FR3102363A1 - PROCESS FOR TREATMENT OF KERATINIC FIBERS BY MEANS OF A COMPOSITION CONTAINING ARGININE AND AN OXIDIZING COMPOSITION - Google Patents

Abstract

The present application relates to a process for treating keratin fibers, in particular human keratin fibers such as the hair, from a composition comprising arginine and from a separate oxidizing composition comprising one or more chemical oxidizing agents. and one or more acrylic anionic associative polymers.

Description

METHOD FOR THE TREATMENT OF KERATIN FIBERS BY MEANS OF A COMPOSITION CONTAINING ARGININE AND AN OXIDIZING COMPOSITION

The subject of the present application is a method for treating keratin fibers, in particular human keratin fibers such as the hair, from a composition comprising arginine and from a separate oxidizing composition comprising one or more chemical oxidizing agents and one or more acrylic anionic associative polymers.

It is known to dye or bleach keratin fibres, and in particular human hair, with dye compositions containing oxidizing agents, alkaline agents and optionally oxidation dye precursors, such as oxidation bases, in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise to colored compounds by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diaminobenzenes, meta-aminophenols, meta- diphenols and certain heterocyclic compounds such as indole compounds.

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

In the field of hair coloring, there is always a need to develop ever more effective coloring compositions. In particular, there is still a need to implement in the coloring/bleaching process compositions having good qualities of use, in particular alkaline and oxidizing compositions which mix easily in order to lead to a ready-to-use composition. homogeneous, easy to distribute on the hair, without risk of dripping. In addition, it is sought to implement compositions making it possible to reduce unpleasant odors during use, to minimize the alterations of keratin fibers or the problems of comfort at the level of the scalp while maintaining a good level of dyeing efficiency.

Thus, the process must also make it possible to dye the keratinous fibers in an intense, tenacious, not very selective, chromatic manner, with a good rise in color, and capable of leading to colorations resistant to the various attacks that the fibers can undergo such as bad weather, washing and perspiration.

These aims are achieved with the present invention, the subject of which is in particular a method for treating keratin fibers, in particular human keratin fibers such as the hair, comprising:
To. at least one step for preparing a composition M comprising the mixture:
i. at least one composition A comprising arginine; with
ii. at least one oxidizing composition B distinct from composition A comprising:
- one or more chemical oxidizing agents, and
- one or more anionic acrylic associative polymers; Then
b. at least one step of applying to said keratin fibers said composition M.

It has been found that the treatment process according to the invention makes it possible to dye keratin fibers satisfactorily, in particular by leading to powerful, tenacious, chromatic, poorly selective colorations, and/or with a good rise in color.

Furthermore, the process according to the invention leads to colorations which are resistant to the various attacks which the keratin fibers may undergo, such as bad weather, light, washing and/or perspiration.

The compositions used in the treatment method according to the invention have good qualities of use, in particular the alkaline and oxidizing compositions mix easily and lead to a homogeneous ready-to-use composition, easy to distribute on the hair. , without risk of drips. In addition, these compositions make it possible to reduce unpleasant odors during use, to minimize the alterations of keratin fibres, while maintaining a good level of effectiveness.

This process of the invention is particularly advantageous when it is associated with oxidation dyes in the form of powder or even beads of oxidation dyes, each containing, preferably a single oxidation base or oxidation coupler. Indeed, the method according to the invention then makes it possible to use a specific coloring composition containing precise contents of oxidation dye precursors specifically chosen in order to obtain exactly the shade desired by the user.

Thus, when the process of the invention is implemented with a multitude of beads of oxidation dyes each containing a single oxidation dye, it makes it possible to combine a very large number of different oxidation precursors, at respectively different, and thus to color the keratin fibers according to a very wide range of possible colors while taking into account the nature and the state of said fibers.

On the other hand, the process according to this embodiment makes it possible to lead to a tinctorial result which is perfectly reproducible from one time to the next.

A subject of the invention is also a process for preparing a coloring composition, for coloring keratin fibres, in particular human keratin fibers such as the hair, comprising the mixture:
To. several solid particles, identical or different, each containing one or more oxidation dye precursors; with
b. at least one composition A comprising arginine; And
vs. at least one oxidizing composition B distinct from composition A comprising:
i) one or more chemical oxidizing agents, and
ii) one or more acrylic anionic associative polymers.

A subject of the invention is also the use of said composition, for the treatment, preferably the coloring/bleaching, of keratin fibers, in particular human keratin fibers such as the hair.

A subject of the invention is also a composition M' for the treatment, preferably coloring/bleaching, of keratin fibres, in particular human keratin fibers such as the hair, comprising arginine, one or more chemical oxidants and one or more several acrylic anionic associative polymers, and optionally one or more oxidation dye precursors.

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

In this description, and unless otherwise specified:

- the expression "at least one" is equivalent to the expression "one or more" and can be substituted therefor;

- the expression "included between" is equivalent to the expression "ranging from" and can be substituted therefor, and implies that the terminals are included;

- By "keratin fibers" according to the present application, is preferably meant human keratin fibers and more particularly the hair.

The treatment process of the invention is preferably a process for dyeing/bleaching keratin fibres.

Oxidation dye precursors
When the treatment process according to the invention is a process for dyeing keratin fibres, the step for preparing composition M comprises mixing with one or more oxidation dye precursors.

According to a preferred embodiment of the invention, the oxidation dye precursor(s) is (are) introduced in the form of solid particles, which are identical or different, each containing one or more dye precursors of oxidation.

According to this embodiment, said precursors may be identical or different from one solid particle to another.

It is observed for this embodiment that the solid particles each containing a single dose of oxidation dye precursor exhibit very good storage stability. In addition, when the solid particles are used in the process of the invention, these disintegrate quickly and lead easily and quickly to a homogeneous mixture with the aqueous compositions used in the process.

Preferably, said solid particles comprise:
- one or more solid particles of a first type P1 containing a single oxidation dye precursor C1; And
- one or more solid particles of a second type P2 containing a single oxidation dye precursor C2;
it being understood that the oxidation dye precursor C1 is different from the oxidation dye precursor C2.

Step a. preparation of a composition M according to the invention therefore preferably comprises the mixture:
- one or more solid particles of a first type P1 containing a single oxidation dye precursor C1; And
- one or more solid particles of a second type P2 containing a single oxidation dye precursor C2; with
- at least one composition A comprising arginine; And
- at least one distinct oxidizing composition B comprising one or more chemical oxidizing agents and one or more anionic acrylic associative polymers;
it being understood that the oxidation dye precursor C1 is different from the oxidation dye precursor C2.
Thus, according to this preference, at least two types of solid particles used in the process according to the invention do not comprise the same oxidation dye precursor.

More preferably, each type of solid particle according to the invention comprises a single oxidation dye precursor in a content of between 0.1 and 50% by weight relative to the total weight of the solid particle containing it.

According to a preferred embodiment, step a. preparation of a composition M further comprises the mixture with one or more solid particles of a third type P3, containing a single oxidation dye precursor C3 different from the coloring precursors C1 and C2, more preferably in a content comprised between 0.1 and 50% by weight relative to the total weight of the solid particle(s) P3. It is thus possible to mix as much oxidation dye precursor as necessary, and this in the respective proportions necessary, to achieve the desired shade.

Thus, according to another preferred embodiment, step a. preparation of a composition M comprises the mixture of n types of solid particles P1 to Pn (with n representing an integer greater than or equal to 3, and preferably between 3 and 20, more preferably between 3 and 15, and more preferably still between 4 and 10), each type of solid particle P1 to Pn containing a single oxidation dye precursor (respectively C1 to Cn), more preferably in a content of between 0.1 and 50% by weight relative to the total weight of the solid particles P1 to Pn respectively, and it being understood that said precursors C1 to Cn are all different from each other.

According to a particular embodiment of the invention, the composition M also comprises the mixture of one or more solid particles of the P'x type (with x representing an integer greater than or equal to 1, and in particular ranging from 1 to n with n as previously described, and preferably between 1 and 20, more preferably between 1 and 15, and even more preferably between 1 and 10) containing a single oxidation dye precursor Cx, more preferably in a content of between 0.1 and 50% by weight relative to the total weight of the solid particle(s) of P'x type; said solid particle of P'x type corresponding to the solid particle Px previously described, unlike the content of oxidation dye precursor Cx.

By way of example of this particular embodiment of the invention, composition M may comprise the mixture:
(i) one or more solid particles of a first type P1 containing a single oxidation dye precursor C1, preferably in a content of between 0.1 and 50% by weight relative to the total weight of the ( solid particle(s) of type P1;
(ii) one or more solid particles of a second type P2 containing a single oxidation dye precursor C2, preferably in a content of between 0.1 and 50% by weight relative to the total weight of the ( solid particle(s) of type P2; And
(iii) one or more solid particles of type P'1 containing only said oxidation dye precursor C1, preferably in a content of between 0.1 and 50% by weight relative to the total weight of the ) solid particle(s) of type P'1; with
(iv) at least one composition A comprising arginine;
(v) at least one distinct oxidizing composition B comprising one or more chemical oxidizing agents and one or more acrylic anionic associative polymers;
Being heard that :
- the oxidation dye precursor C1 is different from the oxidation dye precursor C2;
- the content of oxidation dye precursor C1 contained in the solid particle(s) P1 is different from the content of oxidation dye precursor C1 contained in the solid particle(s) (s) P'1.

Preferably, the oxidation dye precursors, capable of being used in general in the process of the invention, and in particular of being contained in the solid particles, are chosen from oxidation bases and couplers oxidation; more preferentially among the oxidation bases.

According to a preferred embodiment of the invention, the precursor of oxidation dye C1 as defined above is chosen from oxidation bases and the precursor of oxidation dye C2 as defined above is chosen from couplers of oxidation (or vice versa).

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

Among the para-phenylenediamines which may be mentioned 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, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis( β-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(ß-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl- para -phenylenediamine, 2-methoxymethyl-para-phenylenediamine, 2 -fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para -phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2 -thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4'-aminophenyl)pyrrolidine and the corresponding acid addition salts.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para- phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine , 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine and the corresponding acid addition salts.

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

Among the para-aminophenols which are mentioned are, for example, para-aminophenol, 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-amino-2-aminomethylphenol, 4-amino-2-(β- hydroxyethylaminomethyl)phenol and 4-amino-2-fluorophenol and the corresponding acid addition salts.

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

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

Among the pyridine derivatives which may be mentioned are the compounds described for example 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[1,5-a]pyridine oxidation bases or the corresponding addition salts described, for example, in the application of patent FR 2 801 308. Examples which may be mentioned include pyrazolo[1,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1,5-a]pyrid-3-ylamine, 2-morpholin- 4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1,5-a]pyridine-2-carboxylic acid, 2-methoxypyrazolo[1,5-a]pyrid-3- ylamine, (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1,5-a]pyrid-5-yl)ethanol, 2-(3- aminopyrazolo[1,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1,5-a]pyrid-2-yl)methanol, 3,6-diaminopyrazolo[1,5-a]pyridine , 3,4-diaminopyrazolo[1,5-a]pyridine, pyrazolo[1,5-a]pyridine-3,7-diamine, 7-morpholin-4-ylpyrazolo[1,5-a]pyrid- 3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-morpholin-4-ylpyrazolo[1,5-a]pyrid-3-ylamine, 2-[(3-aminopyrazolo [1,5-a]pyrid-5-yl)(2-hydroxyethyl)-amino]ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl)(2-hydroxyethyl)amino ]ethanol, 3-aminopyrazolo[1,5-a]pyridin-5-ol, 3-aminopyrazolo[1,5-a]pyridin-4-ol, 3-aminopyrazolo[1,5-a]pyridin- 6-ol, 3-aminopyrazolo[1,5-a]pyridin-7-ol, 2-β-hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine; 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)(C ₁ -C ₆ )(alkyl)amino group, said alkyl group possibly being substituted by at least one hydroxy, amino or imidazolium group;
b) a heterocycloalkyl group containing 5 to 7 members and 1 to 3 heteroatoms, optionally cationic, optionally substituted by one or more (C ₁ -C ₆ )alkyl groups, such as a di(C ₁ -C ₄ )alkylpiperazinium group; Or
c) a (C ₁ -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 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-triamino -pyrimidine, 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 are the compounds described in patents DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR A-2 733 749 and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-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, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3- tert -butyl-1-methylpyrazole, 4,5-diamino- 1- tert -butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino -1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-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, 3,5-diamino-4-(β-hydroxyethyl)amino-1 -methylpyrazole and the corresponding addition salts. It is also possible to use 4,5-diamino-1-(β-methoxyethyl)pyrazole.

A 4,5-diaminopyrazole will preferably be used and even more preferably 4,5-diamino-1-(β-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 corresponding addition salts: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo [1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-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[1,2-a]pyrazol-1-one, 2 -amino-3-dimethylamino-6,7-dihydro-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.

2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a corresponding salt will preferably be used.

Preferably, 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1 will be used. -one and/or 2-β-hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine and/or a corresponding salt as heterocyclic bases.

According to a preferred embodiment of the invention, the oxidation base(s) are chosen from para-phenylenediamine, para-toluenediamine, para-aminophenol, N,N-bis(β-hydroxyethyl)-para- phenylenediamine, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-β-hydroxyethoxy-3-amino-pyrazolo[1,5-a]pyridine, and their addition salts.

Preferably, when the oxidation dye precursor(s) is (are) contained in one or more solid particles as defined previously and is (are) a base(s) of oxidation, the oxidation base(s) advantageously represent(s) 0.1% to 50% by weight, more preferably 0.3% to 25% by weight, more preferably still 0.4% to 22% by weight, relative to the total weight of the solid particle containing it(them).

By way of example, the oxidation couplers can be chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents, as well as their geometric isomers or optics, their tautomers, their corresponding addition salts or their solvates according to the invention.

Mention may be made, for example, of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-amino-4-(ß-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1 -dimethylaminobenzene, sesamol, 1-ß-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N -methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N-(ß-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2 ,6-bis(ß-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5 -one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole and 6- methylpyrazolo[1,5-a]benzimidazole, 2-methyl-5-aminophenol, 5-N-(ß-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 3-amino-2-chloro-6 -methylphenol, 2-[3-amino-4-methoxyphenyl]amino)ethanol the corresponding addition salts with an acid.

According to a preferred embodiment of the invention, the oxidation coupler(s) are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents, heterocyclic coupling agents , and their corresponding addition salts or solvates, ; more preferably still 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 3-aminophenol, 6-hydroxybenzomorpholine, 5-N-(ß-hydroxyethyl)amino-2-methylphenol, 2, 4-diamino-1-(ß-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 6-hydroxyindole, 4-chloro-1,3-dihydroxybenzene, 2-amino-3-hydroxypyridine, 3- amino-2-chloro-6-methylphenol, α-naphthol, 2-[3-amino-4-methoxyphenyl]amino)ethanol and their addition salts.

Preferably, when the oxidation dye precursor(s) is (are) contained in one or more solid particles as defined previously and is (are) a coupler(s) of oxidation, the oxidation coupler(s) advantageously represent(s) 0.1% to 50% by weight, more preferably 0.3% to 25% by weight, more preferably still 0.4% to 22% by weight, relative to the total weight of the solid particle containing it(these).

Preferably, the total content of oxidation dye precursor(s) present in each solid particle is between 0.1% and 50% by weight, more preferably between 0.3% and 25% by weight, more preferably still between 0.4% and 22% by weight, relative to the total weight of each solid particle containing it(these).

Preferably, the total content of oxidation dye precursor(s) present in composition M advantageously represents 0.0001 to 15% by weight, more preferably 0.001% to 10% by weight, even more preferably 0.005% at 5% by weight, relative to the total weight of composition M.

According to a preferred embodiment, when the oxidation dye precursor(s) are contained in one or more identical or different solid particles as defined above, the content of dye precursor(s) d oxidation (for example C1, C2, and more generally C1 to Cn) advantageously represents 0.1 to 50% by weight, more preferably 0.3% to 25% by weight, more preferably still 0.4% to 22% by weight, relative to the total weight of each solid particle containing it(s) (for example solid particles of type P1, P2, and more generally P1 to Pn respectively).

In general, the addition salts of oxidation bases or oxidation couplers 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.

Direct dyes

When the treatment process according to the invention is a process for dyeing keratin fibres, the step for preparing composition M may optionally comprise mixing with one or more direct dyes.

According to a preferred embodiment of the invention, and in the same way as for the oxidation dye precursors above, the direct dye(s) is (are) introduced under form of solid particles, identical or different, each containing one or more direct dye(s).

According to this embodiment, said direct dye(s) may be identical or different from one solid particle to another.

In particular, the direct dye(s) can be chosen from cationic, anionic, nonionic direct dyes, and mixtures thereof; more particularly among cationic and nonionic direct dyes and mixtures thereof.

Direct dyes can be synthetic or natural.

Examples of suitable direct dyes which may be mentioned are azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

Mention may be made of the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

In particular, the useful direct dyes can be chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or corresponding derivatives:
, An ^- Basic Red 51

, An ^- Basic Orange 31

, An ^- Basic Yellow 87

Among the natural direct dyes that can be used, we can mention hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein. Extracts or decoctions containing these natural dyes and in particular henna-based poultices or extracts can also be used.

Preferably, when the direct dye(s) are present in said solid particles, the direct dye(s) advantageously represent(s) 0.001% to 10% by weight, more preferably 0.005% to 5% by weight , relative to the total weight of each solid particle containing it.

More preferably, when the direct dye(s) are present in the step for preparing composition M, the total content of direct dye(s) present in composition M advantageously represents 0.0001 to 15% by weight, more preferably 0.001% to 10% by weight, more preferably still 0.005% to 5% by weight, relative to the total weight of composition M.

According to another preferred embodiment of the invention, when the treatment process according to the invention is a process for dyeing keratin fibres, the step for preparing composition M comprises mixing with one or more direct dyes and with one or more oxidation dye precursors, more preferably the direct dye(s) and the oxidation dye precursor(s) are in the form of solid particles as described above.

Binding agents
when the oxidation dye precursor(s) and/or the direct dye(s) are contained in one or more solid particles, identical or different, as defined previously, the solid particles (for example solid particles of type P1 and P2 and more generally P1 to Pn) preferably further comprise at least one binding agent.

By "binding agent" is meant in the sense of the invention a compound contributing to the cohesion of the solid particle. The binding agent allows in particular the agglomeration of the various components constituting the solid particle.

By way of example of binding agents, mention may in particular be made of proteins (such as gelatin); saccharides and their derivatives, oligosaccharides and their derivatives including disaccharides (such as sucrose and lactose) in particular in their anhydrous or hydrated forms, and sugar alcohols (such as xylitol, sorbitol and maltitol); polyvinyl alcohol (PVA); polysaccharides and their derivatives (for example, starches, cellulose and/or modified cellulose); alginate; and gums (eg, acacia gum, guar gum).

Examples of suitable modified cellulose include microcrystalline cellulose (MCC), especially in their anhydrous or hydrated forms, and cellulose ethers such as hydroxypropyl cellulose (HPC) and hydroxypropyl methyl cellulose (HPMC).

Preferably, the binding agent(s) are chosen from saccharides and their derivatives, oligosaccharides and their derivatives, polysaccharides and their derivatives, polyvinyl alcohol (PVA), and mixtures thereof; more preferably from lactose in particular in anhydrous or hydrated form, microcrystalline cellulose (MCC) in particular in anhydrous or hydrated form, polyvinyl alcohol (PVA), cellulose ethers such as hydroxypropyl cellulose (HPC) and hydroxypropylmethyl cellulose (HPMC), and mixtures thereof.

Preferably, when the binding agent(s) are present in the solid particles, the total content of binding agent(s) is greater than or equal to 30% by weight; more preferably greater than or equal to 50% by weight; more preferably still between 50% and 99.9% by weight, better still between 60% and 99.9% by weight, even better still between 70% and 99.9% by weight, relative to the total weight of each solid particle the (s) container.

Disintegrating agents
When the oxidation dye precursor(s) and/or the direct dye(s) are contained in one or more solid particles, identical or different, as defined previously, the solid particles (for example solid particles of type P1 and P2 and more generally P1 to Pn) preferably further comprise at least one disintegrating agent.

Within the meaning of the present invention, the term "disintegrants" means a class of agents, preferably a class of polymers, particularly effective in inducing the disintegration of a solid particle (for example a tablet). A special class of disintegrating agents are called "superdisintegrants" because they are generally effective at low concentrations.

Disintegrating agents can be hygroscopic compounds that act by absorbing liquid from a medium when brought into contact with that medium (e.g. water from an aqueous medium). Such absorption may then induce disintegration by causing considerable swelling of the disintegrating agent and/or enhancing capillary action. The swelling pressure exerted by a disintegrating agent swollen in an outward or radial direction can cause a solid particle (eg a tablet) to burst.

By way of example of disintegrating agents, or even superdisintegrating agents, mention may in particular be made of crosslinked celluloses such as croscarmellose (or crosslinked carboxymethylcellulose, which is generally used in the form of the sodium salt) and its derivatives, marketed for example under the Ac-Di-Sol ^® , Explocel ^® , Nymcel ZSX ^® , Pharmacel ^® XL, Primellose ^® , Solutab ^® and Vivasol ^® references; crospovidone (or cross-linked polyvinylpyrrolidone) and its derivatives, marketed for example under the references Crospovidone ^M® , ^Kollidon® and ^{Polyplasdone®} ; cross-linked starch such as sodium starch glycolate, marketed for example under the references ^Explotab® , ^Explotab® CLV, ^Explosol® , ^Primojel® , ^Tablo® and ^Vivastar® ; cross-linked alginic acids, marketed for example under the reference ^Satialgine® ; crosslinked polyacrylic compounds such as ion exchange resins, marketed for example under the references Indion ^® 414, Tulsion ^® 339 and Amberlite ^® IRP; and certain polysaccharides, such as soy polysaccharide, marketed for example under the references ^Emcosoy® superdisintegrant.

Preferably, the disintegrating agent(s) are polymeric; more preferably each type of solid particle comprises at least one disintegrating polymer, more preferably at least one superdisintegrating polymer; more preferably still at least one superdisintegrating polymer chosen from cross-linked polymers of vinylpyrrolidone and its derivatives, and mixtures thereof; even better among crosslinked polyvinylpyrrolidones, crosslinked vinylpyrrolidone/vinyl acetate copolymers, and mixtures thereof.

Preferably, when the disintegrating agent(s) are present in the solid particles, the total content of disintegrating agent(s) is between 0.5 and 15% by weight; more preferably between 1 and 12% by weight, more preferably still between 2% and 10% by weight, relative to the total weight of each solid particle containing it(s).

Antioxidants
When the oxidation dye precursor(s) and/or the direct dye(s) are contained in one or more solid particles, identical or different, as defined previously, the solid particles (for example solid particles of type P1 and P2 and more generally P1 to Pn) preferably further comprise at least one antioxidant.

By way of example of antioxidant agent(s), mention may in particular be made of ascorbic acid, its salts and its derivatives (such as sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate); salicylic acid, its salts and its derivatives (such as sodium salicylate); mercaptans and inorganic sulphites (such as sodium sulphite, sodium bisulphite, sodium metabisulphite, potassium sulphite and thioglycolic acid); 2,6-di-tert-butyl-4-methylphenol (BHT); butylated hydroxyanisole (BHA); sodium dithionite; and their mixtures.

Preferably, the antioxidant agent(s) are chosen from ascorbic acid, its salts and its derivatives (such as sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate); salicylic acid, its salts and its derivatives (such as sodium salicylate), mercaptans and inorganic sulphites (such as sodium sulphite, sodium bisulphite, sodium metabisulphite, potassium sulphite and thioglycolic acid), and mixtures thereof; more preferably from ascorbic acid, sodium sulphite, sodium bisulphite, sodium metabisulphite, sodium salicylate, and mixtures thereof.

Preferably, when the antioxidant agent(s) are present in the solid particles, the total content of antioxidant agent(s) is between 0.1 and 15% by weight; more preferably between 0.3 and 12% by weight, more preferably still between 0.4% and 10% by weight, better still between 0.5 and 5% by weight relative to the total weight of each solid particle containing the .

Lubricating and/or anti-adherent agents
When the oxidation dye precursor(s) and/or the direct dye(s) are contained in one or more solid particles, identical or different, as defined above, the solid particles (for example solid particles of type P1 and P2 and more generally P1 to Pn) preferably further comprise at least one lubricating and/or anti-adherent agent.

Within the meaning of the invention, the term "lubricating and/or anti-adherent agent" is understood to mean a compound making it possible to reduce, or even prevent, the agglomeration of the ingredients of the solid particles, to reduce adhesion (in particular during a compression step), and/or to improve the flow of the ingredients of the solid particles by reducing the friction and the cohesion between the ingredients.

Preferably, the lubricating and/or anti-adherent agent(s) are chosen from magnesium stearate, calcium silicate, magnesium silicate, magnesium carbonate, silicon dioxide, talc, silica, acid stearic acid, sodium stearoyl fumarate, and mixtures thereof; more preferably from silica, magnesium stearate, and mixtures thereof.

Preferably, when the lubricating and/or anti-adherent agent(s) are present in the solid particles, the total content of lubricating and/or anti-adherent agent(s) is between 0.1 and 10% by weight; more preferably between 0.3 and 8% by weight, more preferably still between 0.5% and 5% by weight, relative to the total weight of each solid particle containing it(these).

The top coating layer
When the oxidation dye precursor(s) and/or the direct dye(s) are contained in one or more solid particles, identical or different, as defined above, the solid particles (for example solid particles of type P1 and P2 and more generally P1 to Pn) preferably further comprise an upper coating layer (also called upper film coating layer).

The upper coating layer may optionally comprise cellulose ethers such as those described above.

The top coating layer may optionally include one or more other compounds such as polyethylene glycol (PEG); polyvinyl alcohol (PVA); polyvinylpyrrolidone (PVP); their copolymers (e.g. polyvinyl alcohol-polyethylene glycol PVA/PEG copolymer); sugars such as xanthan; and their mixtures.

Preferably, the upper coating layer comprises at least two different cellulose ethers.

According to a preferred embodiment of the invention, the upper coating layer comprises at least one cellulose ether as described above; more preferably a cellulose ether chosen from carboxymethylcellulose (CMC), ethylcellulose (CE), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), methylhydroxyethylcellulose (MHEC), and mixtures thereof, better still from hydroxypropylcellulose (HPC), hydroxypropyl methylcellulose (HPMC), and mixtures thereof.

More preferably, the upper coating layer comprises hydroxypropylcellulose (HPC) and hydroxypropylmethylcellulose (HPMC).

Preferably according to this embodiment of the invention, the content of cellulose ether(s) present in the upper coating layer is between 30 and 99% by weight; more preferably between 40 and 90% by weight, more preferably still between 50 and 70% by weight, relative to the total weight of the upper coating layer.

According to another preferred embodiment according to the invention, the upper coating layer comprises at least one lubricating and/or anti-adherent agent such as those described previously; more preferably at least one lubricating and/or anti-adherent agent chosen from calcium silicate, magnesium silicate, magnesium carbonate, silicon dioxide, talc, silica, and mixtures thereof; more preferably, the lubricating and/or anti-adherent agent is talc.

Preferably according to this embodiment, the total content of lubricating agent(s) and/or anti-adherent agent(s) present in the upper coating layer is between 1 and 40% by weight; more preferably between 2 and 30% by weight, relative to the total weight of the upper coating layer.

Preferably, the upper coating layer further comprises one or more pigments.

By way of example, the pigments can be white or colored, mineral and/or organic, coated or not. Mention may be made, among the mineral pigments, of metal oxides, in particular titanium dioxide, optionally surface-treated, zirconium, zinc or cerium oxides, as well as iron, titanium or chromium oxides, manganese violet, ultramarine blue, ultramarine pink, chromium hydrate and ferric blue, and mixtures thereof. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum, and mixtures thereof.

According to a preferred embodiment of the invention, the upper coating layer also comprises one or more pigments chosen from zirconium oxides, zinc oxides, cerium oxides, iron oxides, titanium oxides , chromium oxides, manganese violet, ultramarine blue, ultramarine pink, chromium hydrate and ferric blue, and mixtures thereof; more preferably one or more pigments chosen from titanium oxides such as titanium dioxide, iron oxides, chromium oxides, in particular green chromium oxide, and mixtures thereof.

When the upper coating layer comprises one or more pigments, the pigment(s) advantageously represents a total content ranging from 1% to 50% by weight, more preferably 5% to 40% by weight, by relative to the total weight of the upper coating layer.

Preferably, said solid particles as previously described are anhydrous.
The term "anhydrous solid particle" means that the solid particle contains less than 2% by weight of water, preferably less than 1% by weight of water, and even more preferably less than 0.5% by weight of water relative to the total weight of the solid particle, and even said solid particle is free of water. In particular, any water present is not added during the preparation of the solid particle but corresponds to the residual water provided by the mixed ingredients.

Said solid particles as previously described may advantageously be in a spherical or spheroidal form; more preferably in a spherical shape, such as a ball shape.

Preferably, said solid particles have an average volume of between 25 and 125 mm ³ ; more preferably between 30 and 90 mm ³ ; more preferably still between 45 and 65mm ³ .

The volume V of a solid particle in a substantially spherical or spheroidal form can in particular be calculated by the following equation:
V = (4/3).π.r ³
where r represents the radius of the solid particle.

Preferably, said solid particles have an average mass of between 30 and 120mg; more preferably between 40 and 80mg; more preferably between 50 and 70mg.

Preferably, the average hardness of said solid particles is between 2 and 15 kPa; more preferably between 2 and 11 kPa.

The average hardness of said solid particles can for example be measured using a semi-automatic tablet testing system commonly used in the pharmaceutical field, in particular using the Pharmatron ST50 device.

Preferably, the solid particles according to the invention have an average disintegration time in 25 mL of hydrogen peroxide (at 6% by weight of H ₂ O ₂ ) at 25° C. and at atmospheric pressure of less than 60 seconds; more preferably less than 40 seconds; even better between 1 and 30 seconds.

For example, the average disintegration time can be measured using the following method:
1) in a 50mL beaker, 25mL of an oxidizing aqueous composition comprising 6% by weight of hydrogen peroxide are poured; Then
2) 10 identical solid coloring particles according to the invention are added all at once; the contents of the beaker are not mixed; Then
3) the stopwatch is started;
4) the stopwatch is stopped once all the solid particles have clearly disintegrated visually; that is to say once it is observed that the solid particles form a soft mass no longer containing a firm nucleus; and finally
5) the average disintegration time is noted on the chronometer.

Said solid particles are advantageously prepared according to conventional methods for preparing tablets, optionally film-coated, such as the methods used in the pharmaceutical industry.

More particularly, the solid particles according to the invention can be prepared by the dry route according to the following steps:
- grinding of the ingredients of the solid particle; Then
- sieving the powder obtained; Then
- mixing said powder; Then
- direct compression of the mixture obtained in solid particles; and eventually
- coating of the solid particles obtained.

According to another particular method of preparation, the solid particles according to the invention can be prepared by wet granulation according to the following steps:
- premix of the binding agent(s) (for example lactose, microcrystalline cellulose, polyvinyl alcohol (PVA)), and of the dye(s); Then
- spraying on the premix of the disintegrating agent(s) (for example a cross-linked polyvinylpyrrolidone) in solution in one or more solvents such as those described in the paragraph below for the coating composition, in particular in water, for obtaining the desired aggregate; Then
- drying of the aggregate; Then
- grinding of the other ingredients of the solid particle; Then
- sieving of the powder obtained by the grinding and of the aggregate; Then
- mixing of the powders obtained by sieving; Then
- direct compression of the mixture obtained in solid particles; and eventually
- coating of the solid particles obtained.

The coating composition, allowing the coating of the solid particles, comprises one or more cellulose ethers as previously described for the upper coating layer.

Preferably, said coating composition further comprises one or more of the preferred top coating layer ingredients as previously described; more preferentially in contents as previously described in the upper coating layer.

More preferably, said coating composition further comprises one or more solvents chosen from water, C ₁ -C ₆ alcohols, and mixtures thereof; more preferably still chosen from water, ethanol, and mixtures thereof.

By way of example, the coating composition can be prepared from one or more solvents, in particular as described above, and from a mixture containing hydroxypropylmethylcellulose and hydroxypropylcellulose. According to this example, the coating composition may optionally contain one or more fatty substances, preferably liquid at 25° C. and atmospheric pressure, such as one or more fatty alcohols, fatty esters and/or triglycerides, for example chosen from octyldodecanol, isopropyl mysistate vegetable oil and/or caprylic/capric acid triglyceride.

The composition may also optionally contain talc and/or pigments to color the coating, preferably talc and pigments such as titanium dioxide.

The grinding step can in particular be carried out using a grinder, for example of the U5 ^{Quadro® COMIL®} type.

The screening step can in particular be carried out using a granulator, for example of the ROTO P50 type (Zanchetta) or High Shear Mixer P/VAC-10 (Diosna).

The mixing step can in particular be carried out using a mixer, for example of the MB015 Blender type (Pharmatech).

The direct compression step of the mixture can in particular be carried out using a compression table, for example of the PR-1500 (PTK) type.

The step of coating said particles can in particular be carried out using a film-coating station, for example of the LDCS-Pilot HI- ^COATER® (Freund-vector) type.

Membership A:
The treatment method according to the present invention uses at least one composition A comprising arginine.

Preferably, the total arginine content present in composition A is between 0.05 and 25% by weight, more preferably between 0.1 and 15% by weight, more preferably still between 0.5 and 10% by weight, or even between 1 and 5% by weight, relative to the total weight of composition A.

Preferably, the water content of composition A according to the invention is between 30 and 99% by weight; more preferably between 40 and 90% by weight, even better between 50 and 80% by weight, relative to the total weight of composition A.

Additional alkaline agents
Composition A according to the invention preferably also comprises at least one additional alkaline agent other than arginine.

Preferably, the additional alkaline agent(s) can be chosen from organic alkaline agents and inorganic alkaline agents.

Preferably, the additional organic alkaline agent(s) are chosen from organic amines whose pK _b at 25° C. is less than 12, and more preferably less than 10, even more advantageously less than 6. It should be noted that it this is the pK _b corresponding to the highest basicity function. Furthermore, the organic amines do not comprise a fatty, alkyl or alkenyl chain comprising more than ten carbon atoms.

The additional organic alkaline agent(s) are preferably chosen from alkanolamines such as mono-, di- or tri-alkanolamines, comprising one to three C ₁ to C ₄ hydroxyalkyl radicals, identical or not.

By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more alkyl groups, linear or branched, C ₁ to C ₈ carrying one or more hydroxy radicals.

The alkanolamines chosen from monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, 2-amino-2-methyl-1- propanol, triisopropanol-amine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethylamino-methane . Among the alkanolamines, it is very particularly preferred to use monoethanolamine.

The amino acids different from arginine that can be used are of natural or synthetic origin, in their L, D, or racemic form and comprise at least one acid function chosen more particularly from carboxylic, sulphonic, phosphonic or phosphoric acid functions. Amino acids can be in neutral or ionic form.

As amino acids different from arginine which can be used in the present invention, mention may be made in particular of aspartic acid, glutamic acid, alanine, ornithine, citrulline, asparagine, carnitine, cysteine, glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acids other than arginine are basic amino acids comprising an additional amine function optionally included in a cycle or in a ureido function.

The organic amine can also be chosen from organic amines of the heterocyclic type. Mention may in particular be made, in addition to the histidine already mentioned in the amino acids, of pyridine, piperidine, imidazole, triazole, tetrazole, benzimidazole.

The organic amine can also be chosen from amino acid dipeptides. As amino acid dipeptides that can be used in the present invention, mention may be made in particular of carnosine, anserine and balenine.

The organic amine can also be chosen from compounds comprising a guanidine function. As amines of this type which can be used in the present invention, mention may in particular be made, in addition to creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin, agmatine, n -amidinoalanine, 3-guanidino-propionic acid, 4-guanidinobutyric acid and 2-([amino(imino)methyl]amino)-ethane-1-sulfonic acid.

Among the additional inorganic alkaline agents that can be used in the process according to the invention, mention may be made of mineral hydroxides.

The mineral hydroxides can be chosen from hydroxides of alkali metals or alkaline earth metals, of transition metals, of ammonium. As mineral hydroxides, mention may be made, for example, of ammonium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, strontium, manganese hydroxide, zinc hydroxide.

Among the mineral hydroxides, ammonium hydroxide, also called ammonia, is preferred.

The additional inorganic alkaline agent(s) can also be chosen from urea, ammonium salts such as ammonium chloride, ammonium sulphate, ammonium phosphate or ammonium nitrate, silicates, phosphates or carbonates of alkali or alkaline-earth metals, such as lithium, sodium, potassium, magnesium, calcium, barium, and mixtures thereof, preferably from alkali or alkaline-earth metal silicates, in particular alkali or alkaline earth metal metasilicates such as sodium metasilicate

Preferably, the additional alkaline agent(s) other than arginine, useful in the invention, are chosen from ammonia, alkali metal or alkaline earth metal metasilicates, alkanolamines, amino acids in neutral or ionic form, in particular basic amino acids, compounds comprising a guanidine function, and preferably from ammonia, alkali metal or alkaline earth metal metasilicates and alkanolamines.

According to a preferred embodiment of the invention, composition A comprises one or more additional alkaline agents other than arginine; more preferably chosen from ammonia, alkanolamines, alkali metal or alkaline earth metal metasilicates, and mixtures thereof; more preferably still from ammonia, monoethanolamine, sodium metasilicate, and mixtures thereof.

Preferably, when the additional alkaline agent(s) other than arginine are present in composition A, the total content of additional alkaline agent(s) other than arginine is between 0 0.5 and 25% by weight, more preferably between 0.1 and 20% by weight, and even more preferably between 0.5 and 15% by weight, relative to the total weight of composition A.

Advantageously, the pH of the aqueous composition A according to the invention generally varies from 8 to 13, preferably from 9 to 12.5, better still from 10 to 12.5.

Oxidant Composition B:

The treatment method according to the present invention uses at least one oxidizing composition B distinct from composition A comprising one or more chemical oxidizing agents and one or more anionic acrylic associative polymers.

Preferably, the water content of the oxidizing composition B according to the invention is between 30 and 99% by weight; more preferably between 50 and 99% by weight, even better between 60 and 90% by weight, relative to the total weight of the aqueous composition B.

Chemical oxidizing agents
The oxidizing composition B according to the invention comprises one or more chemical oxidizing agents.

By “ chemical oxidizing agent ”, is meant within the meaning of the present invention an oxidizing agent different from the oxygen in the air.

The chemical oxidizing agent(s) (or bleaching agents) that can be used in the present invention can be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, in particular sodium persulphate, potassium persulphate and ammonium persulphate, peracids and oxidase enzymes (with their possible cofactors) among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; more preferably, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, persalts, and mixtures thereof.

Preferably, the total content of chemical oxidizing agent(s) present in the oxidizing composition B is between 0.1 and 35% by weight, more preferably between 0.1 and 30% by weight, and more preferably still between 0.5 and 25% by weight, better still 2 to 12% by weight relative to the total weight of the oxidizing composition B.

Anionic acrylic associative polymers
The oxidizing composition B according to the invention comprises one or more anionic acrylic associative polymers.

It is recalled that “associative polymers” are polymers capable, in an aqueous medium, of combining reversibly with each other or with other molecules.

Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone.

By “hydrophobic zone”, is meant a radical or polymer with a hydrocarbon chain, saturated or not, linear or branched, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms. carbon and more preferably from 18 to 30 carbon atoms.

Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group can come from a fatty alcohol such as for example stearyl alcohol, dodecyl alcohol, decyl alcohol. It can also designate a hydrocarbon-based polymer such as for example polybutadiene.

By "fatty alcohol", within the meaning of the invention, is meant a compound of formula R-OH with R denoting a hydrocarbon chain, saturated or unsaturated, linear or branched, optionally substituted, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

By "fatty acid", within the meaning of the invention, is meant a compound of formula R-COOH where R denotes a hydrocarbon chain, saturated or unsaturated, linear or branched, optionally substituted, comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.

Among the acrylic anionic associative polymers, mention may be made of:
- (a) those comprising at least one hydrophilic unit, and at least one fatty chain allyl ether unit, more particularly those whose hydrophilic unit consists of an ethylenically unsaturated anionic monomer, more particularly still of a vinyl carboxylic acid and most particularly by an acrylic acid or a methacrylic acid or mixtures thereof.
Among these anionic acrylic associative polymers, very particularly preferred according to the invention are the polymers formed from 20 to 60% by weight of acrylic acid and/or methacrylic acid, from 5 to 60% by weight of (meth ) lower alkyl acrylates, from 2 to 50% by weight of fatty chain allyl ether, and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, such as phthalate diallyl, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, and methylene-bis-acrylamide.
Among the latter, the crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10) are very particularly preferred, in particular those sold by the company CIBA under the names SALCARE SC80® and SALCARE SC90® which are 30% aqueous emulsions of a cross-linked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10).
- (b) those comprising i) at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and ii) at least one hydrophobic unit of the (C ₁₀ -C ₃₀ ) alkyl ester type of unsaturated carboxylic acid.
(C ₁₀ -C ₃₀ ) alkyl esters of unsaturated carboxylic acids useful in the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate , dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.
Anionic associative polymers of this type are for example described and prepared according to US Pat.
Among this type of anionic associative polymers, those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C ₁₀ -C ₃₀ alkyl acrylate (hydrophilic unit) will be used more particularly. hydrophobic), and 0 to 6% by weight of crosslinking polymerizable monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C ₁₀ alkyl acrylate -C ₃₀ (hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.
Among said above polymers, very particularly preferred according to the present invention are the products sold by the company GOODRICH under the trade names PEMULEN TR1®, PEMULEN TR2®, CARBOPOL 1382®, and even more preferably PEMULEN TR1®, and product sold by the company SEPPIC under the name COATEX SX®.
Mention may also be made of the acrylic acid/lauryl methacrylate/vinylpyrrolidone terpolymer sold under the name Acrylidone LM by the company ISP.
- (c) acrylic terpolymers comprising:
i) about 20 to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid [A],
ii) about 20 to 80% by weight of a non-surfactant α,β-monoethylenically unsaturated monomer different from [A],
iii) about 0.5 to 60% by weight of a nonionic monourethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate,
such as those described in patent application EP-A-0173109 and more particularly that described in example 3, namely, a terpolymer of methacrylic acid/methyl acrylate/dimethyl metaisopropenyl benzyl isocyanate of ethoxylated behenyl alcohol (40EO) in 25% aqueous dispersion.
- (d) copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an α,β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol.
Preferably, these compounds also comprise, as monomer, an ester of an α,β-monoethylenically unsaturated carboxylic acid and of a C ₁ -C ₄ alcohol.
As an example of this type of compound, mention may be made of ACULYN 22® (INCI name: Acrylates/Steareth-20 Methacrylate Copolymer) sold by the company ROHM and HAAS, which is a methacrylic acid/ethyl acrylate/ oxyalkylenated stearyl methacrylate as well as ACULYN 88 (INCI name: Acrylates/Steareth-20 Methacrylate Crosspolymer) or ACULYN 28 (INCI name: Acrylates/Beheneth-25 Methacrylate Copolymer) also sold by ROHM and HAAS.
- (e) mixtures thereof.

Preferably, the acrylic anionic associative polymer(s) are chosen from polymers not comprising sugar units.

According to a preferred embodiment of the invention, the acrylic anionic associative polymer(s) are chosen from copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an α,β-unsaturated carboxylic acid ester. monoethylenic acid and an oxyalkylenated fatty alcohol.

Preferably, the total content of anionic acrylic associative polymer(s) present in the oxidizing composition B is between 0.01 and 10% by weight, more preferably between 0.05 and 5% by weight, and even more preferably between 0.075 and 3% by weight, better still between 0.1 and 2% by weight, relative to the total weight of the oxidizing composition B .

Preferably, composition A and/or oxidizing composition B used in the process according to the present invention also comprise at least one cationic polymer.

Preferably, the cationic polymer(s) can be chosen from:
(1) alkyl diallyl amine or dialkyl diallyl ammonium cyclopolymers such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (I) or (II):

in which
- k and t are equal to 0 or 1, the sum k + t being equal to 1;
-R₁₂denotes a hydrogen atom or a methyl radical;
-R₁₀and R₁₁, independently of each other, denote a C alkyl group₁-VS₆, a C hydroxyalkyl group₁-VS₅, a C amidoalkyl group₁-VS₄; or R₁₀and R₁₁may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R₁₀and R₁₁, independently of one another, preferably denote a C alkyl group₁-VS₄;
- Y^-is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate.
Mention may more particularly be made of the homopolymer of salts (for example chloride) of dimethyldiallylammonium, for example sold under the name "MERQUAT 100" by the company NALCO, and the copolymers of salts (for example chloride) of diallyldimethylammonium and of acrylamide marketed in particular under the name "MERQUAT 550" or "MERQUAT 7SPR";
(2) diquaternary ammonium polymers comprising recurring units of the following formula (III):

in which:
-R₁₃, R₁₄, R₁₅and R₁₆, identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C hydroxyalkylaliphatic radicals₁-VS₁₂,
or R₁₃, R₁₄, R₁₅and R₁₆, together or separately, constitute with the nitrogen atoms to which they are attached heterocycles optionally comprising a second heteroatom other than nitrogen
or R₁₃, R₁₄, R₁₅and R₁₆represent a C alkyl radical₁-VS₆linear or branched substituted by a nitrile, ester, acyl, amide or -CO-O-R group₁₇-D or -CO-NH-R₁₇-D where R₁₇is an alkylene and D a quaternary ammonium group;
- AT₁and B₁represent divalent polymethylene groups comprising from 2 to 20 carbon atoms, linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings, or one or more oxygen atoms, sulfur 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;
it being understood that A₁, R₁₃and R₁₅can form with the two nitrogen atoms to which they are attached a piperazine ring;
furthermore if A₁denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B₁can also designate a group (CH₂)n-CO-D-OC-(CH₂)_p-, with n and p, identical or different, being integers ranging from 2 to 20, and D denoting:
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: -(CH₂CH₂O)_x-CH₂CH₂- and -[CH₂CH(CH₃)O]_there-CH₂CH(CH₃)- 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 divalent radical -CH₂-CH₂-S-S-CH₂-CH₂-;
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 molar mass (Mn) generally between 1000 and 100000.

More preferentially, the cationic polymer(s) can be chosen from polyquaternium-6, hexadimethrine chloride, and mixtures thereof.

Composition A and/or oxidizing composition B used in the process according to the present invention may optionally also comprise one or more additives such as nacres; fatty substances; vitamins or provitamins; surfactants, especially nonionic surfactants; pH stabilizers; curators; perfumes.

A person skilled in the art will take care to choose the possible additives and their quantity so that they do not harm the properties of the methods and compositions of the present invention.

These additives, when present, are generally present in composition A and/or oxidizing composition B according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of composition A and/or respectively the oxidizing composition B.

Composition A and/or oxidizing composition B used in the process according to the present invention may optionally also comprise one or more organic solvents.

By way of organic solvent, mention may be made, for example, of alkanols, linear or branched, C ₂ to C ₄ , such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, hexylene glycol, dipropylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols or ethers such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The process

When the step for preparing composition M does not include mixing with one or more oxidation dyes and/or with one or more direct dyes, the process of the invention is a process for bleaching keratin fibres, in particular human keratin fibers such as hair.

When the process of the invention is a process for dyeing keratin fibers, in particular human keratin fibers such as the hair, the step for preparing composition M preferably comprises mixing with one or more dye precursors of oxidation.

Advantageously, when the oxidation dye precursor(s) and/or the direct dye(s), preferably the oxidation dye precursor(s), are contained in one or more solid particles, identical or different, as defined previously , step a. for preparing a composition M according to the invention comprises mixing a number N of solid particles when the latter are identical, or several numbers N _x , identical or different, when the solid particles are different.
N is an integer greater than or equal to 2;
and N _x are integers greater than or equal to 1, and x is an index varying from 1 to n with n the number of solid particles of different types.
N and N _x are defined before the use of composition M, depending on the shade desired by the user and/or on specific features of the user such as the pre-existing shade and/or the nature of the keratin fibers.

Preferably, the numbers N and N _x are defined by means of computer software.

More preferably, step a. for preparing a composition M according to the invention comprises mixing a number N ₁ of solid particle(s) of a first type P1 as described above with a number N ₂ of solid particle(s) (s) of a second type P2 as described previously, N ₁ and N ₂ being whole numbers greater than or equal to 1 defined before the use of composition M, depending on the shade desired by the user and/ or specific features of the user such as the pre-existing shade and/or the nature of the keratin fibers.

More preferably still, the numbers N ₁ and N ₂ are defined by means of computer software.

Thus, according to a particular preferred embodiment, step a. preparation of a composition M comprises the mixture of numbers N ₁ to N _n of solid particle(s) respectively of type P1 to Pn (with n representing an integer greater than or equal to 3), the numbers N ₁ with N _n being whole numbers greater than or equal to 1 defined before the use of the composition M, according to the shade desired by the user and/or the specific features of the user such as the pre-existing shade and/or the nature of keratin fibres.

More preferably according to this embodiment, the numbers N ₁ to N _n are defined by means of computer software.

According to a particular embodiment of the invention, step a. for preparing a composition M further comprises mixing said composition A and said oxidizing composition B with several Px-type particles with one or more solid P'x-type particles (with x representing an integer greater than or equal to 1, and in particular ranging from 1 to n with n as previously described, and preferably between 1 and 20, more preferably between 1 and 15, and even more preferably between 1 and 10) containing a single dye Cx ( ie a dye direct Cx or a Cx oxidation dye precursor), better still a single Cx oxidation dye precursor, preferably in a content of between 0.1 and 50% by weight relative to the total weight of the particle(s) (s) solid(s) of type P'x; said solid particle of P'x type corresponding to the solid particle of Px type previously described, unlike the content of Cx dye, better still of Cx oxidation dye precursor.

As an example of this particular embodiment of the invention, step a. preparation of a composition M may comprise the mixture:
(i) a number N ₁ of solid particles of a first type P1 containing a single dye C1, better still a single oxidation dye precursor C1, preferably in a content of between 0.1 and 50% by weight relative to to the total weight of the solid particle(s) of type P1; with
(ii) a number N ₂ of solid particles of a second type P2 containing a single C2 dye, better still a single C2 oxidation dye precursor, preferably in a content of between 0.1 and 50% by weight relative to to the total weight of the solid particle(s) of type P2; with
(iii) a number N′ ₁ of solid particles of type P′1 containing only said dye C1, better still said oxidation dye precursor C1, preferably in a content of between 0.1 and 50% by weight relative to the total weight of the solid particle(s) of type P′1; And
(iv) at least one composition A comprising arginine;
(v) at least one distinct oxidizing composition B comprising one or more chemical oxidizing agents and one or more acrylic anionic associative polymers;
Being heard that :
- the dye C1, better the precursor of oxidation dye C1, is different from the dye C2, better the precursor of oxidation dye C2;
- the content of dye C1, better of precursor of oxidation dye C1, contained in the solid particle(s) P1 is different from the content of dye C1, better of precursor of oxidation dye C1 , contained in the solid particle(s) P'1;
- The numbers N ₁ , N ₂ and N′ ₁ designating whole numbers greater than or equal to 1, identical or different.

Preferably, step a. preparation of a composition M according to the invention is carried out less than two hours, more preferably less than one hour, more preferably still less than 30 minutes, before step b) of application to the keratin fibers of the composition Mr.

According to a particular embodiment of the invention, step a. preparation of a composition M comprises the mixture:
(i) one or more oxidation dye precursors as previously described; more preferably several solid particles, identical or different, each containing one or more oxidation dye precursors as previously described; with
(ii) composition A as previously described; And
(iii) oxidizing composition B distinct from composition A, as previously described; And
(iv) one or more additional aqueous compositions different from said compositions A and B.

According to a preferred embodiment of the invention, step a. preparation of a composition M comprises the mixture:
- one or more oxidation dye precursors as previously described; preferably several solid particles, identical or different, each containing one or more oxidation dye precursors as previously described; with
- at least one composition A comprising arginine and optionally one or more additional alkaline agents other than arginine, as previously described; And
- at least one distinct oxidizing composition B comprising:
(i) at least one chemical oxidizing agent, preferably chosen from those as described above, more preferably from hydrogen peroxide, persalts and mixtures thereof, and
(ii) one or more anionic acrylic associative polymers as described above, preferably chosen from copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an α,β-monoethylenically unsaturated carboxylic acid ester and d an oxyalkylenated fatty alcohol.

Preferably according to this embodiment, the arginine content present in composition A is between 0.05 and 25% by weight, more preferably between 0.1 and 15% by weight, more preferably still between 0.5 and 10 % by weight, and even better between 1 and 5% by weight, relative to the total weight of composition A.

Preferably according to this embodiment, when the additional alkaline agent(s) other than arginine are present in composition A, the total content of additional alkaline agent(s) different from the arginine is between 0.05 and 25% by weight, more preferably between 0.1 and 20% by weight, and even more preferably between 0.5 and 15% by weight, relative to the total weight of composition A.

Preferably according to this embodiment, the total content of chemical oxidizing agent(s) present in the oxidizing composition B is between 0.1 and 35% by weight, more preferably between 0. 1 and 30% by weight, and even more preferably between 0.5 and 25% by weight, better still between 2 and 12% by weight relative to the total weight of the oxidizing composition B.

Preferably according to this embodiment, the total content of anionic acrylic associative polymer(s) present in the oxidizing composition B is between 0.01 and 10% by weight, more preferably between 0.05 and 5% by weight, and even more preferably between 0.075 and 3% by weight, better still between 0.1 and 2% by weight relative to the total weight of the oxidizing composition B.

According to yet another preferred embodiment of the invention, step a. preparation of a composition M comprises the mixture:
- one or more solid particles of type P1 and one or more solid particles of type P2 (and more generally one or more particles of type P1 to Pn), as previously described; with
- at least one composition A comprising arginine and optionally one or more additional alkaline agents other than arginine, as previously described; And
- at least one distinct oxidizing composition B comprising:
(i) at least one chemical oxidizing agent, preferably chosen from those as described above, more preferably from hydrogen peroxide, persalts and mixtures thereof, and
(ii) one or more anionic acrylic associative polymers as described above, preferably chosen from copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an α,β-monoethylenically unsaturated carboxylic acid ester and d an oxyalkylenated fatty alcohol.

Preferably according to this embodiment, the arginine content present in composition A is between 0.05 and 25% by weight, more preferably between 0.1 and 15% by weight, more preferably still between 0.5 and 10 % by weight, and even better between 1 and 5% by weight, relative to the total weight of composition A.

Preferably according to this embodiment, when the additional alkaline agent(s) other than arginine are present in composition A, the total content of additional alkaline agent(s) different from the arginine is between 0.05 and 25% by weight, more preferably between 0.1 and 20% by weight, and even more preferably between 0.5 and 15% by weight, relative to the total weight of composition A.

Preferably according to this embodiment, the total content of chemical oxidizing agent(s) present in the oxidizing composition B is between 0.1 and 35% by weight, more preferably between 0. 1 and 30% by weight, and even more preferably between 0.5 and 25% by weight, better still between 2 and 12% by weight relative to the total weight of the oxidizing composition B.

Preferably according to this embodiment, the total content of anionic acrylic associative polymer(s) present in the oxidizing composition B is between 0.01 and 10% by weight, more preferably between 0.05 and 5% by weight, and even more preferably between 0.075 and 3% by weight, better still between 0.1 and 2% by weight relative to the total weight of the oxidizing composition B.

According to a variant of the invention, the oxidation dye precursors as described above are present in a composition C, distinct from compositions A and B; said composition C being mixed with compositions A and B to obtain composition M.

According to another particular embodiment of the invention, step a. preparation of the composition M can also implement one or more solid particles free of dye.

The mixing of the oxidation dye precursors, or even optionally of the direct dyes, with composition A and oxidizing composition B, and optionally the other compositions, can be carried out by means of a mechanical stirrer, a magnetic stirrer, and /or by hand using for example a coloring brush.

When the oxidation dye precursor(s) (or even the direct dye(s)) are contained in one or more solid particles, identical or different, as defined above, it is understood within the meaning of invention that step a) for preparing a composition M comprises dissolving said solid particles in composition A and oxidizing composition B.

Advantageously, step b) of application to the keratin fibers of composition M according to the invention is carried out for less than 60 minutes, more preferably less than 30 minutes, more preferably still less than 10 minutes, even better still less than 5 minutes, after step a).

The composition M

Composition M, or final composition, is obtained after mixing composition A with distinct oxidizing composition B as described above.

Preferably, the water content of said composition M is between 30 and 99% by weight; more preferably between 50 and 99% by weight, even better still between 50 and 90% by weight, relative to the total weight of said composition M.

Preferably, when composition M comprises one or more oxidation dye precursors, the content of oxidation dye precursor(s) present in composition M advantageously represents from 0.0001 to 15% by weight, more preferably from 0.001% to 10% by weight, more preferably still from 0.005% to 5% by weight, relative to the total weight of composition M.

Preferably, the arginine content present in said composition M ranges from 0.001 to 20% by weight, more preferably from 0.05 to 10% by weight, more preferably still from 0.1 to 5% by weight, even better still from 0 5 to 3% by weight, relative to the total weight of said composition M.

Preferably, the total content of alkaline agent(s) present in said composition M ranges from 0.001 to 30% by weight, more preferably from 0.05 to 20% by weight, more preferably still from 0, 5 to 10% by weight, even better still from 1 to 5% by weight, relative to the total weight of said composition M.

Preferably, the total content of chemical oxidizing agent(s) present in said composition M ranges from 0.001 to 30% by weight, more preferably from 0.05 to 20% by weight, and more more preferably from 0.1 to 15% by weight, and even better still from 1 to 10% by weight, relative to the total weight of said composition M .

Preferably, the total content of anionic acrylic associative polymer(s), present in said composition M ranges from 0.001 to 8% by weight, more preferably from 0.005 to 4% by weight. , and even more preferably from 0.01 to 1% by weight, relative to the total weight of said composition M.

Preferably, the weight ratio of the total mass of composition M on the one hand, to the total mass of solid particles on the other hand, is between 1 and 22, more preferably between 2 and 15; more preferably still between 5 and 12.

Composition M can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for producing a coloring of keratin fibres, and in particular of human hair.

A subject of the invention is also a process for preparing a composition M, for dyeing keratin fibres, in particular human keratin fibers such as the hair, comprising the mixture:
a) one or more oxidation dye precursors, preferably several solid particles, which are identical or different, each containing one or more oxidation dye precursors, more preferably chosen from those as defined previously; with
b) at least one composition A comprising arginine; And
c) at least one oxidizing composition B distinct from composition A comprising:
(i) one or more chemical oxidizing agents, preferably chosen from those as defined previously, and
(ii) one or more anionic acrylic associative polymers, preferably chosen from copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an alcohol oxyalkylenated fat.

Preferably, said solid particles comprise:
- one or more solid particles of a first type P1 containing a single oxidation dye precursor C1; And
- one or more solid particles of a second type P2 containing a single oxidation dye precursor C2;
it being understood that the oxidation dye precursor C1 is different from the oxidation dye precursor C2.

A subject of the invention is also the use of composition M as defined above, for the treatment, preferably for coloring/bleaching, of keratin fibres, in particular human keratin fibers such as the hair.

More particularly, the invention relates to the use of composition M, obtained by the preparation process comprising the mixture:
- one or more oxidation dye precursors, preferably in the form of several solid particles, identical or different, each containing one or more oxidation dye precursors, as described above; with
- at least one composition A comprising arginine and optionally one or more additional alkaline agents different from arginine, as previously described; And
- at least one distinct oxidizing composition B comprising:
(i) at least one chemical oxidizing agent, preferably chosen from those as described above, more preferably from hydrogen peroxide, persalts and mixtures thereof; And
(ii) one or more anionic acrylic associative polymers, preferably chosen from those as described above, more preferably still from copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an unsaturated carboxylic acid ester α,β-monoethylenic and an oxyalkylenated fatty alcohol;
for coloring keratin fibres, in particular human keratin fibers such as the hair.

A subject of the invention is also a composition M' for the oxidation/bleaching of keratin fibres, comprising (i) one or more anionic acrylic associative polymers, (ii) arginine, (iii) one or more chemical oxidants and (iv) optionally one or more oxidation dye precursors.

The composition M' may optionally comprise (v) one or more alkaline agents other than arginine, preferably chosen from ammonia, alkanolamines, alkali metal or alkaline earth metal metasilicates, and mixtures thereof; more preferably still from ammonia, monoethanolamine, sodium metasilicate, and mixtures thereof.

The contents and preferences of the compounds (i) to (v) of the ready-to-use composition M′ are identical to those mentioned above for the composition M.

The following examples serve to illustrate the invention without however being limiting.

Examples

The solid particles and the compositions below according to the present invention were prepared from the ingredients whose contents are indicated, in mass percentage of active ingredient relative to the total weight of the solid particle or of the composition, in the tables below. -below.

Examples of particles
Solid particle without an upper coating layer
Ingredients Quantity MICROCRYSTALLINE CELLULOSE 56 LACTOSE 15 PVP 4.75 MAGNESIUM STEARATE 2 SILICA 1 TOLUENE-2,5-DIAMINE SULPHATE 20 SODIUM SULPHITE 1 WATER 0.25

Examples of top cover layer
Ingredients Quantity Hydroxypropylmethyl Cellulose (HPMC) 45 to 55 Hydroxypropyl cellulose (HPC) 5 to 20 Capric/Caprylic Triglyceride 1 to 10 Talc Qsp 100 Pigments 0 to 40

Examples of solid particle with top coating layer
Ingredients Quantity MICROCRYSTALLINE CELLULOSE 54.4 LACTOSE 14.6 PVP 4.6 MAGNESIUM STEARATE 1.94 SILICA 1.0 TOLUENE-2,5-DIAMINE SULPHATE 19.4 SODIUM SULPHITE 1.0 WATER 0.2 HYDROXYPROPYL METHYLCELLULOSE 1.46 HYDROXYPROPYLCELLULOSE 0.29 TALC 0.44 CAPRYLIC/CAPRIC TRIGLYCERIDE 0.15 PIGMENTS 0.51 ALUMINA 0.01

Ingredients Quantity MICROCRYSTALLINE CELLULOSE 77.2 LACTOSE 14.6 PVP 0.1 MAGNESIUM STEARATE 1 SILICA 0.54 RESORCINOL 0.85 HYDROXYPROPYL METHYLCELLULOSE 1.45 HYDROXYPROPYLCELLULOSE 0.30 TALC 0.4 CAPRYLIC/CAPRIC TRIGLYCERIDE 0.15 PIGMENTS 0.5 ALUMINA 0.01 VP/VA COPOLYMER 2.9

Ingredients Quantity MICROCRYSTALLINE CELLULOSE 63.5 LACTOSE 9.7 PVP 0.1 MAGNESIUM STEARATE 1 SILICA 0.5 RESORCINOL 16.5 ASCORBIC ACID 2.9 HYDROXYPROPYL METHYLCELLULOSE 1.5 HYDROXYPROPYLCELLULOSE 0.3 TALC 0.44 CAPRYLIC/CAPRIC TRIGLYCERIDE 0.15 PIGMENTS 0.5 ALUMINA 0.01 VP/VA COPOLYMER 2.9

Ingredients Quantity MICROCRYSTALLINE CELLULOSE 76.2 LACTOSE 15.5 PVP 0.5 MAGNESIUM STEARATE 1.0 SILICA 1.0 2,4-DIAMINOPHENOXYETHANOL HYDROCHLORIDE 1.0 SODIUM METABISULPHITE 1.94 WATER 0.02 HYDROXYPROPYL METHYLCELLULOSE 1.45 HYDROXYPROPYLCELLULOSE 0.29 TALC 0.44 CAPRYLIC/CAPRIC TRIGLYCERIDE 0.15 PIGMENTS 0.5 ALUMINA 0.01

Ingredients Quantity MICROCRYSTALLINE CELLULOSE 69.4 LACTOSE 11.6 PVP 2.8 MAGNESIUM STEARATE 1.0 SILICA 0.5 m-AMINOPHENOL 7.8 SODIUM METABISULPHITE 3.9 WATER 0.15 HYDROXYPROPYL METHYLCELLULOSE 1.46 HYDROXYPROPYLCELLULOSE 0.29 TALC 0.44 CAPRYLIC/CAPRIC TRIGLYCERIDE 0.15 PIGMENTS 0.5 ALUMINA 0.01

Oxidizing composition
Ingredients Quantity (g) Hydrogen peroxide 12 Stabilizer, sequestrant Q's Phosphoric acid Qs pH = 2.2 ± 0.2 Water Qs 100

Alkaline composition 1
Ingredients Quantity Arginine 3 Ammonium hydroxide 2 Monoethanolamine 5.8 sodium metasilicate 2 Polyquaternium-6 2 Hexadimethrine chloride 1.2 EDTA 0.2 Hydroxypropyl methyl cellulose (HPMC) 0.2 Cetyl hydroxyethyl cellulose 0.45 PEG-40 Stearate 1.8 Oleth-30 1.5 Oleic acid 3 C ₂₀ -C ₂₂ fatty alcohols 3 Stearamide MEA 4.8 Steareth-2 5.5 Water Qsp 100

Alkaline composition 2
Ingredients Quantity Arginine 3 Monoethanolamine 5.8 sodium metasilicate 2 Polyquaternium-6 2 Hexadimethrine chloride 1.2 EDTA 0.2 Hydroxypropyl methyl cellulose (HPMC) 1.2 Cetyl hydroxyethyl cellulose 0.45 PEG-40 Stearate 1.8 Oleth-30 1.5 Oleic acid 3 C ₂₀ -C ₂₂ fatty alcohols 3 Stearamide MEA 4.8 Steareth-2 5.5 Water Qsp 100

Thickening composition
Ingredients Quantity Hydrogen peroxide 12 Cetearyl alcohol 8 Acrylates/Beheneth-25 methacrylate copolymer, under the reference Aculyn 28 from ROHM and HAAS 0.4 Ceteareth-33 2 sequestrants, stabilizers Q's Phosphoric acid Qs pH = 2.2 ± 0.2 Water Qsp 100

Process for coloring keratin fibers
A composition (M) for coloring keratin fibers is prepared in a bowl according to the following steps:
(1) 100 coated solid particles (i.e. 6g) according to table 4 above, 58 coated solid particles (i.e. 3.48g) according to table 6 above, 22 coated solid particles (i.e. 1.32g) according to table 5 above, 21 coated solid particles (i.e. 1.26 g) according to Table 7 above, and 14 coated solid particles (i.e. 0.84 g) according to Table 8 above, are mixed with 12 g of oxidizing composition according to Table 9 above and 36 g of water stabilized and adjusted to pH 2.2; then after at least 30 seconds
(2) the mixture obtained in step (1) is mixed with 24 g of thickening composition according to Table 12 above, 28.8 g of alkaline composition 1 according to Table 10 above and 19.2 g of alkaline composition 2 according to Table 11 above.

An aqueous composition (M), homogeneous in which the coated solid particles have dispersed in the composition, is thus obtained.

The composition (M) obtained is then applied to locks of 90% white natural Caucasian hair (locks of BN hair) at the rate of 10 g of composition (M) per 1 g of hair. After leaving on for 30 minutes at 27° C., the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

Results for coloring:
The colorimetric data of each of the locks are then measured in the CIELab system with a DATA COLOR SF600X spectrophotometer (illuminant D65, angle 10° and specular component included). In this L* a* b* system, L* represents the brightness, a* indicates the green/red color axis and b* the blue/yellow color axis. The higher the value of L*, the lighter or less intense the color. Conversely, the lower the value of L*, the darker or more intense the color. The higher the value of a* the more red the shade and the higher the value of b* the more yellow the shade.

The increase in color on the hair therefore corresponds to the variation in coloring between the locks of colored BN hair and the locks of uncolored (ie untreated) BN hair, is measured by the ∆E according to the following equation:

In this equation, L*, a* and b* represent the values measured after coloring the BN hair and L ₀ *, a ₀ * and b ₀ * represent the values measured for the locks of untreated BN hair. The higher the value of ∆E, the better the color rise.

The results are grouped in the table below:
I* To* b* ΔE Strand of untreated BN hair 57.78 1.40 13.97 - Strand of treated BN hair 23.57 2.39 5.25 35.32

It appears from the results of the table that the keratin fibers treated with the composition (M) prepared according to the preparation process of the invention are colored intensely and with a good rise in color.

It has also been found that composition (M) is easy to produce and to distribute over the locks of hair, in particular without dripping.

Keratin fiber bleaching process
A composition (N) for bleaching keratin fibers is prepared in a bowl by mixing 12g of oxidizing composition according to Table 9 above with 36g of water stabilized and adjusted to pH 2.2, then with 24g of thickening composition according to Table 12 above and 48g of alkaline composition 1 according to Table 10 above.

A homogeneous aqueous composition (N) is thus obtained.

The composition (N) obtained is then applied to locks of natural Caucasian hair with a height of tone 4 (HT4) at the rate of 10 g of composition (N) per 1 g of hair. After leaving on for 30 minutes at 27° C., the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

Results for fading:
The color of the locks was evaluated in the CIE L* a* b* system, using a DATA COLOR SF600X spectrophotometer (illuminant D65, angle 10° and specular component included). In this L* a* b* system, the three parameters denote respectively the intensity of the color (L*), a* indicates the green/red color axis and b* the blue/yellow color axis.

The higher the value of L*, the more the locks are discolored. The higher the value of a* the more red the shade and the higher the value of b* the more yellow the shade.

The bleaching efficacy is evaluated by the variation in the color of the locks before and after treatment with the composition (N), and measured by (ΔE*) according to the following equation:

In this equation, L*, a* and b* represent the values measured on the locks of HT4 hair treated with composition (N), and L ₀ *, a ₀ * and b ₀ * represent the values measured on the locks of untreated HT4 hair.

The greater the value of ΔE*, the greater the difference in color of the lock before and after treatment, which shows a more extensive discoloration.

The results are grouped in the table below:
I* To* b* ΔE Strand of untreated HT4 hair 21.33 2.84 3.24 - Strand of HT4 treated hair 26.22 6.91 9.43 8.88

It appears from the results of the above table that the keratin fibers treated with the composition (N) prepared according to the preparation process of the invention are significantly bleached (L ^* >L ₀ and ΔE high).

It has also been found that composition (N) is easy to produce and to distribute over the locks of hair, in particular without dripping.

Claims (22)

A method of treating keratinous fibers comprising:

1. at least one step for preparing a composition M comprising the mixture:
   1. at least one composition A comprising arginine; with
   2. at least one oxidizing composition B distinct from composition A, comprising:
      • one or more chemical oxidizing agents, and
      • one or more acrylic anionic associative polymers; Then
2. at least one step of applying to said keratin fibers said composition M.

Method according to the preceding claim, characterized in that step a. preparation of composition M includes mixing with one or more oxidation dye precursors; preferably said oxidation dye precursor(s) is (are) introduced in the form of solid particles, identical or different, each containing one or more oxidation dye precursors oxidation. Process according to the preceding claim, characterized in that the said solid particles comprise:
- one or more solid particles of a first type P1 containing a single oxidation dye precursor C1; And
- one or more solid particles of a second type P2 containing a single oxidation dye precursor C2;
it being understood that the oxidation dye precursor C1 is different from the oxidation dye precursor C2. Process according to any one of Claims 2 or 3, characterized in that the said solid particles comprise n types of solid particles P1 to Pn, with n representing an integer greater than or equal to 3, and preferably between 3 and 20, more preferentially between 3 and 15, and more preferentially still between 4 and 10; each type of solid particle P1 to Pn containing a single oxidation dye precursor, respectively C1 to Cn, and
it being understood that said precursors C1 to Cn are all different from each other. Process according to any one of Claims 2 to 4, characterized in that the oxidation dye precursors are chosen from oxidation bases and oxidation couplers; preferably from oxidation bases. Process according to Claim 3, characterized in that the oxidation dye precursor C1 is chosen from oxidation bases and the oxidation dye precursor C2 is chosen from oxidation couplers. Process according to either of Claims 5 and 6, characterized in that the oxidation base(s) is (are) chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases, and the corresponding addition salts; more preferably from para-phenylenediamine, para-toluenediamine, para-aminophenol, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, 4,5-diamino-1-(β-hydroxyethyl)pyrazole, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-β-hydroxyethoxy-3-amino-pyrazolo[1,5-a] pyridine, and their addition salts. Process according to any one of Claims 5 or 6, characterized in that the oxidation coupler is chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents, heterocyclic coupling compounds, and their corresponding addition salts or solvates; more preferably from 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 3-aminophenol, 6-hydroxybenzomorpholine, 5-N-(ß-hydroxyethyl)amino-2-methylphenol, 2, 4-diamino-1-(ß-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 6-hydroxyindole, 4-chloro-1,3-dihydroxybenzene, 2-amino-3-hydroxypyridine, 3- amino-2-chloro-6-methylphenol, α-naphthol, 2-[3-amino-4-methoxyphenyl]amino)ethanol and their addition salts. Process according to any one of claims 2 to 8, characterized in that the total content of oxidation dye precursor(s) represents from 0.1 to 50% by weight; preferably 0.3 to 25% by weight; more preferably from 0.4 to 22% by weight, relative to the total weight of each solid particle containing it(these). A method according to any of claims 2 to 9, characterized in that said solid particles comprise at least one antioxidant agent; preferably chosen from (a) ascorbic acid, its salts and its derivatives such as sodium ascorbate, erythorbic acid, ascorbyl palmitate, ascorbyl laurate, (b) salicylic acid, its salts and its derivatives such as sodium salicylate, (c) mercaptans and inorganic sulphites such as sodium sulphite, sodium bisulphite, sodium metabisulphite, potassium sulphite and thioglycolic acid , and mixtures thereof; more preferably selected from ascorbic acid, sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium salicylate, and mixtures thereof; more preferably still in a total content of between 0.1 and 15% by weight, better still between 0.3 and 12% by weight, even better between 0.4% and 10% by weight, or even between 0.5 and 5% by weight, relative to the total weight of each solid particle containing it(these). Process according to any one of Claims 2 to 10, characterized in that the said solid particles are anhydrous. Process according to any one of Claims 2 to 11, characterized in that the said solid particles have an average volume of between 25 and 125 mm ³ ; preferably between 30 and 90 mm ³ ; more preferably between 45 and 65mm ³ . Process according to any one of the preceding claims, characterized in that the arginine content in composition A is between 0.05 and 25% by weight, preferably between 0.1 and 15% by weight, more preferably between 0 5 and 10% by weight, more preferably still between 1 and 5% by weight, relative to the total weight of composition A. Process according to any one of the preceding claims, characterized in that the arginine content in composition M is between 0.001 and 20% by weight, preferably between 0.05 and 10% by weight, more preferably between 0.1 and 5% by weight, more preferably still between 0.5 and 3% by weight, relative to the total weight of composition M. Process according to any one of the preceding claims, characterized in that the said chemical oxidizing agent or agents are chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, in particular sodium persulfate, potassium persulfate and ammonium persulfate, peracids and oxidase enzymes such as peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases, and mixtures thereof; preferably, the chemical oxidizing agent(s) are chosen from hydrogen peroxide, persalts, and mixtures thereof. Process according to any one of the preceding claims, characterized in that the said anionic acrylic associative polymer(s) are chosen from:
(a) acrylic anionic associative polymers comprising at least one hydrophilic unit and at least one allyl ether unit with a fatty chain,
(b) acrylic anionic associative polymers comprising i) at least one hydrophilic unit of olefinic unsaturated carboxylic acid type and ii) at least one hydrophobic unit of unsaturated carboxylic acid (C ₁₀ -C ₃₀ ) alkyl ester type,
(c) acrylic terpolymers comprising i) about 20 to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid [A], ii) about 20 to 80% by weight of an α,β-unsaturated monomer -monoethylenic non-surfactant different from [A], iii) approximately 0.5 to 60% by weight of a non-ionic mono-urethane reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate,
(d) copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylenated fatty alcohol, and mixtures thereof; preferably from copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an α,β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol,
(e) mixtures thereof. Process according to any one of the preceding claims, characterized in that the total content of anionic acrylic associative polymer(s) present in the oxidizing composition B is between 0.01 and 10% by weight, more preferably between 0.05 and 5% by weight, and even more preferably between 0.075 and 3% by weight, better still between 0.1 and 2% by weight, relative to the total weight of the oxidizing composition B Process according to any one of the preceding claims, characterized in that the total content of anionic acrylic associative polymer(s) is between 0.001 and 8% by weight, preferably between 0.005 and 4 % by weight, more preferably between 0.01 and 1% by weight, relative to the total weight of said composition M. Method according to any one of the preceding claims, characterized in that step a. preparation of a composition M is implemented less than two hours, preferably less than one hour, more preferably less than 30 minutes, before step b. application on keratin fibres. Process for preparing a composition M, for coloring keratin fibres, comprising mixing:

1. one or more oxidation dye precursors, preferably chosen from those as defined in any one of claims 2 to 12; with
2. at least one composition A comprising arginine; And
3. at least one oxidizing composition B distinct from composition A comprising:
   1. one or more chemical oxidizing agents, preferably selected from those as defined in claim 15, and
   2. one or more associative anionic acrylic polymers, preferably chosen from copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an α,β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol.

Use of composition M as defined in any one of Claims 1 to 18, for the treatment, preferably for coloring/bleaching, of keratin fibres. Composition for the oxidation/bleaching of keratin fibers comprising (i) one or more anionic acrylic associative polymers, preferably chosen from copolymers comprising among their monomers an α,β-monoethylenic unsaturated carboxylic acid and a carboxylic acid ester with α,β-monoethylenic unsaturation and an oxyalkylenated fatty alcohol, (ii) arginine, (iii) one or more chemical oxidants, preferably chosen from hydrogen peroxide, persalts, and mixtures thereof, ( iv) optionally one or more oxidation dye precursors, and optionally (v) one or more alkaline agents other than arginine, preferably chosen from ammonia, alkanolamines, alkali or alkaline earth metal metasilicates, and their mixtures; more preferably still from ammonia, monoethanolamine, sodium metasilicate, and mixtures thereof.