 to 2000, and in particular from 50 to 150, wherein n may range from 0 to 1999, and in particular from 49 to 149, wherein m may range from 1 to 2000, particularly from 1 to 10;

R is a monovalent radical of formula -C _q H _2q L, wherein is a number from 2 to 8 and L is an optionally quaternized group selected from:

-N (R ') -CH ₂ -CH ₂ -N (R') ₂

-N (R ') ₂

-N * (R ') ₃ A'

-N '(R') ₂ (H) A '

-N ⁺ (R ') (H) 2A-N (R') -CH 2 -CH 2 -N ⁺ (R ') (H) 2A';

wherein R 'denotes hydrogen, phenyl, benzyl or a monovalent hydrocarbon radical, for example an alkyl radical of 1 to 20 atoms, and A' denotes a halide ion such as fluoride, chloride, bromide or iodide.

The product corresponding to this definition is a polymer known as "trimethylsilylamodimethicone" corresponding to formula III below:

CH (CH3) ₃ SÍOSiOI

CH, ^H '

SiOI

P

CHCH,

I ch ₂

NH

AND

P

CH,

AND

NH,

-Si (CA,)

3'3 (III) wherein n and m are as defined above for formula II. Such polymers are described, for example, in patent application EP-A-95238.

(c) cationic silicone polymers corresponding to the formula:

© O

R 1 —CH ₂ —CHOH-CH ₂ -N (R 1) ₃ Q ^-R 1n * 1

R— Si j

R

Si-O

Si-O

Si-R, (IV) wherein

R 1 represents a monovalent hydrocarbon radical having 1 to 18 carbon atoms, in particular a C ₁ -C 18 alkyl radical or a C ₂ -C ₁₈ alkenyl radical, for example methyl;

R ₂ is a divalent hydrocarbon radical, in particular Ci-Cu or CjCis alkylene radical, such as C, C ₈ divalent alkyleneoxy radical;

Q 1 is a halide ion, especially chloride;

r represents an average statistical value of from 2 to 20, in particular from 2 to 8;

s means an average statistical value of from 20 to 200, and in particular from 20 to 50.

These polymers are described in more detail in U.S. Patent 4,185,087.

One polymer in this class is the polymer sold by Union Carbide under the trade name "Ucar Silicone ALE 56".

When these silicone polymers are used, their use together with cationic and / or nonionic surfactants is particularly preferred.

For example, a product sold under the name "Cationic Emulsion DC 929" by Dow Corning may be used, which includes, in addition to amodimethicone, a cationic surfactant containing a mixture of products corresponding to the formula:

CH,

R3CH,

Cl

CH, wherein R 3 is an alkenyl and / or C 14 -C 22 alkyl radical derived from tallow fatty acids known under the CTFA name "talowtrimonium chloride", in combination with a nonionic surfactant of the formula: C 9 H 19 -C 6 H 4 known as "Nonoxynol 10".

The use may also be for instance the product sold under the name "Cationic Emulsion DC 939" by Dow Corning, which comprises, besides amodimethicone cationic surfactant which is trimethylcetylamoniumchlorid, in combination with a nonionic surfactant of formula Ci3H27- (OC2 4 ₁₎ and ₂ -OH, known by the CTFA as "trideceth-12".

Another commercial product that can be used in accordance with the invention is the product sold under the name "Dow Corning Q2 7224" by Dow Corning, containing in combination the trimethylsilylamodimethicone of formula III described above, a nonionic surfactant of the formula: known under the CTFA name "octoxynol-40", the second nonionic surfactant of the formula. C ₁₂ H _{25 -} (OCH ₂ -CH ₂ ) 6 -OH, known under the CTFA name "isolaureth-6" and propylene glycol.

The compositions of the invention comprise the aminosilicones defined above in an amount by weight which is between 0.05% and 10%, preferably between 0.1% and 5%, and even more preferably between 0.2% and 3%, based on the total weight of the composition.

The present invention also relates to a composition for direct use in the oxidative dyeing of keratin fibers, in particular human keratin fibers such as hair, comprising, in a medium suitable for dyeing, at least one oxidizing base and, where appropriate, one or more coupling agents characterized by: by including:

(a) at least one 2-electron oxidoreducase type enzyme in the presence of at least one donor for said enzyme, (b) at least one aminosilicone.

The nature of the oxidation bases used in the ready-to-use dye is not a critical factor. They may in particular be selected from p-phenylenediamines, double bases, p-aminophenols, 0-aminophenols and heterocyclic oxidation bases.

• · '99 - ·· ♦ ··. · V,: ·. · ··.

• 9 ..... 9 - 9 9 •··

9 9 9 9 9

9 9 9 9 9 9 9 9 9

Among the p-phenylenediamines which can be used as oxidizing bases in the dye compositions according to the invention, the following are mentioned in particular:

where

- R4 is hydrogen, C1 -C4 alkyl, C1 -C4 monohydroxyalkyl, C2 -C4 polyhydroxyalkyl radical, _(Ci-C4) alkoxy (Ci-C4) alkyl, C1-C4 alkyl group substituted with a nitrogenous group, a phenyl group or a 4'aminophenyl group;

-R ₅ is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, (C 1 -C ₄ ) alkoxy (C 1 -C ₄ ) alkyl, C 1 -C 4 alkyl substituted with nitrogen;

- R 5 represents a hydrogen atom, a halogen atom such as a chlorine atom, a bromine atom, an iodine or a fluorine atom, a C 1 -C ₄ alkyl group, a C 1 -C 4 monohydroxyalkyl group, a C 1 -C 4 hydroxyalkoxy group, acetylamino (C 1 -C ₄ ) alkoxy a C 1 -C ₄ mesylaminoalkoxy group or a carbamoylamino (C 1 -C ₄ ) alkoxy group,

-R 7 represents a hydrogen atom or a halogen atom or a C 1 -C ₄ alkyl group.

Of the nitrogenous groups of formula V above include in particular the amino, mono _(Ci-4) alkylamino, di _(Ci-4) alkylamino, tri _(Ci-4) alkylamino, monohydroxy _(Ci-4) alkylamino, imidazolinium and ammonium groups .

Among the p-phenylenediamines of formula (V) above, mention may be made in particular of p-phenylenediamine, polyylenediamine, 2-chloro-p-phenylenediamine, 2,3-di-ethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6 -diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-N , N-diethyl-3-methylaniline, N, N-bis (3-hydroxyethyl) -p-phenylenediamine, 4-amino-N, N-bis (phydroxyethyl) -2-methylaniline, 4-amino-2-chloro-N , N-bis (p-hydroxyethyl) aniline, 2-β-hydroxyethyl-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, Ν- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p -phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl-p-hydroxyethyl) -p-phenylenediamine, Ν- (β, γ-dihydroxypropyl-p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-phenylenediamine, 2-p-hydroxyethyloxy-p-phenylenediamine, 2-p-acetylaminoethyloxy-phenylenediamine and N- (p-methoxyethyl) -p-phenylenediamine and their acid addition salts .

Among the p-phenylenediamines of the general formula V above, p-phenylenediamine, ptoluylenediamine, 2-isopropyl-p-phenylenediamine, 2-β-hydroxyethyl-p-phenylenediamine, 2-β-hydroxyethyloxy-p-phenylenediamine, 2,6 -dimethyl-p-phenylenediamine, 2,6-diethyl-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, N, N-bis (p-hydroxyethyl) -p-phenylenediamine, 2-

Chloro-p-phenylenediamine and 2-β-acetylaminethyloxy-p-phenylenediamine and their acid addition salts.

The term double base according to the invention is to be understood as referring to compounds containing at least two aromatic rings bearing amino and / or hydroxyl groups.

Among the double bases which are used as oxidizing bases in the dye compositions of the invention, mention may be made in particular of the compounds corresponding to formula VI below and their acid addition salts.

(VI) where:

Z ₁ and Z ₂ , which may be the same or different, represent a hydroxyl or -NH ₂ group, which may be substituted by a C 1 -C 4 alkyl radical or a Y-bonding bridge;

- the bonding bridge Y is a linear or branched alkylene chain having 1 to 14 carbon atoms which may be interrupted or terminated by one or more nitrogen groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and optionally substituted by one or more hydroxyls or C 1 -C 6 alkoxy radicals.

-R 8 and R 9 represent a hydrogen atom or a halogen atom, a C 1 -C 4 alkyl radical, a C 1 -C 4 monohydroxyalkyl radical, a C ₂ -C 4 polyhydroxyalkyl radical, a C 1 -C 4 aminoalkyl radical or a bonding bridge of Y;

R 10, R 11, R 12, R 13, R 14 and R 16, which may be the same or different, represent a hydrogen atom, a Y-bonding bridge or a C 1 -C 4 alkyl radical;

it being understood that the compound of formula VI contains only one Y-linker bridge per molecule.

Among the nitrogen groups of the general formula VI above, mention may be made in particular of amino, mono (C 1 -C 4) alkylamino, di (C 1 -C 4) alkylamino, tri (C 1 -C 4) alkylamino, monohydroxy (C 1 -C 4) alkylamino, imidazolinium and ammonium residues.

Among the double bases of formula VI above, mention may be made in particular of N, N'-bis (3-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, N, N'-bis (P- N, N'-bis (4-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (Phydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N , N'-bis (4methylaminofenyljtetramethylendiamin, N, ^N'-bis (ethyl) -N, N'-bis (4'-amino-3 methylfenyljethylendiamin al, 8-bis (2,5-diaminophenoxy) -3,5-dioxaoctane and acid addition salts thereof.

Flfl fl fll fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl fl Fl Fl

N, N'-bis (3-hydroxyethyl) -N, N'bis (4'-aminophenyl) -1,3-diaminopropanol and 1,8-bis (2,5-diaminophenoxy) - 3,5-dioxaoctane or an acid addition salt thereof.

Among the p-aminophenols which can be used as oxidizing bases in the dye compositions according to the invention, the compounds corresponding to the general formula (VII) below are mentioned in particular. and their acid addition salts:

where:

-Ri6 represents a hydrogen or halogen atom or a C1 -C4 alkyl, C1 -C4 monohydroxyalkyl, (C, -C4) alkoxy (C, -C4) alkyl, C1-C4 aminoalkyl or hydroxy _(Ci-C4) alkylamino- (C, -C4) alkyl residue,

-R 17 represents a hydrogen or halogen atom or 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 (C 1 -C 4) alkoxy (C 1 -C 4) alkyl radical, and is to be taken provided that at least one of R 16 or R 17 is hydrogen.

Among the p-aminophenols of formula VII above, mention may be made in particular of p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol,

4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (O-hydroxyethylaminoiminomethyl) phenol and 4-amino-2-fluorophenol and their acid addition salts.

Among the o-aminophenols which can be used as oxidizing bases in the dye compositions according to the invention, mention may be made in particular of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and

5-acetamido-2-aminotenol and their acid addition salt.

Among the heterocyclic bases which can be used as oxidation bases in the dye compositions according to the invention, mention may be made in particular of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and pyrazolopyrimidine derivatives and their acid addition salts.

Among the pyridine derivatives, mention may be made in particular of the compounds described, for example, in GB patents

And GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3aminopyridine, 2,3-diamino-6-methoxypyridine, 2- (p-methoxyethyl) amino-3-amino- 6-methoxypyridine and 3,4-diaminopyridine, and acid addition salts thereof.

Among the pyrimidine derivatives, mention may be made in particular of the compounds described, for example, in DE

359,399 or Japanese application JP 88-169,571 or WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5 , 6 ······················

Triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine and their acid addition salts.

Among the pyrazole derivatives, mention is made in particular of the compounds described in patents DE 3,843,892, DE 4,133,957 and in 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-pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3 -methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5 hydrazinopyrazole, 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- (p-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-hydroxymethylpyrazole, 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'-aminoethyl) amino-1,3-dimethylpyrazole,

3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (P-hydroxyethyl) amino-1-methylpyrazole and acid addition salts thereof.

Among the pyrazolopyrimidine derivatives, mention may be made in particular of the pyrazolo [1,5-a] pyrimidines of the general formula VIII below, and their acid or base addition salts and their tautomeric forms, if a tautomeric equilibrium exists:

N ⁵ y

Mn i ^{NR a R} , ₉ lp [NR ₂₀ R ₂₁ ] _q (VIII) where:

- R 18, R 19, R 20 and R 21, which may be the same or different, represent a hydrogen atom, a C 1 -C 4 alkyl radical, an aryl radical, a C 1 -C 4 hydroxyalkyl radical, a C 2 -C 4 polyhydroxyalkyl radical, (C 1 -C ₄ ) alkoxy ( C 1 -C ₄ ) alkyl radical, C 1 -C 4 aminoalkyl radical (it is possible to protect an amine with an acetyl, ureide or sulphonyl radical), (C 1 -C ₄ ) alkylamino (C 1 -C ₄ ) alkyl radical, di [(C 1 -C ₄ ) alkyl ] amino (C 1 -C ₄ ) alkyl radical (it is possible for dialkyl radicals to form a 5- or 6-membered carbon ring or heterocycle), hydroxy (C 1 -C ₄ ) alkyl- or di [hydroxy (C 1 -C ₄ ) alkyl an amino (C 1 -C ₄ ) alkyl radical;

- X radicals, which may be the same or different, represent a hydrogen atom, a C 1 -C ₄ alkyl radical, an aryl radical, a C 1 -C ₄ hydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a C 1 -C ₄ aminoalkyl radical, -C ₄ ) alkylamino (C 1 -C ₄ ) alkyl radical, di [(C ₁ -C ₄ ) alkyl] amino (C 1 -C ₄ ) alkyl radical (it is possible for the dialkyl radicals to form a 5- or 6-membered carbon ring or heterocycle) , hydroxy _(Ci-4) alkyh or di [hydroxy _(Ci-4) alkyl] amino _(Ci-4) alkyl radical, a (C _t -C ₄₎ alkyl- or di _[(Ci-4) alkyl] amino residue; a halogen atom, a carboxylic acid group or a sulfonic acid group;

i is 0, 1, 2 or 3;

p is 0 or 1;

q is 0 or 1;

9: ι

9 9 ·

<* ··

A · 9

-n isOnebol;

with the proviso that

- the sum of p + q is other than 0;

when p + q is 2, then n is equal to 0 and the groups NR ₁₈ R ₂₀ and NR 20 R 21 occupy positions 2,3; 5.6; 6.7; 3.5 or 3.7;

when p + q is equal to 1, then n is equal to 1 and the group NR ₁₈ R 19 (or NR 20 R 21) and the group OH occupy positions 2,3; 5.6; 6.7; 3.5 or 3.7.

When the pyrazolo [1,5-a] pyrimidines of formula (VIII) above are such that they contain a hydroxyl group to a nitrogen atom at one of the 2, 5 or 7 cc positions, there is a tautomeric equilibrium, represented, for example, by the following scheme.

Among the pyrazolo [1,5-a] pyrimidines of the general formula (VIII) above, in particular:

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-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;

3-aminopyrazolo [1,5-a] pyrimidin-7-ol;

3-aminopyrazolo [1,5-a] pyrimidin-5-ol;

2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;

2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;

2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;

2 - [(7-aminopyrazolo [1,5-a] pyrimidin-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-tetramethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

and their addition salts and tautomeric forms thereof, if a tautomeric equilibrium exists.

The pyrazolo [1,5-a] pyrimidines of formula VIII above may be prepared by cyclization starting from aminopyrazole according to the procedures described in the following references.

EP 628559 Beiersdorf-Lilly.

R. Vihsdu, H. Navedul, Indian J. Chem., 34b (5), 514, 1995.

- N.S. Ibrahim, K.U. Sadek, F.A. Abdel-Al, Arch. Pharm., 320, 240, 1987.

- R.H. Springer, M.B. Scholten, D.E. O'Brien, T. Novinson, J.P. Miller, R.K. Robins, J. Med. Chem., 25, 235 (1982).

- T. Novinson, R.K. Robins, T.R. Matthews, J. Med. Chem., 20, 296 (1977).

US 3907799 ICN Pharmaceuticals.

The pyrazolo [1,5-a] pyrimidines of formula VIII above may be prepared by cyclization starting from hydrazine, according to the procedure described in the following references:

- A. McKillop and R.J. Kobilecki, Heterocycles, 6 (9), 1355 (1977).

• 9 9 «9 9 • 9 9

9 9

9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

98 9 «999

9 9 9 9 9 • 9 9

9 «

- E. Alcade, J. De Mendoza, J.M. Marcia-Marquin, C. Almera, J. Elguero, J. Heterocyclic Chem., 11 (3), 423, 1974.

- K. Saito, I. Hori, M. Higarashi, H. Midorikawa, Bull. Chem. Soc. Japan, 47 (2), 476 (1974).

The oxidation bases of the invention preferably represent 0.0005 to 12 wt. based on the total weight of the ready-to-use coloring agent, and even more preferably 0.005 to 6% by weight, based on this weight.

Coupling agents are those commonly used in oxidative dye compositions, for example m-phenylenediamines, m-aminophenols and m-diphenols, mono- or polyhydroxylated naphthalene derivatives, sesamol and derivatives thereof, and heterocyclic compounds such as indole derivatives, indoline derivatives derivatives, benzimidazole derivatives, benzmorpholine derivatives, pyrazolazole derivatives, pyrolazole derivatives, imidazolazole derivatives, pyrazolopyrimidine derivatives, pyrazole-3,5-dione derivatives, pyrrolo [3,2-d] oxazole derivatives, pyrazolo [3,4-d] thiazole derivatives , thiazoloazole Soxide derivatives and thiazoloazole S, S-dioxide derivatives and their acid addition salts.

In particular, the coupling reagents are selected from the group consisting of 2-methyl-5-aminophenol,

5-N- (p-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1 - (β-hydroxyethyloxy) benzene, 2-amino-4- (3-hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one and 1-phenyl-3-methylpyrazol-5-one and their acid addition salts .

If present, the coupling agents preferably comprise from 0.0001 to 10% by weight, based on the total weight of the ready-to-use dye, more preferably from 0.005 to 5% by weight. due to this weight.

In general, the acid addition salts that can be used in the context of the coloring compositions of the invention (oxidizing bases and coupling agents) are particularly selected from hydrochlorides, hydrobromides, sulfates, tartarates, lactates and acetates.

The dye compositions of the invention may also contain, in addition to the oxidation bases defined above and optionally combined coupling agents, direct dyes to enrich shades. These direct dyes may in particular be selected from nitro-dyes, azo-dyes and anthraquinone dyes.

The present invention also provides a method for dyeing keratin fibers, particularly human keratin fibers such as hair, by using ready-to-use coloring agents as defined above.

According to this process, the at least one ready-to-use dye composition as defined above is applied to the fibers for a period of time sufficient to develop the desired coloration, after which the hair is rinsed, optionally washed with shampoo, and rinsed and dried again.

The time required to develop coloring to keratin fibers is usually between 3 and 60 minutes, more preferably between 5 and 40 minutes.

9 9

9 9

9 9

9

99 * 99

9 9 9

99

9 9

9 9

9 99

99 »

99

9 9 ·

9 9 9

9 9 9 9

99

According to one specific embodiment of the invention, the process comprises a first step comprising, on the one hand, a separately deposited composition A comprising in the environment suitable for dyeing, at least one oxidizing base and optionally at least one coupling agent as defined above, and B, comprising in an environment suitable for staining at least one 2-electron oxidoreductase enzyme in the presence of at least one donor for said enzyme and at least one aminosilicone and mixing them at the time of use prior to application of the composition to keratin fibers.

According to another specific embodiment of the invention, the aminosilicone is incorporated into composition A.

A further object of the invention is a multi-compartment dyeing kit or device or multi-compartment equipment or any multi-compartment packaging system comprising in the first compartment composition A as defined above and in the second compartment composition B as defined above. The device may be provided with means to apply the desired composition to the hair, such as the device described in French Patent No. 2,586,913 filed under the name of the applicant of the present invention.

It is also an object of the present invention to provide a novel method of treating keratin substance, particularly hair, to obtain a permanent treatment of such hair, particularly in the form of a permanent model, the process comprising the following steps: (i) a reducing agent is applied to the keratin substance to be treated wherein the keratin substance is first placed on the mechanical tensioning means, (ii) the keratin substance is optionally rinsed, (iii) an oxidizing agent as defined above is applied to the optionally rinsed keratin substance, (iv) the keratin substance is optionally rinsed again.

The first step (i) of this process consists in applying a hair reducing agent. This application is done individually or at a time.

For example, the reducing agent comprises at least one reducing agent, which may be selected, in particular, from thioglycolic acid, cysteine, cysteamine, glycerol thioglycolate, thiolactic acid or thiolactic and thioglycolic acid salts.

The usual tensioning of the hair to a shape corresponding to the desired final shape for the hair (e.g., curls) can be accomplished by suitable means, in particular by suitable mechanical means which are suitable and known per se to maintain tight hair, such as curlers and the like.

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

Before performing the optional rinsing (ii), the hair to which the reducing agent has been applied can be allowed to stand for several minutes, usually between 5 minutes and 1 hour, preferably between 10 and 30 minutes, so that the reducing agent has sufficient time to act on the hair. This phase is usually carried out at a temperature of from 35 ° C to 45 ° C, the hair preferably being protected by a cap.

In the optional second process step (step (ii)) the hair impregnated with the reducing agent is thoroughly rinsed with water.

11 11 11

1 1111 1111

11 11 11 1111

1,111 11,111 111,111

1111114 1 1

111 11 11 11 11 11

Further, in the third step (step (iii)), the oxidizing agent according to the invention is applied to the hair thus rinsed, fixing the new hair shape.

Similar to the application of the reducing agent, the hair to which the oxidizing agent is applied is then left to rest for at least several minutes, usually between 3 and 30 minutes, preferably between 5 and 15 minutes.

If the hair is kept taut by external means, these means (e.g., curlers) are removed from the hair before or after the fixation stage.

Finally, in the final step according to the invention (step (iv)), which is also optional, the hair impregnated with the oxidizing agent is rinsed thoroughly, usually with water.

Soft hair is obtained which is easy to comb. The hair is wavy.

The oxidizing agent according to the invention can also be used in decolorizing keratin fibers, in particular hair.

The decolorizing step of the invention comprises the step of applying an oxidizing agent of the invention to keratin fibers in the presence or absence of an oxidizing auxiliary. Conventionally, the second step of the bleaching process of the invention is the step in which the keratin fibers are rinsed.

An environment suitable for keratin fibers (or carrier) for ready-to-use colorants and oxidizing agents used for the permanent modeling or decolorization of keratin fibers according to the invention usually consists of water or a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvents, for example, C1-C4 alkanols such as ethanol and isopropanol are used; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether and aromatic alcohols such as benzyl alcohol and phenoxy ethanol, similar products and mixtures thereof.

The solvents may be present in an amount preferably between 1 and 40% by weight. to the total weight of the colorant, more preferably between 5 and 30% by weight.

The pH of the ready-to-use coloring agents and oxidizing agents used for the permanent modeling or bleaching of keratin fibers according to the invention is selected so as not to adversely affect the enzyme activity of the 2-electron oxidoreductase.

Typically, the pH is between 5 and 11, preferably between 6.5 and 10. It can be adjusted to the desired value using acidifying or alkalinizing agents usually used for dyeing keratin fibers.

As acidifying agents, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or lactic acid and sulfonic acid can be used.

Ftft ftftft ftft ftftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft ftft

As alkalinizing agents, for example, aqueous ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines, 2-methyl-2-aminopropanol and their derivatives, sodium hydroxide, potassium hydroxide and compounds of formula IX can be used:

X _of R ₂₄

Where W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl residue; R 22, R 23, R 24 and R 25, which may be the same or different, represent a hydrogen atom or C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl.

The ready-to-use dye compositions and the oxidative compositions for permanent modeling or bleaching of keratin fibers according to the invention may also contain various adjuvants commonly used in dyeing, permanent modeling or bleaching compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants. substances or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, enzymes other than 2-electron oxidoreductases used according to the invention, such as peroxidases, penetrating agents, masking agents, fragrances, buffers, dispersing agents, conditioners, film forming agents, preservatives and quenching agents.

It should further be appreciated that one skilled in the art may optionally select other compounds such that the advantageous properties intrinsically associated with the compositions of the invention are not or substantially not adversely affected by their addition.

The ready-to-use coloring and oxidizing agents used for the permanent modeling or decolorization of keratin fibers according to the invention may be in various forms, for example in the form of liquids, creams or gels or in other forms which are optionally pressurized or in any other form suitable for dyeing , permanent modeling or bleaching of keratin.

Direct-dye dyes, oxidizing dyes and 2-electron oxidoreductases are present in said composition, which must not contain oxygen gas to prevent premature oxidation of the oxidizing dyes.

Specific examples illustrating the invention are set forth below. In the text above and unless otherwise indicated, percentages are by weight. The examples are given by way of illustration only and in no way limit the scope of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Example of coloring agent 1

A ready-to-use dye composition (grams content) was prepared i

· 99 999 999 999 999 999 999 999 999 999 999 999 999 999 999 999 999 999 11 999 99 9

1118 9 9

99 99 91

Example 1

- Arthrobacter globiformis uricase at a concentration of 20 International Units (I.U.) / Mg, sold by Sigma

- Uric acid

- p-phenylenediamine

- Resorcinol

- Polydimethylsiloxane containing aminoethylaminopropyl groups in a concentration of 35% in water, sold under the name Dow Corning 939 Emulsion

- Demineralized water

1.5 g 1.5 g 0.324 g 0.33 g

1.2 g qs 100g

The ready-to-use dye composition above was applied to curls of natural gray hair containing 90% white hair for 30 minutes. The hair was then rinsed, washed with conventional shampoo and dried.

Curls of hair dyed with matt dark-blond color were obtained.

Example 2

Oxidizing agent for permanent bleaching

- Arthrobacter globiformis uricase at a concentration of 20 International Units (I.U.) / Mg, sold by Sigma

- Uric acid

- Ethanol

- (C 5 -C 16 alkyl polyglucoside as an aqueous solution containing 60% active material (A.M.) sold under the name Oramix CG110 by SEPPIC

- Mixture of polydimethylsiloxane containing aminoethylaminoisobutyl / polydimethylsiloxane groups under the trade name

Dow Corning Q2 8220 Fluid

- 2-Methyl-2-amino-1-propanol q with pH

- Demineralized water qs

1.8 g 1.65 g

20,0 g

8,0 g

1.0 g 9.5

100 g

Claims (25)

PATENT CLAIMS I • i 00 00 • 0 0 9 • 0 0 0 • 90 «00 9 9 99 99 Cosmetic and / or dermatological composition intended for the treatment of keratin fibers, in particular human keratin fibers and in particular human hair, characterized in that it contains on a carrier suitable for keratin fibers: (a) at least one 2-electron oxidoreductase enzyme in the presence of at least one donor for said enzyme, (b) at least one aminosilicon. Cosmetic and / or dermatological composition according to claim 1, characterized in that the 2 electron oxidoreductase is selected from uricases of animal, microbiological or biotechnological origin. Cosmetic and / or dermatological composition according to claim 1 or 2, characterized in that the oxidoreductases represent 0.01 to 20% by weight, based on the total weight. Cosmetic and / or dermatological composition according to claim 3, characterized in that the oxidoreductases represent 0.1 to 5% by weight, based on the total weight of the composition. Cosmetic and / or dermatological composition according to claim 2, characterized in that the donor (or substrate) for said 2-oxidoreductase is selected from uric acid and its salts. Cosmetic and / or dermatological composition according to any one of the preceding claims, characterized in that the donors represent 0.01 to 20% by weight, based on the total weight of the composition. Cosmetic and / or dermatological composition according to claim 6, characterized in that the donors represent 0.1 to 5% by weight, based on the total weight of the composition. Cosmetic and / or dermatological composition according to any one of claims 1 to 7, characterized in that the aminosilicone is selected from: (a) polysiloxanes corresponding to formula I: CH, OH HIM Si-o l ch ₃ - Si-O I (CH ₂ ) ₃ NH (ch ₂ j ₂ nh ₂ O) • 44 4 4 4 4 9 4 ·· · * 4 • 44 4 · · 4 * 444 4 4 4 4 4 4 4 Where χ and y are integers dependent on molecular weight, usually such that said molecular weight is between 5000 and 500000; (b) cationic silicone polymers having the formula: R _and G ₃ . _and -Si (OSiG ₂ ) _n - (OSiGbR ₂ .b) _m -O-SiG ₃ - _and -R _a (II) wherein: G is hydrogen or phenyl, OH or C 1 -C 8 alkyl, for example methyl, ethyl, and is 0 or an integer of 1 to 3, especially 0, b is 0 or 1, especially 1, and m are numbers such that the sum (n + m) ranges from 1 to 2000, and in particular from 50 to 150, wherein n may range from 0 to 1999, and in particular from 49 to 149, wherein m may range from 1 to 2000, in particular from 1 to 10; R is a monovalent radical of formula -C _q H _2q L, wherein is a number from 2 to 8 and L is an optionally quaternized group selected from: -N (R ') -CH ₂ -CH ₂ -N (R') ₂ -N (R ') ₂ -N ⁺ (R ') ₃ A' -N ⁺ (R ') 2 (H) A-N ⁺ (R') (H) 2A-N (R ') -CH ₂ -CH ₂ -N ⁺ (R') (H) ₂ A '; wherein R 'denotes hydrogen, phenyl, benzyl or a monovalent hydrocarbon radical, for example an alkyl radical of 1 to 20 atoms, and A' denotes a halide ion such as fluoride, chloride, bromide or iodide. (c) cationic silicone polymers having the formula: T ¹ R - Si ¹ I R R 1 = -CH ₂ -CHOH-CH ₂ -NN (R 1) ₃ Q ° Si ί βίSi — R ί (iv) where R 1 represents a monovalent hydrocarbon radical having 1 to 18 carbon atoms, in particular a C 1 -C 18 alkyl radical or a C ₂ -C ₁₆ alkenyl radical, for example methyl; R ₂ is a divalent hydrocarbon radical, in particular Ci-Cis alkylene radical or a _Ci-Cig, for example Ci-Cg divalent alkyleneoxy radical; Q 'is a halide ion, especially chloride; r represents an average statistical value of from 2 to 20, in particular from 2 to 8; s means an average statistical value of from 20 to 200, and in particular from 20 to 50. Cosmetic and / or dermatological composition according to any one of claims 1 to 8, characterized in that the concentration of aminosilicone is in the range of 0.05% to 10% by weight, based on the total weight of the composition and preferably between 0.1 and 5%. 9 9 99 9 9 9 9 9 9 9 9 9 9 9 9,999,999,999,999,999 9 9 9 9 9 9 9 * · ··· 99 99 99 99 99 Ready-to-use cosmetic and / or dermatological composition according to any one of claims 1 to 9 for the oxidative dyeing of keratin fibers, in particular human keratin fibers such as hair, characterized in that it also comprises, in an environment suitable for keratin fibers, at least one oxidative a base and optionally one or more coupling agents. Cosmetic and / or dermatological composition according to claim 10, characterized in that the oxidation bases are selected from the group consisting of p-phenylenediamines, double bases, o- or p-aminophenols and heterocyclic bases, as well as addition salts thereof. with acids. Cosmetic and / or dermatological composition according to claim 10 or 11, characterized in that the oxidation bases are present in concentrations ranging from 0.0005 to 12% by weight, based on the total weight of the composition. Cosmetic and / or dermatological composition according to claim 10, characterized in that the coupling agents are selected from the group consisting of m-phenylenediamines, maminophenols, m-diphenols and heterocyclic coupling agents and acid addition salts of these compounds. Cosmetic and / or dermatological composition according to claim 10 or 13, characterized in that the coupling agents are present in concentrations ranging from 0.0001 to 10% by weight, based on the total weight of the composition. Cosmetic and / or dermatological composition according to claim 11 or 13, characterized in that the acid addition salts for oxidizing bases and coupling agents are selected from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates. Cosmetic and / or dermatological composition according to any one of claims 10 to 15, characterized in that it also contains direct dyes. Cosmetic and / or dermatological composition according to any one of claims 1 to 16, characterized in that the environment suitable for keratin fibers (or support) consists of water or a mixture of water and at least one organic solvent. Cosmetic and / or dermatological composition according to claim 17, characterized in that the organic solvent is present in an amount preferably in the range of 1 to 40% by weight based on the total weight of the composition and even more preferably in the range of 5 to 30% by weight. . Cosmetic and / or dermatological composition according to any one of claims 1 to 18, characterized in that the pH is in the range of 5 to 11 and preferably in the range of 6.5 to 10. Cosmetic and / or dermatological composition according to any one of claims 1 to 19, characterized in that it also contains various adjuvants commonly used in hair coloring, permanent modeling or bleaching compositions selected from the group consisting of anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, enzymes other than 9 9 9 9. · · T t t t t t 2 electron oxidoreductases, penetrating agents, masking agents, fragrance agents, buffers, dispersing agents, conditioners, film forming agents • • • • • • • • , preservatives and quenching agents. A method for dyeing keratin fibers and in particular human keratin fibers, such as hair, characterized in that at least one ready-to-use dye composition as defined in claims 10 to 20 is applied to said fibers for a time sufficient to development of the desired coloration. A method according to claim 21, characterized in that it comprises a first step comprising, on the one hand, a separately deposited composition A comprising in the medium suitable for dyeing at least one oxidizing base and optionally at least one coupling agent as defined in of any one of claims 10 to 16, and on the other hand, composition B comprising in an environment suitable for staining at least one 2-electron oxidoreductase enzyme in the presence of at least one donor for said enzyme as defined in any one of the preceding claims, followed by mixing at the time of use, before the composition is applied to the keratin fibers, wherein component A or component B comprises an aminosilicone as set forth in the preceding claims. A multi-compartment dyeing kit or device, comprising a first compartment comprising composition A as defined in claim 22 and a second compartment comprising composition B as defined in claim 22. 24. A method of treatment of a keratinous substance, in particular a hair, in order to obtain a permanent treatment of said hair, in particular in a permanent permanent form, characterized in that the process comprises the following steps: (i) a reducing agent is applied to the keratinous substance to be treated wherein the keratin substance is first placed on the mechanical tensioning means, (ii) the keratin substance is optionally rinsed, (iii) an oxidizing agent is applied to the optionally rinsed keratin substance as defined in claims 1 to 9 and 17 to 20, (iv) the keratin substance is optionally rinsed again. 25. A method of treating keratin fibers, in particular hair, to discolour them, said method comprising applying an oxidizing agent as defined in any one of claims 1 to 9 and 17 to 20, optionally comprising an oxidizing aid and a second rinsing step keratin fibers.