FR3090352A1 - Process for coloring and / or lightening keratin fibers comprising a colored indicator - Google Patents

Abstract

The invention relates to a process for dyeing and / or lightening keratin fibers, in particular human keratin fibers such as the hair, comprising a step of mixing an alkaline composition i) and a composition ii) comprising at least one chemical oxidizing agent, at least one of the compositions i) and ii) comprising a direct dye capable of changing color on contact with free radical species derived from oxygen, until the mixture of the compositions i ) and ii) shows a color change visible to the naked eye.

Description

Description

Title of the invention: Process for coloring and / or lightening keratin fibers comprising a colored indicator

The present invention relates to a process for dyeing and / or lightening keratin fibers, in particular human keratin fibers such as the hair, comprising a step of mixing an alkaline composition i) and a composition ii) comprising at least one chemical oxidizing agent, at least one of the compositions comprising a direct dye capable of changing color on contact with free radical species derived from oxygen, until the mixture of compositions i ) and ii) shows a color change visible to the naked eye.

The dyeing and / or lightening processes of human keratin fibers usually used generally consist in using two compositions: an aqueous composition comprising at least one oxidizing agent and an alkaline composition (comprising an oxidation dye in the case of 'a coloring process), which are mixed together before use.

In the case of lightening, the oxidizing agent has the role of degrading the melanin of the hair, which, depending on the nature of the oxidizing agent present, leads to a more or less pronounced lightening of the fibers. .

[0004] In the case of coloring, its role is to activate the oxidation of the oxidation coloring precursors and the formation of colored species.

The generally preferred oxidizing agent is hydrogen peroxide.

The mixing conditions of the alkaline and oxidizing compositions, in particular the mixing time and the manner of mixing, are likely to vary from one user to another, and can have an impact on the rheological properties and the qualities of use of the mixture applied to keratin fibers. The mixture must not be too liquid so as not to flow, when it is applied, onto the face, the scalp, or outside the areas which it is proposed to treat, and be sufficiently fluid to allow good distribution and good spreading along the keratin fibers.

The mixing conditions of the alkaline and oxidizing compositions can also influence the dye performance if the solubilization of the active ingredients such as the dyes is not sufficient.

[0008] There is therefore a real need for a coloring and / or bleaching process allowing the user to mix the alkaline and oxidizing compositions more reproducible in terms of viscosity and better homogenization of the active ingredients in the mixture, so as to lead to better controlled dyeing and / or lightening performance on keratin fibers.

The Applicant has thus surprisingly discovered that the use in at least one of the alkaline and oxidizing compositions used in a coloring and / or lightening process, of a direct dye capable of changing color at contact with free radicals derived from oxygen, which acts as an indicator of the optimal time for mixing said compositions, makes it possible to satisfy this need.

The invention therefore relates to a process for dyeing and / or lightening keratin fibers, in particular human keratin fibers such as the hair, comprising a step of mixing an alkaline composition i) and a composition ii) comprising at least one chemical oxidizing agent, at least one of the compositions i) and ii) comprising a direct dye capable of changing color on contact with free radical species derived from oxygen, until that the mixture of compositions i) and ii) exhibits a color change visible to the naked eye.

More specifically, the invention relates to a process for coloring and / or lightening keratin fibers, in particular human keratin fibers such as the hair, comprising at least the following steps: a) mixing

i) a composition comprising at least one alkaline agent and optionally at least one oxidation dye precursor and ii) a composition comprising at least one chemical oxidizing agent, at least one of the compositions i) and ii) comprising at least one direct dye capable of changing color on contact with free radicals derived from oxygen, until the mixture of compositions i) and ii) exhibits a color change visible to the naked eye, then

b) applying to the keratin fibers the mixture of compositions i) and ii).

By “visible color change” of the mixture of compositions i) and ii), it is meant that the delta E (ΔΕ) between the composition resulting from the mixture of compositions i) and ii) defined above, comprising a dye direct capable of changing color on contact with free radicals derived from oxygen, and a composition resulting from the mixture of compositions i ') and ii') identical to compositions i) and ii) but free of direct dye capable of changing color in contact with free radicals derived from oxygen, is less than or equal to 10, preferably less than or equal to 8, better still less than or equal to 6.

The parameter ΔΕ is evaluated according to the following protocol.

The colorimetric parameters of the compositions are measured in the CIE system L * a * b * using a spectrocolorimeter such as a Konica Minolta CM2600d spectrocolorimeter (illuminant D65, angle 10 °, specular component included) in which L * represents the intensity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis.

The values of ΔΕ are calculated from the values of L * a * b * measured.

ΔΕ, which is the variation in color between the composition resulting from the mixture of compositions i) and ii), comprising a direct dye capable of changing color on contact with free radicals derived from oxygen, and a composition resulting from the mixture of compositions i ') and ii') identical to compositions i) and ii) but free of direct dye capable of changing color in contact with free radicals derived from oxygen, is calculated from the formula:

in which Li *, ai * and bi * represent the values measured on the composition resulting from the mixture of compositions i) and ii) used according to the method according to the invention, and L _o *, a ₀ * and b ₀ * represent the values measured on the composition resulting from the mixture of compositions i ') and ii') identical to compositions i) and ii) but free of direct dye capable of changing color in contact with free radicals derived from oxygen.

The change in color visible to the naked eye of the mixture of compositions i) and ii) is due to the gradual degradation of the color of the direct dye capable of changing color on contact with free radicals derived from oxygen, once brought into contact with the free radicals derived from oxygen generated during the bringing together of the alkaline composition and of the composition comprising the chemical oxidizing agent.

Thus, after a certain mixing time determined by the particular choice of dye, the mixture of the compositions changes color, in particular becomes significantly less colored, even colorless, which indicates that the mixture has a satisfactory viscosity allowing a desired quality of applications and obtaining effective dyeing properties, and is ready to be applied to keratin fibers.

The mixture of the compositions resulting from the process according to the invention has good qualities of use, in particular of application and distribution on the keratin fibers, in particular the hair. In particular, it is easy to use, does not drip and allows easy and homogeneous spreading and distribution along the hair.

When the method according to the invention is a coloring method, it also makes it possible to obtain powerful, intense, chromatic and / or not very selective colorings, that is to say colorations which are homogeneous along fiber, with the smallest possible color deviations throughout the same keratin fiber, which generally comprises areas that are differently sensitized (that is to say damaged) from its tip to its root.

When the method according to the invention is a lightening process, it allows good lightening performance to be obtained, in particular a strong and homogeneous lightening from root to tip.

The invention also relates to the use of a direct dye capable of changing color on contact with free radicals derived from oxygen, as an indicator of the mixing time of compositions i) and ii).

By "indicator time for mixing compositions i) and ii)" means a dye whose color changes over time and which indicates that said mixture has a satisfactory viscosity allowing a quality of applications desired and obtaining effective dye properties, and that it is thus ready to be applied to keratin fibers.

Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and examples which follow.

In what follows, and unless otherwise indicated, the limits of a range of values are included in this area, in particular in the expressions "between" and "ranging from ... to .. . "

The expression "at least one" used in the present description is equivalent to the expression "one or more".

In the dyeing and / or lightening process for keratin fibers, in particular human keratin fibers such as the hair, of the invention, the direct dye capable of changing color on contact with free radical species derived oxygen can be chosen from dyes of triarylmethane or methine cyanine types, and mixtures thereof.

The triarylmethane type dyes are especially chosen from the compounds of formula (I) below, their optical isomers, their geometric isomers, their tautomers, their acid or base salts, organic or inorganic, their solvates such as hydrates and their mixtures:

i + iR ₍ (i)

NOT ' '

formula (I) in which,

R i, R 2, R ’i and R’ 2 identical or different, represent:

• a hydrogen atom, • a C ₁ to C ₂ o, preferably C 1 to C ₄ , alkyl radical, linear or branched, such as methyl, ethyl and propyl, or • a benzyl radical optionally substituted by one or more groups SO ₃ or SO ₃ H;

• the radicals R ₃ , independently of one another, identical or different, represent:

• an alkyl radical -C _6, preferably C, to C _4, linear or branched, • a hydroxy radical, • a group SO ₃ or SO ₃ H, • or else two adjacent radicals R ₃ together form a ring 6 unsaturated links, preferably aromatic such as benzo, optionally substituted by one or more group SO ₃ or SO ₃ H;

• q is an integer ranging from 0 to 4, preferably from 1 to 4;

• R 4 represents:

• a hydrogen atom, or • a radical -NR ₅ R ₆ , with R ₅ and R _6j independently of one another, identical or different, representing: - a hydrogen atom, - an alkyl radical in to C _6, preferably C, to C _4, linear or branched, such as methyl, ethyl and propyl;

It being understood that:

❖ the radical R ₂ is present or absent, symbolized by the dotted link, when R ₂ is present then the nitrogen atom which carries it is in cationic ammonium form, when R ₂ is absent then the nitrogen atom which carries it is not charged, (+) is not present, and ❖ the compound of formula (I) optionally comprises one or more An anions and optionally one or more M ⁺ cations to ensure the electroneutrality of the molecule ;

with:

- An representing an anion, preferably chosen from bromide, chloride, methylsulfate, toluenesulfonate ions or a mixture of these ions; and

- M ⁺ representing a cation, preferably chosen from sodium, potassium, magnesium, calcium, zinc, ammonium ions or a mixture of these ions.

Preferably, R _b R ₂ , R \ and R ' ₂ , are identical in formula (I) as defined above.

More particularly, the dyes of the triarylmethane type are chosen from the following compounds, their optical isomers, their geometric isomers, their tautomers, their acid or base salts, organic or inorganic, their solvates such as hydrates and their mixtures:

[Tables 1]

Acid Blue 9 λυ ex. W; ~ :: 6¾ , .S XH Acid Green 50 • X ' Basic Violet 14 __ / \ __ / P- \ _s // “ό 'y- Basic Blue 7 T * ”'® j *'

The dyes of methine cyanine type are in particular chosen from the compounds of formula (II), their organic or mineral acid salts, optical isomers, geometric isomers, and solvates such as hydrates:

[0033]

[0034]

(Π) formula (II) in which:

• n represents an integer ranging from 1 to 3, preferably such as 1;

• Ra and Rb, identical or different, represent a hydrogen atom or an alkyl group Ci-C _4; particularly Rb represents a hydrogen atom and more particularly Ra and Rb represent a hydrogen atom;

• R ¹ represents a hydrogen atom or an alkyl group Ci-C _6, preferably C _r C ₄ linear or branched, such as methyl;

• R ² and R ³ together form with the carbon atoms which carry them an optionally substituted benzo ring;

• R ⁴ and R ⁵ , identical or different, represent:

• a hydrogen atom, or • an amino radical -NR ⁶ R ⁷ with R ⁶ and R ⁷ are identical or different, representing a hydrogen atom or an alkyl group Ci-C ₆ optionally carrying a halogen atom, halogen, preferably R ⁶ represents an unsubstituted alkyl radical and R ⁷ an alkyl radical carrying a halogen atom;

• W represents a group CRR ', with R and R' identical or different, representing a hydrogen atom or a C _r C ₄ alkyl group; preferably a C _r C ₄ alkyl group, such as methyl;

• Q represents an anionic counterion.

Preferably, R ₄ is a hydrogen atom and R ⁵ is preferably positioned on the carbon atom 4 of the phenyl ring, R ⁵ represents in particular a group -NR ⁶ R ⁷ in the formula (II) as defined below. -above.

In a particular embodiment, the dye of methine cyanine type is Basic Red 13 of the following formula:

or one of its optical isomers, geometric isomers, tautomers, acid or base salts, organic or inorganic, solvates such as hydrates, or mixtures thereof. In a preferred embodiment of the invention, at least one direct dye capable of changing color on contact with free radical species derived from oxygen can be chosen from Acid Blue 9, Acid Green 50, Basic Violet 14, Basic Blue 7, Basic Red 13 and their mixtures.

The direct dye (s) capable of changing color on contact with free radical species derived from oxygen can be contained in composition i) or ii) in an amount ranging from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight, better still from 0.075 to 1% by weight relative to the total weight of the composition i) or ii).

Preferably, the direct dye (s) capable of changing color on contact with free radical species derived from oxygen are contained in composition i) or ii), or in both, better in composition i) or ii). More preferably, the direct dye (s) capable of changing color on contact with free radical species derived from oxygen are contained in composition ii).

The term "alkaline agent" means any agent which makes it possible to increase the pH of the composition in which it is found.

It can be mineral or organic.

More particularly, the alkaline agent (s) which can be used in composition i) of the invention can (be) chosen from:

a) ammonia or ammonium hydroxide,

b) alkanolamines such as mono-, di- and triethanolamines, isopropanolamine, 2-amino-2-methyl-1-propanol, as well as their derivatives, c) oxyethylenated and / or oxypropylenated ethylenediamines, d) mineral or organic hydroxides,

e) alkali metal silicates such as sodium metasilicates,

f) preferably basic amino acids such as arginine, glycine, lysine, omithine, citrulin and histidine, or their alkali or alkaline earth metal salts, g) particularly carbonates and bicarbonates of primary, secondary or tertiary amine, of alkali or alkaline-earth metal, or of ammonium, and

h) the compounds of formula (III) below:

Rx _{v Rz} (m)

N-X-N

Rt wherein X is an alkylene Ci-C ₆ linear or branched, optionally substituted by one or more hydroxyl groups or alkyl-C _6, more Ci -C _4; Rx, Ry, Rz and Rt, which are identical or different, represent a hydrogen atom, an alkyl group Ci-C ₆ hydroxyalkyl, Ci-C ₆ aminoalkyl or Ci-C _6.

Examples of such compounds of formula (III) that may be mentioned include

1,3-diaminopropane and 1,3-diamino-2-propanol.

The mineral or organic hydroxides are preferably chosen from the hydroxides of an alkali metal, the hydroxides of an alkaline earth metal, such as sodium or potassium hydroxides, the hydroxides of a transition metal, such as the hydroxides of the metals of groups III, IV, V and VI of the periodic table of the elements, the hydroxides of the lanthanides or actinides, the quaternary ammonium hydroxides, and guanidinium hydroxide.

The hydroxide can be formed in situ such as, for example, guanidine hydroxide, formed by the reaction of calcium hydroxide and guanidine carbonate.

The preferred alkaline agents are chosen in particular from ammonia, ammonium hydroxide, alkanolamines such as monoethanolamine, triethanolamine and 2-amino-2-methyl-1-propanol, the hydroxides of a alkali or alkaline earth metal, ammonium or sodium carbonate, ammonium or sodium bicarbonate, alkali metal silicates such as sodium metasilicates, arginine, sodium or potassium glycinate and their mixtures, better among ammonia, ammonium hydroxide, alkanolamines such as monoethanolamine and their mixtures.

The alkaline agent (s) as defined above may be present in a total content, for example, from 0.01 to 20% by weight, in particular from 0.1 to 15% by weight, and preferably from 1 to 10% by weight, better still from 2 to 9% by weight relative to the total weight of the composition i).

Among the chemical oxidizing agents which can be used in composition ii) of the invention, mention may in particular be made of hydrogen peroxide, the compounds capable of producing hydrogen peroxide by hydrolysis such as urea peroxide, or persalts such as perborates, percarbonates and persulfates, hydrogen peroxide being particularly preferred.

Preferably, the chemical oxidizing agent (s) is or are used in a total proportion ranging from 2 to 30% by weight, preferably from 3 to 20% by weight , better still from 5 to 15% by weight relative to the total weight of the composition ii).

In a preferred embodiment, the process uses one or more chemical oxidants, preferably hydrogen peroxide.

Composition i) may also comprise one or more oxidation dyes.

Oxidation dyes are generally chosen from one or more oxidation bases, optionally combined with one or more coupling agents.

By way of example, the oxidation bases are chosen from para-phenylenediamines, bis (phenyl) alkylenediamines, para-aminophenols, orthoaminophenols and heterocyclic bases and the corresponding addition salts.

Among the para-phenylenediamines which may be mentioned, there are for example para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2, 6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, Ν, Ν-dimethyl-para-phenylenediamine, Ν, Ν-diethyl-para- phenylenediamine, Ν, Ν-dipropyl-para-phenylenediamine, 4- amino-N, N-diethyl 1- 3-methylaniline, N, N-bis ^ -hydroxyethyl) -para-phenylenediamine, 4-N, N -bis ^ -hydroxyethyl) arnino-2-methylaniline, 4-N, N-bis (B-hydroxyethyl) amino-2-chloroaniline, 2- β-hydroxyethyl-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - ^ - hydroxypropyl) -para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl- para-phenylenediamine, Nethyl-N - ^ - hydroxyethyl) -para-phenylenediamine, N ^, Y-dihydr oxypropyl) -para-phenylenediamine, N (4'-aminophenyl) -para-phenylenediamine, N-phenyl-para-phenylenediamine, 2- β-hydroxyethyloxy-para-phenylenediamine, 2 ^ -acetylaminoethyloxy-para-phenylenediamine, N ^ -methoxyethyl) -para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2 ^ -hydroxyethylamino-5-aminotoluene and 3-hydroxy-l- (4'-aminophenyl) pyrrolidine and the corresponding addition salts with an acid.

Among the aforementioned para-phenylenediamines, paraphenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2- β-hydroxyethyl-para-phenylenediamine, 2 ^ -hydroxyethyloxy-para- are particularly preferred phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (hydroxyethyl) -para-phenylenediamine, 2-chloro-para-phenylenediamine and 2 ^ -acetylaminoethyloxy-para-phenylenediamine and the corresponding addition salts with an acid.

Among the bis (phenyl) alkylenediamines which may be mentioned, there is for example N, N'-bis ^ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropanol, N, N'-bis ^ -hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis ^ -hydroxyethyl ) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis (4'- amino-3'-methylphenyl) ethylenediamine and 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane and the corresponding addition salts.

Among the para-aminophenols which are mentioned, there are for example paraaminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino -3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-ammo-2-ammomethylphenol, 4-ammo-2 - ^ - hydroxyethylaminomethyl) phenol and 4-amino-2-fluorophenol and the corresponding addition salts with an acid.

Among the ortho-aminophenols which may be mentioned, there are for example 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol and corresponding addition salts.

Among the heterocyclic bases which may be mentioned, there are for example the derivatives of pyridine, pyrimidine and pyrazole.

Among the pyridine derivatives which may be mentioned, there are the compounds for example described in patents GB 1 026 978 and GB 1 153 196, for example 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine and 3,4-diaminopyridine and the corresponding addition salts.

Other pyridine oxidation bases which are useful in the present invention are the 3-aminopyrazolo [l, 5-a] pyridme oxidation bases or the corresponding addition salts described, for example, in patent application FR 2 801 308. Examples which may be mentioned include pyrazolo [1,5-a] pyrid-3-ylamine, 2-acetylaminopyrazolo [1,5-a] pyrid-3-ylamme, 2 -morpholm-4-ylpyrazolo [1,5-a] pyrid-3-ylamine, 3-aminopyrazolo acid [1,5-a] pyridme-2-carboxylic, 2-methoxypyrazolo [1,5-a] pyrid -3-ylamme, (3-ammopyrazolo [1,5-a] pyrid-7-yl) methanol, 2- (3-aminopyrazolo [1,5-a] pyrid-5-yl) ethanol, 2- (3-ammopyrazolo [1,5-a] pyrid-7-yl) ethanol, (3-ammopyrazolo [1,5-a] pyrid-2-yl) methanol, 3,6-diaminopyrazolo [1,5- a] pyridme, 3,4-diaminopyrazolo [1,5-a] pyridme, pyrazolo [1,5-a] pyridine-3,7-diamme, 7-morpholm-4-ylpyrazolo [1,5-a ] pyrid-3-ylamine, pyrazolo [1,5-a] pyridine-3,5-diamme, 5-morpholm-4-ylpyrazolo [1,5-a] pyrid-3-ylamine, 2 - [( 3-ammopyrazolo [1,5-a] pyrid-5-yl) (2-hydroxyethyl) -ammo] ethanol, 2 - [(3-ammopyrazolo [1,5-a] pyrid-7-yl) (2-hydroxyethyl) ammo] ethanol, 3-aminopyrazolo [1,5-a] pyridm-5-ol, 3-aminopyrazolo [1,5-a] pyridin-4-ol, 3-aminopyrazolo [1,5-a] pyridm-6-ol, 3- aminopyrazolo [1,5-a] pyridin-7-ol, 2 ^ -hydroxyethoxy-3-ammo-pyrazolo [1,5-a] pyridine; the

2- (4-dimethylpiperazinium-1-yl) -3-amino-pyrazolo [1,5-a] pyridine; and the corresponding addition salts.

More particularly, the oxidation bases which are useful in the present invention are chosen from 3-aminopyrazolo- [1,5-a] -pyridines and preferably substituted on the carbon atom 2 by:

a) a (di) (Ci-C ₆ ) (alkyl) amino group, said alkyl group being able to be substituted by at least one hydroxy, amino, imidazolium group;

b) a heterocycloalkyl group containing 5 to 7 members and 1 to 3 heteroatoms, optionally cationic, optionally substituted by one or more (Ci-C ₆ ) alkyl groups, such as a di (Ci-C ₄ ) alkylpiperazinium group; or

c) an (Ci-C ₆ ) alkoxy group optionally substituted by one or more hydroxy groups such as a β-hydroxyalkoxy group and the corresponding addition salts.

Among the pyrimidine derivatives which may be mentioned, there are the compounds described, for example, in patents DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application 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, 2,5,6-triaminopyrimidine and their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.

Among the pyrazole derivatives which may be mentioned, there are the compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FRA-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1 - ^ - hydroxyethyl) 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, l-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole, 4,5-diamino -l-tert-butyl-3-methylpyrazole, 4,5-diamino-1 - ^ - hydroxyethyl) -3-methylpyrazole, 4,5-diamino- 1-ethyl-3-methylpyrazole, 4,5-diamino -l-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-isop ropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5-triaminopyrazole, 3,5- diamino-1-methyl-4-methylaminopyrazole, the

3,5-diarnino-4 - ^ - hydroxyethyl) amino-1-methylpyrazole and the corresponding addition salts. It is also possible to use 4,5-diamino-1 - ([> - mcthoxyctiiyl) pyrazolc.

A 4,5-diaminopyrazole will be used preferably and even more preferably 4,5-diamino-1 - ^ - hydroxyethyl) pyrazole and / or a corresponding salt.

Pyrazole derivatives which may also be mentioned include diamino-N, N-dihydropyrazolopyrazolones and in particular those described in patent application FR-A-2 886 136, such as the following compounds and the addition salts corresponding: 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-l-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-l-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-l-one, 2-amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1, 2-a] pyrazol-1-one, 4,5-diamino-1,2-dimethyl -1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-di- (2- hydroxyethyl) -1,2-dihydropyrazol-3-one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [l, 2-a] pyrazol-l-one , 2-amino-3-dimethylamino-6,7-diliydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro -1H, 6H-pyridazino [1,2-a] pyrazol-1-one, 4-amino-1,2-diethyl-5- (pyrrolidin-1 -yl) -1,2-dihydropyrazol-3-one, 4-amino-5- (3-dimethylaminopyrrolidin-1 -yl) -1,2-diethyl-1,2-dihydropyrazol-3-one, 2, 3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1, 2-a] pyrazol-1-one.

Preferably use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [l, 2-a] pyrazol-l-one and / or a corresponding salt.

Preferably 4,5-diamino-l - ^ - hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [l, 2-a] pyrazol -l-one and / or a corresponding salt as heterocyclic bases.

The composition according to the invention may optionally comprise one or more coupling agents advantageously chosen from those traditionally used in the coloring of keratin fibers.

Among these coupling agents, mention may in particular be made of metaphenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents as well as the corresponding addition salts.

Mention may for example be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-l- (B-hydroxyethyloxy ) benzene, 2-amino-4- (B-hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureidoaniline, 3- ureido-1-dimethylaminobenzene, sesamol, 1B-hydroxyethylamino-3,4-methylenedioxybenzene, Γα-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, lN- (B-hydroxyethyl) amino-3,4-methylenedioxybenzene, 2,6- bis (B-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2 , 6-dimethylpyrazolo [1,5-b] -1,4,4-triazole, 2,6-dimethyl [3,2-c] -1,4,4-triazole and 6-methylpyrazolo [1,5 -a] benzimidazole, 2-methyl-5-aminophenol, 5-N- (B-hy droxyethyl) amino-2-methylphenol, 3-aminophenol, 3-amino-2-chloro-6-methylphenol, the corresponding addition salts with an acid and the corresponding mixtures.

In general, the addition salts of oxidation bases and coupling agents which can be used in the context of the invention are in particular chosen from addition salts with an acid, such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base (s) each represents (s) advantageously 0.001% to 10% by weight, and preferably 0.005% to 5% by weight relative to the total weight of the composition i).

The coupling agent (s), if they are present, each advantageously represent 0.001% to 10% by weight and preferably 0.005% to 5% by weight relative to the total weight of the composition i).

The compositions i) and / or ii) may also comprise at least one additive chosen from fatty substances preferably liquid, preferably nonionic surfactants, cationic polymers and their mixtures.

Or the composition (s) i) and / or ii) may (wind) further comprise one or more fatty substances, preferably liquid (s) (or oil (s)).

By "fatty substance" is meant an organic compound insoluble in water at ordinary temperature (25 ° C) and at atmospheric pressure (760 mm Hg) (solubility less than 5% and preferably 1% even more preferably at 0.1%). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms or a chain of at least two siloxane groups. In addition, fatty substances are generally soluble in organic solvents under the same conditions of temperature and pressure, such as, for example, chloroform, ethanol, benzene, petrolatum oil or decamethylcy15 clopentasiloxane.

By "oil" means a "fatty substance" which is liquid at room temperature (25 ° C), and at atmospheric pressure (760 mm Hg or 1.013.105 Pa).

The term “non-silicone oil” is understood to mean an oil not containing a silicon atom (Si) and a “silicone oil” an oil containing at least one silicon atom.

[0078] More particularly, the fatty substance is chosen from hydrocarbons C ₆ -C _6, non-silicone oils (hydrocarbon) to more than 16 carbon atoms, vegetable, animal, mineral or synthetic triglycerides d vegetable or synthetic origin, fluorinated oils, fatty alcohols, non-salified fatty acids, fatty acid esters and / or fatty alcohol different from triglycerides, silicones, and mixtures thereof.

It is recalled that within the meaning of the invention, the alcohols, esters and fatty acids more particularly have at least one hydrocarbon group, linear or branched, saturated or unsaturated, comprising 6 to 30 carbon atoms, optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If unsaturated, these compounds can have one to three carbonecarbon double bonds, conjugated or not.

[0080] As hydrocarbons C ₆ -C _6, there may be mentioned alkanes, C ₆ -C _6, the latter being linear, branched, optionally cyclic.

As examples, mention may be made of hexane, dodecane, isoparaffins such as isohexadecane and isodecane.

The following compounds can also be mentioned:

- A mixture of branched C1 ₅ -C ₆ alkanes, for example that which is marketed by the company SEPPIC under the name EMOGREEN L15;

- a mixture of linear and / or branched C13-C15 alkanes, for example that which is marketed by the company SEPPIC under the name EMOSMART L15.

Hydrocarbon oils of more than 16 carbon atoms can be linear or branched. They can be chosen from mineral oils, paraffin oils, petrolatum, petrolatum oil, polydecenes, hydrogenated polyisobutene such as Parléam®, squalane, squalene and their mixtures,

Among the hydrocarbon oils of plant origin, there may be mentioned the refined vegetable perhydrosqualene marketed under the name fitoderm by the company Cognis; vegetable squalane sold for example under the name Squalive by the company Biosynthis.

As hydrocarbon oils of animal origin, there may be mentioned perhydrosqualene.

The triglycerides of plant or synthetic origin are preferably chosen from liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms such as the triglycerides of heptanoic or octanoic acids or, more particularly from those present in vegetable oils such as, for example, sunflower, corn, soybean, squash, grapeseed, sesame, hazelnut, apricot, macadamia, macaw, arara, sunflower, castor oil, avocado, jojoba oil, shea butter oil or synthetic triglycerides of caprylic / capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel , and mixtures thereof.

The fluorinated oils can be chosen from perfluoromethylcyclopentane and perfluoro-1,3 dimethylcyclohexane, sold under the names of FLUTEC® PCI and FLUTEC® PC3 by the company BNFL Fluorochemicals; perfluoro1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names of PF 5050® and PF 5060® by the company 3M, or else bromoperfluorooctyle sold under the name FORALKYL® by the company Atochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® by the company 3M.

The fatty alcohols which are suitable for implementing the invention are more particularly chosen from saturated or unsaturated, linear or branched alcohols, containing from 8 to 30 carbon atoms. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol linolenic alcohol, ricinoleic alcohol, undecylenic alcohol or linoleic alcohol and their mixtures.

The fatty acids which can be used in the context of the invention are more particularly chosen from carboxylic acids, saturated or unsaturated, linear or branched, comprising from 6 to 30 carbon atoms, in particular from 9 to 30 carbon atoms . They are advantageously chosen from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and isostearic acid. These fatty acids are in the composition of the invention not salified with organic or mineral bases so as not to give rise to soaps.

With regard to fatty acid esters and / or fatty alcohols, different from the triglycerides mentioned above and vegetable waxes; include in particular esters of mono- or polybasic aliphatic saturated or unsaturated, linear Ci-C ₂₆ or branched C ₃ -C ₂₆ mono or saturated or unsaturated aliphatic polyhydric, linear Ci-C ₂₆ or branched C ₃ -C ₂₆ , the total number of carbon of the esters being greater than or equal to 6, more advantageously greater than or equal to 10.

Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; the alkyl lactate Cl ₂ -Ci5; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso) stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; acetyl methyl ricinoleate; myristyle stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, myristyl myristate , stearyl hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and mixtures thereof.

[0092] Still in the context of this variant, it is also possible to use esters of di or tricarboxylic acids, C ₄ -C ₂₂ alcohols and Ci-C ₂₂ and esters of mono-, di- or tricarboxylic acids and 'di, tri, tetra or pentahydroxy alcohols, C ₂ -C ₂₆ .

Mention may in particular be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl teteasononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; and polyethylene glycol distearates and mixtures thereof.

Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl, stearyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, myristates d alkyls such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate and mixtures thereof.

Or the composition (s) can (wind) also comprise, as fatty ester, esters and di-esters of sugars of C ₆ -C ₁₀ fatty acids. preferably enCi ₂ -C ₂₂ . It is recalled that the term “sugar” is understood to mean oxygenated hydrocarbon compounds which have several alcohol functions, with or without aldehyde or ketone function, and which contain at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.

As suitable sugars, mention may be made, for example, of sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives, in particular alkylated, such as methylated derivatives such as methylglucose.

The sugar and fatty acid esters can be chosen in particular from the group comprising the esters or mixtures of sugar esters described above and of C ₆ -C _30j fatty acids, preferably enCi ₂ -C ₂ 2 , linear or branched, saturated or unsaturated. If unsaturated, these compounds can comprise one to three carbonecarbon double bonds, conjugated or not.

The esters according to this variant can also be chosen from mono-, di-, tri- and tetra-esters, polyesters and their mixtures.

These esters can be, for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or their mixtures such as in particular the mixed oleo-palmitate, oleo-stearate, palmitostearate esters.

More particularly, mono- and di-esters are used and in particular the mono- or di-oleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, sucrose, glucose or methylglucose.

By way of example, mention may be made of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

Examples of esters or mixtures of fatty acid sugar esters can also be cited:

- the products sold under the names L160, L140, LUO, L90, L70, SL40 by the company Crodesta, respectively designating the palmito-stearates of sucrose formed from 73% of monoester and 27% of di- and tri-ester, from 61 % of monoester and 39% of di-, tri-, and tetra-ester, of 52% of monoester and 48% of di-, tri-, and tetra-ester, of 45% of monoester and 55% of di-, tri-, and tetra-ester, 39% monoester and 61% di-, tri-, and tetra-ester, and sucrose mono-laurate;

- the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% di-triester-polyester;

- the sucrose mono-di-palmito-stearate marketed by the company Goldschmidt under the name Tegosoft® PSE.

The fatty substance (s) do not comprise an oxyalkylenated C ₂ -C _{3 unit} . Preferably they do not contain a glycerolated motif. More particularly, fatty substances are different from fatty acids.

Preferably, the fatty substance is a liquid compound at the temperature of 25 ° C and at atmospheric pressure, or oil.

According to a preferred variant, the fatty substances are not silicone.

The fatty substance (s) is or are preferably chosen from C ₆ -C ₆ hydrocarbons, hydrocarbon oils with more than 16 carbon atoms, of vegetable, animal, mineral or synthetic origin, fatty alcohols, fatty acid and / or fatty alcohol esters, or mixtures thereof.

More particularly, the fatty substance (s) is or are chosen from linear or branched hydrocarbon oils, of mineral or synthetic origin, of more than 16 carbon atoms or their mixtures, such as those described below above, and for example mineral oil, and fatty alcohols such as those described above, and for example cetearyl alcohol, and their mixtures.

When the composition i) used in the process of the invention comprises one or more fatty substances, their total content preferably varies from 1 to 60% by weight, more preferably from 2 to 30% by weight, better from 5 to 25% by weight, even more preferably from 10 to 20% by weight, by weight relative to the total weight of the composition i).

When the composition i) used in the process of the invention comprises one or more liquid fatty substances, their total content preferably varies from 1 to 60% by weight, more preferably from 2 to 30% by weight, better from 3 to 20% by weight, even more preferably from 5 to 15% by weight, relative to the total weight of the composition i).

When the composition ii) used in the process of the invention comprises one or more fatty substances, their total content preferably varies from 1 to 80% by weight, more preferably from 5 to 70% by weight, better from 10 to 65% by weight, even more preferably from 20 to 60% by weight relative to the total weight of the composition ii).

When the composition ii) used in the process of the invention comprises one or more liquid fatty substances, their total content preferably varies from 1 to 80% by weight, more preferably from 5 to 70% by weight, better from 10 to 65% by weight, even more preferably from 20 to 60% by weight, by weight relative to the total weight of the composition ii).

The surfactants which can be used as additives are in particular chosen from anionic, cationic, amphoteric or zwitterionic, and nonionic surfactants, and more particularly from nonionic surfactants.

Preferably the nonionic surfactant (s) are chosen from oxyalkylenated (OA) nonionic surfactants, better oxyethylenated.

According to a particular embodiment, the composition (s) i) and / or ii) comprises (s) at least one oxyalkylenated non-ionic surfactant (OA) comprising a number of OA units ranging from 1 to 9 and at least one oxyalkylenated (OA) nonionic surfactant comprising at least 10 OA units.

Preferably, the oxyalkylenated nonionic surfactants according to the invention are chosen from oxyethylenated nonionic surfactants.

Preferably, according to this embodiment, the composition i) or ii) used according to the invention comprises at least one oxyethylenated (EO) nonionic surfactant comprising a number of EO units ranging from 1 to 9 and at least one oxyethylenated (EO) nonionic surfactant comprising at least 10 EO units.

The oxyethylenated nonionic surfactants comprising a number of OE units ranging from 1 to 9 and the oxyethylenated nonionic surfactants comprising at least 10 OE units can be chosen from the following categories:

❖ oxyethylenated (C ₈ -C ₂₄ ) alkyl phenols, ❖ fatty alcohols, C ₈ -C ₃₀ , preferably C12-C22, saturated or unsaturated, linear or branched, oxyethylenated, ❖ amides, C ₈ -C ₃₀ , saturated or unsaturated, linear or branched, oxyethylenated, ❖ esters of C ₈ -C ₃₀ acids, ₃₀ saturated or unsaturated, linear or branched, and of polyethylene glycols, ❖ esters of C ₈ -C ₃₀ acids, saturated or not, linear or branched, and of polyoxyethylenated sorbitol, ❖ oxyethylenated, saturated or unsaturated vegetable oils, and their mixtures.

Preferably, the oxyethylenated nonionic surfactant comprising at least 10 OE units and the oxyethylenated nonionic surfactant comprising from 1 to 9 OE units are chosen from C ₈ -C ₃ fatty alcohols, oxyethylenated, preferably Ci ₂ - C ₂₂ , better in C14-C20, saturated or unsaturated, linear or branched, preferably linear such as cetyl alcohol, oleic alcohol, oleocetyl alcohol, behenyl alcohol, cetearyl alcohol, stearyl alcohol , and mixtures thereof, and more preferably stearyl alcohol.

Preferably used as oxyethylenated nonionic surfactant comprising from 1 to 9 EO units, oxyethylenated nonionic surfactants comprising from 2 to 8, preferably from 2 to 4 EO units, such as for example adducts ethylene oxide and stearyl alcohol such as stearyl alcohol 2 EO (CTFA name steareth-2).

The oxyethylenated nonionic surfactants comprising at least 10 OE units used in the invention may in particular have a number of oxyethylenated groups ranging from 10 to 50, preferably from 15 to 30 and better still from 15 to 25, such as for example the Adducts of ethylene oxide and stearyl alcohol such as stearyl alcohol 20 EO (name CTFA steareth-20).

The total content of nonionic surfactant (s) oxyalkylenated (s), preferably oxyethylenated (s) comprising from 1 to 9 oxyalkylene units, preferably oxyethylene in composition i) or ii) can range from 0 , 1 to 15% by weight, preferably from 0.5 to 10% by weight and better still from 1 to 6% by weight relative to the total weight of the composition i) or ii).

The total content of oxyalkylenated, preferably oxyethylenated nonionic surfactants comprising at least 10 oxyalkylene groups, preferably oxyethylene, in composition i) or ii) may range from 0.1 to 15% by weight, preferably from 0 , 5 to 10% by weight, better still 1 to 5% by weight relative to the total weight of the composition i) or ii).

The total amount of non-ionic oxyalkylenated, preferably oxyethylenated, surfactants in composition i) or ii) can range from 1 to 25% by weight, preferably from 2 to 15% by weight and better still from 3 to 7% by weight relative to the total weight of the composition i) or ii).

Composition i) or ii) may also contain one or more cationic polymers.

The term “cationic polymer” means any polymer comprising cationic groups and / or groups that can be ionized into cationic groups. Preferably, the cationic polymer is hydrophilic or amphiphilic. The preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and / or quaternary amine groups which can either be part of the main polymer chain or be carried by a lateral substituent directly linked thereto.

The cationic polymers capable of being used preferably have a weight-average molar mass (Mw) of between 500 and 5.10 ⁶ approximately, preferably between 10 ³ and 3.10 ⁶ approximately.

Among the cationic polymers preferred in the process of the invention, mention may in particular be made of the homopolymer of salts (for example chloride) of dimethyldiallylammonium for example polyquatemium-6, such as that sold under the name MERQUAT 100 by the NALCO, and the copolymers of salts (for example chloride) of diallyldimethylammonium and of acrylamide sold in particular under the name MERQUAT 550 or MERQUAT 7SPR.

Among the cationic polymers preferred in the process of the invention, mention may also be made of quaternary diammonium polymers containing recurring units corresponding to the following formula (IV):

In which:

- Rio, Ru, R12 θί Rb, identical or different, represent aliphatic, alicyclic, arylaliphatic or hydroxyalkylaliphatic radicals containing from 1 to 6 carbon atoms; or else R ₁₀ , R _n , R ₁₂ and R ₁₃ , together or separately, constitute with the nitrogen atoms to which they are attached heterocycles optionally containing a second heteroatom other than nitrogen; or else R ₁₀ , Ru, R ₁₂ and R ₁₃ represent a linear or branched C _r C ₆ alkyl radical, substituted by a nitrile, ester, acyl, amide or -CO-OR _[4 -D or -CO- NH-R ₁₄ -D where R ₁₄ is an alkylene and D a quaternary ammonium group;

- Ai and Bi represent polymethylenic groups containing from 2 to 8 carbon atoms, linear or branched, saturated or unsaturated, and which can contain, linked to or inserted in the main chain, one or more aromatic rings, or one or several oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

- X denotes an anion derived from a mineral or organic acid;

- Ai, Rio and Ri ₂ can form with the two nitrogen atoms to which they are attached a piperazine ring;

- in addition if Ai denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, Bi can also denote a group

- (CH ₂ ) _n -CO-D-OC- (CH ₂ ) _n - in which D denotes:

a) a glycol residue of formula: -O-Z-O-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas:

- (CH ₂ -CH ₂ -O) _X -CH ₂ -CH ₂ - or - [CH ₂ -CH (CH ₃ ) -O] _y -CH ₂ -CH (CH ₃ ) where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative;

c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or else the bivalent radical

-CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -;

d) a ureylene group of formula: -NH-CO-NH-.

Preferably, X is an anion such as chloride or bromide.

These polymers have a number average molecular mass (Mn) generally between 1000 and 100,000.

One can use more particularly the polymers which consist of recurring units corresponding to the following formula (V):

i: ·

--------- N (GH,} .: (CH 4; -X ·. · <·. · X ·:

x X '

In which R ₁₀ , Ru, R _[2 and R _n , identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms approximately, n and p are whole numbers varying from 2 to 8 approximately and, X is an anion derived from a mineral or organic acid. Mention may in particular be made of the polymer of designation INCI Hexadimethrine chloride, such as the compound of commercial designation MEXOMERE PO offered by the company CHIMEX.

When one or more cationic polymers are present in composition i) or ii) their total amount can range from 0.01 to 5% by weight, preferably from 0.05 to 25% by weight and better still from 0 , 1 to 2% by weight relative to the total weight of the composition i) or ii).

Preferably, the mixture weight ratio between compositions i) and ii), that is to say the weight ratio i) / ii) varies from 0.1 to 5, preferably from 0.2 to 2 , better from 0.5 to 1.5, even more preferably from 0.5 to 1.

Preferably, the time for mixing the compositions i) and ii) varies from 20 seconds to 4 minutes, preferably from 30 seconds to 3 minutes, better still from 45 to 150 seconds before said mixture is applied to the keratin fibers.

According to one embodiment, the coloring and / or lightening method according to the invention further comprises a step consisting in leaving the mixture of compositions i) and ii) on the keratin fibers, preferably of 1 approximately 60 minutes, and more preferably approximately 10 to 45 minutes.

According to one embodiment, the coloring and / or lightening method according to the invention further comprises a rinsing and / or washing step.

A subject of the invention is finally the use of a direct dye capable of changing color on contact with free radicals derived from oxygen, such as those described above, as an indicator of the time of mixing of compositions i) and ii) as defined above.

The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

The alkaline and oxidizing compositions were prepared from the following ingredients.

The proportions are indicated in% by weight of active material relative to the total weight of the composition.

[Paintings!]

Alkaline compositions Base A Base B1 Base B2 Steareth-2 1.35 1.35 1.35 Steareth-20 2.75 2.75 2.75 Cetearyl alcohol 8 8 8 Mineral oil 8 8 8 EDTA 0.5 0.5 0.5 Sodium metabisulfite 0.22 0.22 0.22 Hexadimethrine chloride 0.22 0.22 0.22 Ammonium hydroxide 7 7 7 Polyquatemium-6 0.37 0.37 0.37 Indicator dye- Acid Blue 9- Acid green 50 - 0.1- -0.1 Water qs 100 100 100

[Tables3]

Oxidizing compositions Oxidant A Oxidant B1 Oxidant B2 Mineral oil 50 50 50 Steareth-2 3.5 3.5 3.5 Steareth-20 1.5 1.5 1.5 Tocopherol 0.2 0.2 0.2 Tetrasodium pyrophosphate 0.04 0.04 0.04 Tetrasodium etidronate 0.2 0.2 0.2 Sodium salicylate 0.035 0.035 0.035 Hydrogen peroxide 12 12 12 Indicator dye- Acid Blue 9- Basic Red 13 - 0.1- -0.1 Water qs 100 100 100

The following mixtures were then produced in an alkaline composition / oxidizing composition weight ratio of 1/2:

- Base A + Oxidant A,

- Base A + Oxidant Bl,

- Base A + Oxidant B2,

- Base Al + Oxidant A, and

- Base A2 + Oxidant A.

The colorimetric parameters of the mixtures were then measured in the CIE system L * a * b * using a Konica Minolta CM2600d spectrocolorimeter (illuminant D65, angle 10 °, specular component included) in which L * represents the color intensity, a * indicates the green / red color axis and b * the blue / yellow color axis.

We followed the evolution of the color parameters L * a * b * of the mixtures over time, then we calculated the ΔΕ as defined above. It represents the variation in color between the mixture comprising a colored indicator (Base Al or A2 + Oxidant A) or (Base A + Oxidant B1 or B2) and the mixture not comprising a colored indicator (Base A + Oxidant A) . The results are shown in Table 4 below.

[Tables4]

Mixing time (seconds) L * (D65) a * (D65) b * (D65) ΔΕ Base A + Oxidant A 60 92.12 -1.95 1.53 - Base A + Oxidant B1 30 75.18 -21.71 -16.32 31.6 60 77.52 -18.72 -13.2 26.7 90 79.28 -16.14 -10.76 22.7 120 83.32 -9.14 -4.96 13.1 150 85.67 -4.48 -1.5 7.6 180 86.54 -2.86 -0.28 5.9 210 86.94 -2.16 0.27 5.3 Base A + Oxidant B2 60 92.48 -0.73 3.75 2.6 Base B1 + Oxidant A 30 80.68 -16.59 -11.47 22.7 60 85.92 -7 -3.87 9.7 90 87.57 -3.57 -1.41 5.7 120 88.13 -2.53 -0.58 4.6 Base B2 + Oxidant A 60 91.38 -2.88 6.65 5.3

With Acid Blue 9 in the oxidizing composition (oxidizing Bl), the optimal mixing time is around 2 minutes 30 seconds.

With Acid Blue 9 in the alkaline composition (Base Bl), Basic Red 13 (oxidant B2) and Acid Green (Base B2), the optimal mixing time is one minute.

Claims (1)

Claims [Claim 1] Process for dyeing and / or lightening keratin fibers, in particular human keratin fibers such as the hair, comprising a step of mixing an alkaline composition i) and a composition ii) comprising at least one chemical oxidizing agent , at least one of compositions i) and ii) comprising a direct dye capable of changing color on contact with free radical species derived from oxygen, until the mixture of compositions i) and ii) has a change in color visible to the naked eye. [Claim 2] Method according to claim 1, characterized in that it comprises at least the following steps: • mix i) a composition comprising at least one agent alkaline and optionally at least one oxidation dye precursor and ii) a composition comprising at least one chemical oxidizing agent, at least one of the compositions i) and ii) comprising at least one direct dye capable of changing color on contact of free radicals derived from oxygen, until the mixture of compositions i) and ii) exhibits a color change visible to the naked eye, then • apply the mixture of ingredients to the keratin fibers positions i) and ii). [Claim 3] Process according to claim 1 or 2, characterized in that the direct dye capable of changing color on contact with free radical species derived from oxygen is chosen from dyes of the triarylmethane or methine cyanine types, and their mixtures. [Claim 4] Process according to Claim 3, characterized in that the dyes of the triarylmethane type are chosen from the compounds of formula (I) below, their optical isomers, their geometric isomers, their tautomers, their acid or base salts, organic or inorganic , their solvates such as hydrates and their mixtures: ^R ; MR, ©

formula (I), in which, • R i, R 2, R ’i and R’ 2 identical or different, represent: • a hydrogen atom, • a C ₁ to C ₂ o, preferably C 1 to C ₄ , alkyl radical, linear or branched, such as methyl, ethyl and propyl, or • a benzyl radical optionally substituted by one or more groups SO ₃ or SO ₃ H; • the radicals R ₃ , independently of one another, identical or different, represent: • an alkyl radical -C _6, preferably C, to C _4, linear or branched, • a hydroxy radical, • a group SO ₃ or SO ₃ H, • or else two adjacent radicals R ₃ together form a ring 6 unsaturated links, preferably aromatic such as benzo, optionally substituted by one or more group SO ₃ or SO ₃ H; • q is an integer ranging from 0 to 4, preferably from 1 to 4; • R 4 represents: • a hydrogen atom, or • a radical -NR ₅ R ₆ , with R ₅ and R ₆ independently of one another, identical or different, representing: - a hydrogen atom, - a C 1 to C ₆ , preferably C 1 to C ₄ , alkyl radical, linear or branched, such as methyl, ethyl and propyl; Being heard that : ❖ the radical R ₂ is present or absent, symbolized by the dotted link, when R ₂ is present then the nitrogen atom which carries it is in cationic ammonium form, when R ₂ is absent then the nitrogen atom which carries it is not charged, (+) is not present, and ❖ the compound of formula (I) optionally comprises one or more An anions and optionally one or more M ⁺ cations to ensure the electroneutrality of the molecule ; with: - An representing an anion, preferably chosen from bromide, chloride, methylsulfate, toluenesulfonate ions or a mixture of these ions; and - M ⁺ representing a cation, preferably chosen from sodium, potassium, magnesium, calcium, zinc, ammonium ions or a mixture of these ions. [Claim 5] Method according to claim 4, characterized in that R ,, R ₂ , R 'i and R' ₂ , are identical. [Claim 6] Process according to claim 3, characterized in that the dyes of methine cyanine type are chosen from the compounds of formula (II), their organic or mineral acid salts, optical isomers, geometric isomers, and the solvates such that hydrates:

formula (II) in which: n represents an integer ranging from 1 to 3, preferably such as 1; Ra and Rb, identical or different, represent a hydrogen atom or an alkyl group Ci-C _4; particularly Rb represents a hydrogen atom and more particularly Ra and Rb represent a hydrogen atom; R ¹ represents a hydrogen atom or an alkyl group Ci-C _6, preferably C _r C ₄ linear or branched, such as methyl; R ² and R ³ form together with the carbon atoms which carry an optionally substituted benzo ring; • R ⁴ and R ⁵ , identical or different, represent: • a hydrogen atom, or • an amino radical -NR ⁶ R ⁷ with R ⁶ and R ⁷ identical or different, representing a hydrogen atom or an alkyl group in C ₁ -C ₆ optionally carrying a halogen atom, preferably R ⁶ represents an unsubstituted alkyl radical and R ⁷ an alkyl radical carrying a halogen atom; • W represents a group CRR ', where R and R' identical or different, representing a hydrogen atom or an alkyl group Ci-C _4; preferably an alkyl group C ₄ such as methyl; • Q represents an anionic counterion. [Claim 7] Process according to any one of the preceding claims, characterized in that the direct dye capable of changing color on contact with free radical species derived from oxygen is chosen from Acid Blue 9, Acid Green 50, Basic Violet 14, Basic Blue 7, Basic Red 13 and their mixtures. [Claim 8] Process according to any one of the preceding claims, characterized in that the direct dye (s) capable of changing color on contact with free radical species derived from oxygen are contained in composition i) or ii) in a total amount ranging from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight, better still from 0.075 to 1% by weight relative to the total weight of the composition i) or ii). [Claim 9] Process according to any one of the preceding claims, characterized in that the alkaline composition i) comprises one or more alkaline agents chosen from ammonia, ammonium hydroxide, alkanolamines such as monoethanolamine, triethanolamine and 2- amino-2-methyl-1-propanol, the hydroxides of an alkali or alkaline earth metal, ammonium or sodium carbonate, ammonium or sodium bicarbonate, alkali metal silicates such as metasilicates sodium, arginine, sodium or potassium glycinate and their mixtures, better among ammonia, ammonium hydroxide, alkanolamines such as monoethanolamine and their mixtures. [Claim 10] Process according to any one of the preceding claims, characterized in that the alkaline composition i) comprises one or more alkaline agents in a total content ranging from 0.01 to 20% by weight, in particular from 0.1 to 15% by weight , and preferably from 1 to 10% by weight, relative to the total weight of the composition i). [Claim 11] Process according to any one of the preceding claims, characterized in that the oxidizing agent is hydrogen peroxide. [Claim 12] Process according to any one of the preceding claims, characterized in that the chemical oxidizing agent (s) is or are used in a total content ranging from 2 to 30% by weight, preferably from 3 to 20% by weight, better still from 5 to 15% by weight relative to the total weight of the composition ii). [Claim 13] Process according to any one of the preceding claims, characterized in that the compositions i) and / or ii) further comprise at least one additive chosen from preferably liquid fatty substances, preferably nonionic surfactants, cationic polymers and their mixtures. [Claim 14] Method according to any one of the preceding claims, characterized in that the weight ratio of mixture between the compositions i) and ii) varies from 0.1 to 5, preferably from 0.2 to 2, better still from 0.5 to 1 , 5. [Claim 15] Process according to any one of the preceding claims, characterized in that the time for mixing the compositions i) and ii) varies from 20 seconds to 4 minutes, preferably from 30 seconds to 3 minutes, better still from 45 to 150 seconds, before said mixture is applied to keratin fibers. [Claim 16] Method according to any one of the preceding claims, characterized in that the ΔΕ is less than or equal to 10, preferably less than or equal to 8, said ΔΕ being calculated from colorimetric parameters in the CIE system L * a * b * measured using a spectrocolorimeter, and corresponding to the formula: Δ E =, * - L _Q “+ (a ₅ * - a _c *) + - (b- * —b _o . in which Li *, ai * and bi * represent the values measured on the composition resulting from the mixture of compositions i) and ii), and L _o *, a ₀ * and b ₀ * represent the values measured on the composition resulting from the mixture of compositions i ') and ii ') identical to compositions i) and ii) but free of direct dye capable of changing color on contact with free radicals derived from oxygen. [Claim 17] Method according to any one of the preceding claims, characterized in that it further comprises a step consisting in allowing the mixture of compositions i) and ii) to be placed on the keratin fibers, preferably from 1 to 60 minutes approximately, and more preferably from 10 to 45 minutes approximately. [Claim 18] Use of a direct dye capable of changing color in contact with free radicals derived from oxygen, as defined in claims 3 to 7, as an indicator of the mixing time of compositions i) and ii) as defined in the claims 1 and 2. [Claim 19] Use according to claim 18, characterized in that the ΔΕ is less than or equal to 10, preferably less than or equal to 8, said ΔΕ being calculated from colorimetric parameters in the CIE system L * a * b * measured by means of 'a spectrocolorimeter, and corresponding to the formula: Δ.Ε = in which Li *, ai * and bi * represent the values measured on the composition resulting from the mixture of compositions i) and ii), and L _o *, a ₀ * and b ₀ * represent the values measured on the composition resulting from the mixture of compositions i ') and ii') identical to compositions i) and ii) but free of direct dye capable of changing color in contact with free radicals derived from oxygen. FRENCH REPUBLIC