WO2002022095A1 - Oxidation dyeing composition for keratinous fibres comprising a 5-halogeno-ortho-amino-phenol derivative in position-4 - Google Patents

Abstract

.The invention concerns a ready-to-use oxidation dyeing composition for keratinous fibres, and in particular human keratinous fibres such as hair, comprising, in a medium suited for dyeing, at least an oxidation dye selected among derivatives in position-4 of 5-halogeno-ortho.amino-phenols, and at least an oxidizing agent, and the oxidation dyeing method using said composition.

Description

 KERATIN FIBER OXIDATION DYE COMPOSITION COMPRISING A DERIVATIVE IN POSITION-4 OF 5-HALOGENO-ORTHO-

AMINO PHENOL

The subject of the invention is a ready-to-use composition for the oxidation dyeing of keratin fibers, and in particular human keratin fibers such as the hair comprising, in a medium suitable for dyeing, at least one dye of oxidation chosen from derivatives in position-4 of 5-halogeno-ortho-amino-phenols, and at least one oxidizing agent, as well as the oxidation dyeing process using this composition.

It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dyes and in particular oxidation dye precursors, in particular ortho or paraphenylenediamines, ortho or paraaminophenols, heterocyclic bases, generally called oxidation bases. The precursors of oxidation dyes, or oxidation bases, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds.

We also know that we can vary the shades obtained with these oxidation bases by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, meta-aminophenols, metadiphenols and certain compounds. heterocyclic.

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

The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity and to exhibit good resistance to agents. exterior (light, bad weather, washing, permanent ripple, perspiration, friction).

The oxidation dyeing of keratin fibers is generally carried out in an alkaline medium, in the presence of hydrogen peroxide. However, it can also be carried out using oxidizing systems other than hydrogen peroxide such as enzymatic systems. Thus, it has already been proposed to dye keratin fibers, in particular in patent application EP-A-0 310 675, with compositions comprising an oxidation base and optionally a coupler, in combination with enzymes of the oxidoreductase type. with 2 electrons, such as pyranose oxidase, glucose oxidase or even uricase, in the presence of a donor for said enzymes. It has also already been proposed, in particular in patent applications FR-A-2112549, FR-A-2694018, EP-A-504005, WO 95/07988, W095 / 33836, W095 / 33837, WO96 / 00290, WO97 / 19998, W097 / 19999, W097 / 37633, WO / 98/40471 and US Pat. No. 3,251,742, dyeing keratin fibers with compositions comprising in particular an oxidation dye and a laccase type enzyme (4-electron oxidoreductase) ). Finally, it has also been proposed to use peroxidase for dyeing keratin fibers in the presence of small amounts of hydrogen peroxide, as described in patents EP-548,620, BE-775,110 and US-3,893,803 .

With the oxidation dyes conventionally used in oxidation dyeing, it is not always easy to obtain natural shades, this is particularly true in oxidative systems of enzymatic nature.

The Applicant has now discovered that it is possible to obtain new dyes, capable of leading to tenacious coloring, and in particular to light, the nuances of which are natural, by associating at least one oxidation dye chosen from derivatives in position-4 of 5-halo-ortho-amino-phenols to an oxidizing system and more particularly to an enzymatic oxidizing system comprising at least one 2-electron or 4-electron oxidoreductase or a peroxidase. This discovery is the basis of the present invention.

The first object of the invention is therefore a ready-to-use composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, comprising at least one derivative in a medium suitable for dyeing in position-4 of the 5-ha! ogén-ortho-amino-phenols of formula (1) defined below, and at least one oxidizing agent.

in which,

R denotes a hydrogen atom or a C1-C5 alkyl radical,

X denotes a halogen atom chosen from fluorine, bromine, iodine or chlorine, and their addition salts with an acid.

The addition salts with an acid of the oxidation dyes of formula (I) are in particular chosen from hydrochlorides, phosphates, hydrobromides, sulfates and tartrates, lactates and acetates.

The subject of the invention is also a process for the oxidation dyeing of keratin fibers using this ready-to-use dye composition.

The oxidation dye (s) of formula (I) according to the invention are compounds well known to those skilled in the art and in particular described and prepared in German patent 670584. They have hitherto never been proposed as oxidation dyes in oxidation dye of keratin fibers.

According to the present invention, among the derivatives in position-4 of 5-halo-ortho-amino-phenols of formula (I) it is very particularly preferred to use the compound of formula (I) for which R denotes a methyl radical and X denotes a chlorine atom.

The oxidation dye (s) of formula (I) used in accordance with the invention preferably represent from 0.001 to 10% by weight approximately of the total weight of the composition and even more preferably from 0.01 to 8% approximately of this weight .

Oxidizing agent

In the ready-to-use composition according to the invention, the oxidizing agent can be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, persalts such as perborates and persulfates . The use of hydrogen peroxide is particularly preferred. This oxidizing agent advantageously consists of a solution of hydrogen peroxide, the titer of which can vary, more particularly, from approximately 1 to 40 volumes, and even more preferably from approximately 5 to 40.

It is also possible to use, as oxidizing agent, one or more enzymes of the 2-electron or 4-electron oxidoreductase type or of the peroxidase type.

A ready-to-use composition which is particularly preferred according to the present invention is a ready-to-use composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, comprising in a medium suitable for dyeing , at least one derivative in position-4 of the 5-halo-ortho-amino-phenols of formula (I) defined above, and at least one enzyme chosen from oxidoreductases with 2 electrons, oxidoreductases with 4 electrons or peroxidases.

The 2-electron oxidoreductase (s) used in the ready-to-use dye composition according to the invention are used in the presence of a donor for the said enzyme (s), and can in particular be chosen from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, uricases, choline oxidases, sarcosine oxidases, bilirubin oxidases and amino acid oxidases. According to the invention, the 2-electron oxidoreductase is preferably chosen from uricases of animal, microbiological or biotechnological origin.

By way of example, mention may in particular be made of uricase extracted from boar liver, the uricase of Arthrobacter globiformis, as well as the uricase of Aspergillus flavus.

The 2-electron oxidoreductase (s) can be used in pure crystalline form or in a diluted form in an inert diluent for said 2-electron oxidoreductase.

The 2-electron oxidoreductase (s) in accordance with the invention preferably represent from 0.01 to 20% by weight approximately of the total weight of the composition, and even more preferably from 0.1 to 5% by weight approximately of this weight.

We can also define the amount of enzyme according to its activity.

The enzymatic activity of the 2-electron oxidoreductases in accordance with the invention can be defined from the oxidation of the donor under aerobic conditions. One unit U corresponds to the quantity of enzyme leading to the generation of one μmole of H2O2 per minute at a pH of 8.5 and at a temperature of 25 ° C. Preferably, the quantity of 2-electron oxidoreductase according to the invention is between 10 and 10 ⁸ U units approximately per 100 g of dye composition.

According to the invention, the term “donor” is intended to mean the various substrates also necessary for the operation of said one or more 2-electron oxidoreductases.

The nature of the donor (or substrate) for said enzyme varies depending on the nature of the 2-electron oxidoreductase which is used. For example, as a donor for pyranose oxidases, mention may be made of D-glucose, L-sorbose and D-xylose; as a donor for glucose oxidases, mention may be made of D-glucose; as a donor for the glycerol oxidases, mention may be made of glycerol and dihydroxyacetone; as a donor for lactate oxidases, there may be mentioned lactic acid and its salts; as the donor for pyruvate oxidases, mention may be made of pyruvic acid and its salts; as uricase donors, mention may be made of uric acid and its salts; as a donor for the choline oxidases, mention may be made of choline and its addition salts with an acid such as choline hydrochloride, and betaine aldehyde; as a donor for sarcosine oxidases, mention may be made of sarcosine, (a N-methyl-L-leucine, N-methyl-DL-alanine, and N-methyl-DL-valine; and finally, as donor for bilirubin oxidases, there may be mentioned bilirubin.

The donor (s) (or substrates) used in accordance with the invention preferably represent from 0.01 to 20% by weight approximately of the total weight of the composition according to the invention and even more preferably from 0.1 to 5% by about this weight.

The 4-electron oxidoreductase (s) used in the ready-to-use dye composition in accordance with the invention can in particular be chosen from laccases, tyrosinases, catechol oxidases and polyphenol oxidases.

According to a particular and preferred embodiment of the invention, the 4-electron oxidoreductase (s) are chosen from laccases.

These laccases can in particular be chosen from laccases of plant origin, of animal origin, of fungal origin (yeasts, molds, fungi) or of bacterial origin, the organisms of origin being able to be mono- or multicellular. Laccases can also be obtained by biotechnology.

Among the laccases of plant origin which can be used according to the invention, mention may be made of laccases produced by plants carrying out chlorophyll synthesis, such as those indicated in patent application FR-A-2 694 018.

Mention may in particular be made of the laccases present in the extracts of Anacardiaceae such as for example the extracts of agnifera indica, of Schinus soft or of Pleiogynium timoriense; in extracts from Podocarpaceae; of Rosmarinus off. ; Solanum tuberosum; Iris sp. ; from Coffea sp. ; Daucus carrota; of Vinca minor; Persea americana; Catharenthus roseus; from Musa sp. ; Malus pumila; Gingko biloba; Monotropa hypopithys (sucepin), Aesculus sp. ; Acer pseudoplatanus; of Prunus persica and Pistacia palaestina.

Among the laccases of fungal origin, possibly obtained by biotechnology, which can be used according to the invention, mention may be made of the laccase (s) obtained from Polyporus versicolor, Rhizoctonia pratola and Rhus vernicifera as described for example in patent applications FR- A-2 112 549 and EP-A-504005; the laccases described in patent applications WO95 / 07988, W095 / 33836, W095 / 33837, WO96 / 00290, W097 / 19998 and W097 / 19999, the content of which is an integral part of the present description, for example the laccase (s) obtained Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyricularia orizae, and their variants. We can also cite the laccase (s) from Trametes versicolor, Fomes fomentarius, Chaetomium thermophile, Neurospora crassa, Coriolus versicolor, Botrytis cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus ostreatus, Aspergillus nidulans, Podospora anserina, Agaricus bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum, Thelephora terrestris, Cladosporium cladosporioides, Cerrena unicolor, Coriolus hirsutus Coprinus cinereus, Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and their variants.

More preferably, laccases of fungal origin, possibly obtained by biotechnology, will be chosen.

The enzymatic activity of the laccases used in accordance with the invention and having syringaldazine among their substrates can be defined from the oxidation of syringaldazine in aerobic condition. The Lacu unit corresponds to the quantity of enzyme catalyzing the conversion of 1 mmol of syringaldazine per minute at a pH of 5.5 and at a temperature of 30 ° C. Unit U corresponds to the quantity of enzyme producing an absorbance delta of 0.001 per minute, at a wavelength of 530 nm, using syringaldazine as substrate, at 30 ° C. and a pH 6.5. The enzymatic activity of the laccases used according to the invention can also be defined from the oxidation of paraphenylenediamine. The ulac unit corresponds to the quantity of enzyme producing an absorbance delta of 0.001 per minute, at a wavelength of 496.5 nm, using paraphenylenediamine as substrate (64 mM), at 30 ° C and at a pH of 5.

In general, the 4-electron oxidoreductase (s) in accordance with the invention preferably represent from 0.01 to 20% by weight approximately of the total weight of the dye composition ready for use, and even more preferably from 0 , 1 to 5% by weight approximately of this weight.

In particular, and when one or more laccases are used, the amount of laccase (s) present in the ready-to-use dye composition in accordance with the invention will vary depending on the nature of the laccase (s) used. Preferably, the amount of laccase (s) is between 0.5 and 2000 Lacu approximately (either between 10000 and 40.10 ⁶ units U approximately or between 20 and 20.10 ⁶ units ulac) per 100 g of dye composition ready for use. 'employment.

The peroxidase (s) used in the ready-to-use dye composition in accordance with the invention can in particular be chosen from the enzymes belonging to subclass 1.11.1 described in the work Enzyme

Nomenclature, Académie Press Inc., 1984. Some of them require the presence of a donor to function. This is the case, in particular for NADH peroxidases (1.11.1) [donor = NADH], fatty acids peroxidases (1.11.1.3) [donor = fatty acid, for example palmitate], NADPH peroxidases

(1.11.1.2), [donor = NADPH], cytochrome-c peroxidases (1.11.1.5)

[donor = ferrocytochrome c], iodide peroxidases (1.11.1.8) [donor = iodide], chlorides peroxidases (1.11.10) [donor = chloride], L. ascorbates peroxidases (1 .11.1.11) [donor = L.ascorbate], glutathione peroxidases (1.11.1.9) [donor = glutathione].

Other peroxidases work without a donor; this is the case for catalases (1.11.1.6) and simplex peroxidases (1.11.1.7).

According to the invention, simplex peroxidases (1.11.1.7) are preferably used. All peroxidases work in the presence of hydrogen peroxide which is supplied as is or generated in situ by the enzymatic route [oxidase (s) with 2 electrons and donor (s) in the presence of air].

The peroxidases used can be of plant, animal, fungal or bacterial origin. They can also be obtained by biotechnology. Thus, peroxidases can for example be obtained from apple, apricot, barley, black radish, beet, cabbage, carrot, corn, cotton, garlic, grapes, mint, rhubarb, soy, spinach, coprin, bovine milk, microorganisms such as Acetobacter peroxidans, Staphylococcus faecalis, Arthromyces ramosus.

The unit of activity of peroxidase simplex (1.11.1.7) can be defined as being the quantity of simplex enzyme forming 1 mg of purpurogalline from pyrogallol in 20 s at pH 6 and at 20 ° C. By way of example, the black radish peroxidase P6782 from SIGMA has an activity of approximately 250 units per mg.

The concentration of use of this type of enzyme therefore varies between 25 and 5.10 ^ units per 100g of composition.

The peroxidase (s) in accordance with the invention preferably represent from 0.0001 to 20% by weight approximately of the total weight of the composition, and even more preferably from 0.001 to 10% by weight approximately of this weight.

The ready-to-use dye composition according to the invention preferably contains at least one oxidation dye precursor or oxidation base. The nature of these oxidation bases is not critical.

They can in particular be chosen from paraphenylenediamines, double bases, para-aminophenols, ortho-aminophenols other than those of formula (I) and heterocyclic oxidation bases. Among the paraphenylenediamines which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may in particular be made of the compounds of formula (II) below and their addition salts with an acid:

in which :

Ri represents a hydrogen atom, a C1-C4 alkyl radical, Cι-C ₄ monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, alkoxy (C * r

C) alkyl (C * ι-C), C-ι-C alkyl substituted by a nitrogen group, phenyl or

4'-aminophenyl; R ₂ represents a hydrogen atom, an alkyl radical in C-ι-C ₄ , monohydroxyalkyle in CC or polyhydroxyalkyle in C ₂ -C, alkoxy (C -

C ₄ ) alkyl (CrC ₄ ) or C-ι-C alkyl substituted by a nitrogen group;

Ri and R ₂ can also form, with the nitrogen atom which carries them, an optionally substituted nitrogen heterocycle; R ₃ represents a hydrogen atom, a halogen atom such as a chlorine atom, a Cι-C alkyl radical, sulfo, carboxy, C ₁ -C ₄ monohydroxyalkyl or C1-C ₄ hydroxyalkoxy, acetylaminoalkoxy in Cι-C ₄ , mesylaminoalkoxy in

C1.-C4 or carbamoylaminoalkoxy in Cι-C ₄ , R ₄ represents a hydrogen atom, halogen or an alkyl radical in CC ₄ .

Among the nitrogen groups of formula (I) above, mention may in particular be made of the amino, monoalkyl (Cι-C ₄ ) amino, dialkyl (Cι-C) amino, trialkyl (Cι-C) amino, monohydroxyalkyl (C) radicals -ι-C ₄ ) amino, imidazolinium and ammonium.

Among the paraphenylenediamines of formula (I) above, there may be mentioned more particularly paraphenylenediamine, paratoluylenediamine, 2-chloro-paraphenylenediamine, 2,3-dimethyl-paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 2 , 6-diethyl-paraphenylenediamine, the 2,5-dimethyl-paraphenylenediamine, N, N-dimethyl-paraphenylenediamine, N, N-diethyl-paraphenylenediamine, N, N-dipropyl-paraphenylenediamine, 4-amino-N, N-diethyl-3-methyl- aniline, NN-bis- (β-hydroxyethyl) - paraphenylenediamine, 4-amino-N, N-bis- (β-hydroxyethyl) -3-methyl-aniline, 4-amino-3-chloro-N, N -bis- (β-hydroxyethyl) -aniline, 2-β-hydroxyethyl- paraphenylenediamine, 2-fluoro-paraphenylenediamine, 2-isopropyl- paraphenylenediamine, N- (β-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl- paraphenylenediamine, N, N-dimethyl-3-methyl- paraphenylenediamine, N, N- (ethyl, β-hydroxyethyl) -paraphenylenediamine, N- (β, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl ) - paraphenylenediamine, N-phenyl-paraphenylenediamine, 2-β-hydroxyethyloxy-paraphenylenediamine, and their addition salts with an acid. Among the para-phenylenediamines of formula (I) above, very particularly preferred are para-phenylenediamine, paratoluylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 6-dimethyl-paraphenylene diamine, 2,6-diethyl-paraphenylenediamine, 2,3-dimethyl- paraphenylenediamine, N, N-bis- (β-hydroxyethyl) -paraphenylenediamine, 2-chloro-paraphenylenediamine, and their addition salts with an acid.

According to the invention, the term “double bases” is intended to mean compounds comprising at least two aromatic rings on which are carried amino and / or hydroxyl groups.

Among the double bases which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may in particular be made of the compounds corresponding to the following formula (III), and their addition salts with an acid:

in which :

- Zi and Z ₂ , identical or different, represent a hydroxyl radical or -NH _{2 which} can be substituted by a Cι-C alkyl radical or by a link arm Y;

- the link arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched which can be interrupted or terminated by one or more nitrogen groups and / or by one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, and optionally substituted by one or more hydroxyl or C ₁ -C 6 alkoxy radicals;

- R ₅ and R ₆ represent a hydrogen or halogen atom, an alkyl radical in C ₁ -C ₄ monohydroxyalkyl, C ₁ -C ₄ polyhydroxyalkyl, C ₂ -C ₄ aminoalkyl C1.-C ₄ or a link arm Y;

- R, R ₈ , R9, R10, R ₁₁ and R- < ₂ , identical or different, represent a hydrogen atom, a linker Y or a C ₁ -C ₄ alkyl radical;

it being understood that the compounds of formula (III) have only one linker arm Y per molecule.

Among the nitrogen groups of formula (III) above, there may be mentioned in particular the amino, monoalkyl (Cι-C ₄ ) amino, dialkyl (Cι-C ₄ ) amino, trialkyl (C ₁ -C) amino _l monohydroxyalkyl radicals (Cι-C) amino, imidazolinium and ammonium.

Mention may more particularly be made, among the double bases of formulas (III) above, of N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol , 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, 1,8-bis- (2,5-diaminophenoxy) -3,5- dioxaoctane, and their addition salts with an acid.

Among these double bases of formula (III), N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, 1,8-bis- (2,5-diaminophenoxy) - 3,5-dioxaoctane or one of their addition salts with an acid are particularly preferred.

Among the para-aminophenols which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may in particular be made of the compounds corresponding to the following formula (IV), and their addition salts with an acid:

in which :

Ri ₃ represents a hydrogen atom, a halogen atom such as fluorine, an alkyl radical in Cι-C ₄ , monohydroxyalkyl in C ₁ -C ₄ , alkoxy (Cι-C) alkyl (Cι-C ₄ ) or aminoalkyl in C1-C ₄ , or hydroxyalkyl (Cι-C) aminoalkyl in C ₁ -C ₄ . R ₁ represents a hydrogen atom or a halogen atom such as fluorine, alkyl C1.--C ₄ monohydroxyalkyl, C ₁ -C ₄ polyhydroxyalkyl, C ₂ -C ₄ aminoalkyl, C 1 -C 4 , C1-cyanoalkyl _. -C ₄ or alkoxy (Cι-C ₄ ) alkyl (C ₁ -C).

Among the para-aminophenols of formula (IV) above, mention may more particularly be made of para-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluoro-phenol, 4-amino -3-hydroxymethyl-phenol, 4-amino-2-methyl-phenol, 4-amino-2-hydroxymethyl-phenol, 4-amino- 2-methoxymethyl-phenol, 4-amino-2-aminomethyl-phenol , 4-amino- 2- (β-hydroxyethyl-aminomethyl) -phenol, and their addition salts with an acid. Among the ortho-aminophenols which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made more particularly of 2-amino-phenol, 2-amino-1-hydroxy-5-methyl-benzene, 2-amino-1-hydroxy-6-methyl-benzene, 5-acetamido-2-amino-phenol, and their addition salts with an acid.

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

Among the pyridine derivatives, mention may more particularly be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) -amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- (β-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

Among the pyrimidine derivatives, mention may be made more particularly of the compounds described for example in German patents DE 2,359,399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent applications WO 96/15765, such as 2,4, 5,6-tetra-aminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2, 5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo- [1,5-a] -pyrimidine-3,7- diamine; 2,5-dimethyl-pyrazolo- [1,5-a] - pyrimidine-3,7-diamine; pyrazoIo- [1,5-a] -pyrimidine-3,5-diamine; 2,7-dimethyl-pyrazolo- [1,5-a] -pyrimidine-3,5-diamine; 3-amino-pyrazolo- [1,5-a] -pyrimidin-7-ol; 3-amino-pyrazolo- [1,5-a] -pyrimidin-5-ol; 2- (3-amino pyrazolo- [1,5-a] -pyrimidin-7-ylamino) ethanol, 2- (7-amino-pyrazolo- [1,5-a] - pyrimidin-3-ylamino) -ethanol, 2 - [(3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) ~ (2-hydroxy-ethyl) -amino] -ethanol, 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 5,6-dimethyl-pyrazolo- [1,5-a] -pyrimidine- 3,7- diamine, 2,6-dimethyl-pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, 2, 5, N7, N7-tetramethyl-pyrazolo- [1,5-a] -pyrimidine-3,7-diamine, and their addition salts and tautomeric forms, when there is a tautomeric equilibrium and their salts 'addition with an acid.

Among the pyrazole derivatives, mention may more particularly be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4,5-diamino-1-methyl-pyrazole, 4,5-diamino-1-hydroxyethyl-pyrazole, 3,4-diamino-pyrazole, 4,5-diamino-1- (4'- chlorobenzyl) -pyrazole, 4,5-diamino 1, 3-dimethyl-pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino 1-methyl-3-phenyl-pyrazole , 4-amino-1, 3-dimethyl-5-hydrazino-pyrazole, 1-benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1- methyl pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5-diamino-1- (β- hydroxyethyl) -3-methyl pyrazole, 4,5-diamino-1 -ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl-pyrazole, 4 , 5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl-pyra zole, 4,5-diamino-3-methyl-1-isopropyl-pyrazole, 4-amino-5- (2'-aminoethyl) amino-1, 3-dimethyl-pyrazole, 3,4,5-triamino -pyrazole, 1-methyl-3,4,5-triamino-pyrazole, 3,5-diamino 1-methyl-4-methylamino-pyrazole, 3,5-diamino-4- (β-hydroxyethyl) amino 1 -methyl-pyrazole, and their addition salts with an acid.

According to a preferred embodiment of the invention, the oxidation base (s) are chosen from paraphenylenediamines.

The oxidation base (s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition ready for use according to the invention, and even more preferably from 0.005 to 8% by weight approximately. of this weight.

Additional couplers

The ready-to-use dye composition in accordance with the invention may also contain one or more additional couplers other than those of formula (I) according to the invention and usually used in oxidation dyeing chosen from meta-aminophenols, metaphenylenediamines, metadiphenols, naphthols and heterocyclic couplers such as, for example, indole derivatives, indolinic derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1, 3-benzodioxoles, quinolines and their addition salts with an acid.

These couplers are more particularly chosen from 2-methyl-5-amino-phenol, 5-N- (β-hydroxyethyl) -amino-2-methyl-phenol, 3-amino-phenol,

1, 3-dihydroxy-benzene, 1, 3-dihydroxy-2-methyl-benzene, 4-chloro-

1, 3-dihydroxy-benzene, 2,4-diamino-1- (β-hydroxyethyloxy) -benzene, 2-amino-4-

(β-hydroxyethylamino) -l-methoxy-benzene, 1, 3-diamino-benzene, 1, 3-bis- (2,4-diaminophenoxy) -propane, sesamol, α-naphthol, 1 - acetoxy-2-methylnaphthalene, 6-hydroxy-indole, 4-hydroxy-indole, 4-hydroxy-N-methyl-indole, 3- (4-hydroxy-1-methyl-1 H-) chloride indol-5-yl-methyl) -1-methyl-pyridinium, 6-hydroxy-indoline, 2,6-dihydroxy-4-methyl-pyridine, 3,5-diamino-2,6-dimethoxy-pyridine, 1-H-3-methyl-pyrazoIe-5-one, 1-phenyl-3-methyl-pyrazole-5-one, and their addition salts with an acid.

When they are present, these additional couplers preferably represent from 0.0001 to 15% by weight approximately of the total weight of the dye composition ready for use and even more preferably from 0.001 to 10% approximately.

The addition salts with an acid of these oxidation dyes (bases and couplers) present in the dye compositions of the invention are especially chosen from hydrochlorides, hydrobromides, sulfates and tartrates, lactates and acetates.

Direct dyes

The ready-to-use dye composition in accordance with the invention may also contain one or more direct dyes, in particular for modifying the shades by enriching them with reflections. These direct dyes can in particular then be chosen from nitro, azo or anthraquinone, neutral, cationic or anionic dyes in the proportion by weight of approximately 0.001 to 20% and preferably from 0.01 to 10% of the total weight of the composition.

Dye medium

The medium suitable for dyeing (or support) the ready-to-use dye composition in accordance with the invention generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. Mention may be made, as organic solvent, of C 1 -C 4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, those described in French patent application 2,773,475, the content of which is an integral part of the invention, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogues and their mixtures.

The solvents, when they are present in the medium, can represent approximately 0.5 to 20% and, preferably approximately 2 to 10% by weight of the total weight of the dye composition ready for use.

When the oxidizing agent is an enzyme, the pH of the ready-to-use composition in accordance with the invention is chosen so that the enzymatic activity of the 2-electron or 4-electron oxidoreductase or of the peroxidase is sufficient. It is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately.

When the oxidizing agent is a peroxide, a persalt or a bromate, the pH is between these same values; it can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers.

Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, acid sulfuric, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines, 2-methyl 2-amino 1-propanol and their derivatives, sodium or potassium hydroxides and the compounds of formula (V) below:

^{Rl 5} \ _X ^R 17

N -W- N (V)

/ \ r \ ₁₆ Γ ₁₈ in which W is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; R15 R-iδ, R17 and Rι _8, identical or different, represent a hydrogen atom, an alkyl radical in C ₁ -C ₄ hydroxyalkyl or C ₁ -C _4.

The ready-to-use composition according to the invention also preferably comprises, in the composition containing the 4-position derivative (s) of the 5-halo-ortho-amino-phenols of formula (I), at least one thickening polymer of anionic, nonionic, cationic, or amphoteric type comprising at least one fatty chain.

Among the thickening polymers comprising at least one fatty chain and of anionic type, there may be mentioned:

- (I) those comprising at least one hydrophilic unit, and at least one allyl ether unit with fatty chain, more particularly those whose hydrophilic unit consists of an anionic ethylenically unsaturated monomer, more particularly still by a vinyl carboxylic acid and most particularly with an acrylic acid or a methacrylic acid or mixtures thereof, and the fatty chain allyl ether unit of which corresponds to the monomer of formula (I) below:

CH ₂ = CR 'CH ₂ OB _n R (I) in which R' denotes H or CH ₃ , B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl, cycloalkyl radicals, comprising from 8 to 30 carbon atoms, preferably 10 to 24, and more particularly still from 12 to 18 carbon atoms. A unit of formula (I) more particularly preferred is a unit in which R 'denotes H, n is equal to 10, and R denotes a stearyl radical (Cι ₈ ).

Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479.

Among these fatty chain anionic thickening polymers, 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 of formula (I), and from 0 to 1% by weight of a crosslinking agent which is a copolymerizable polyethylene unsaturated monomer well known, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide. Among the latter, very particularly preferred are the crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) stearyl alcohol ether (Steareth 10), in particular those sold by the company ALLIED COLLOIDS under the names SALCARE SC 80 and SALCARE SC90 which are 30% aqueous emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10).

- (11) those comprising at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit of alkyl ester (Cι ₀ -C ₃₀ ) type of unsaturated carboxylic acid. Preferably, these polymers are chosen from those in which the hydrophilic unit of olefinic unsaturated carboxylic acid type corresponds to the monomer of formula (II) below:

CH ₂ ICC OH (||)

R ₁ O in which, R denotes H or CH ₃ or C ₂ H ₅ , that is to say acrylic acid, methacrylic acid or ethacrylic acid units, and of which the hydrophobic unit of alkyl ester type (C ₁₀ -C ₃₀ ) of unsaturated carboxylic acid corresponds to the monomer of formula (III) below:

in which, R ₂ denotes H or CH ₃ or C ₂ H ₅ (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH ₃ (methacrylate units), R ₃ denoting an alkyl radical in C10-C30, and preferably in Cι ₂ -C ₂₂ .

(C ₁₀ -C ₃₀ ) alkyl esters of unsaturated carboxylic acids according to 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 polymers of this type are for example described and prepared, according to US Pat. Nos. 3,915,921 and 4,509,949. Among this type of anionic thickening polymers with a fatty chain, use will be made more particularly of polymers formed from a mixture of monomers comprising:

(i) essentially acrylic acid,

(ii) an ester of formula (III) described above and in which R ₂ denotes H or CH ₃ , R ₃ denotes an alkyl radical having from 12 to 22 carbon atoms, (iii) and a crosslinking agent, which is a well known copolymerizable polyethylene unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide. Among this type of anionic thickening polymers with a fatty chain, use will be made more particularly of those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of Cι ₀ -C alkyl acrylate ₃₀ (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or else those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of alkyl acrylate in Cι ₀ -C ₃₀ (hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among said polymers above, very particularly preferred according to the present invention, the products sold by the company GOODRICH under the trade names PEMULEN TR1, PEMULEN TR2, CARBOPOL 1382, and even more preferably PEMULEN TR1, and the product sold by SEPPIC under the name COATEX SX.

- (III) terpolymers of maleic anhydride / - C oC ₃₈ olefin / alkyl maleate such as the product (maleic anhydride / α-olefin C ₃ oC ₃₈ / isopropyl maleate copolymer) sold under the name PERFORMA V 1608 by NEWPHASE TECHNOLOGIES.

- (IV) acrylic terpolymers comprising:

(a) about 20% to 70% by weight of an α, β-monoethylenically unsaturated carboxylic acid,

(b) about 20 to 80% by weight of a non-surfactant α, β-monoethylenically unsaturated monomer other than (a), (c) about 0.5 to 60% by weight of a mono-urethane nonionic 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 methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate behenyl alcohol ethoxylated (40OE) terpolymer in 25% aqueous dispersion.

- (V) 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 α, β-monoethylenically unsaturated carboxylic acid and of alcohol in

C1C4.

As an example of this type of compound, mention may be made of ACULYN 22 sold by the company ROHM and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer. The nonionic type fatty chain thickening polymers used according to the invention are preferably chosen from:

- (1) celluloses modified by groups comprising at least one fatty chain; as an example, we can cite:

- hydroxyethylcelluloses modified by groups comprising at least one fatty chain such as alkyl, arylalkyl, alkylaryl groups, or their mixtures, and in which the alkyl groups are preferably C ₈ -C ₂₂ , such as the product NATROSOL PLUS GRADE 330 CS (C-alkyls, ₆ ) sold by the company AQUALON, or the product BERMOCOLL EHM 100 sold by the company BEROL NOBEL,

- those modified with polyalkylene glycol ether groups of alkyl phenol, such as the product AMERCELL POLYMER HM-1500 (polyethylene glycol (15) nonyl phenol ether) sold by the company AMERCHOL.

- (2) hydroxypropylguars modified by groups comprising at least one fatty chain such as the product ESAFLOR HM 22 (C ₂₂ alkyl chain) sold by the company LAMBERTI, the products RE210-18 (C ₄ alkyl chain ι ₄ ) and RE205-1 (C ₂₀ alkyl chain) sold by the company RHONE POULENC.

- (3) copolymers of vinyl pyrrolidone and hydrophobic fatty chain monomers; as an example, we can cite:

- ANTARON V216 or GANEX V216 products (vinylpyrrolidone / hexadecene copolymer) sold by the company I.S.P.

- ANTARON V220 or GANEX V220 products (vinylpyrrolidone / eicosene copolymer) sold by the company I.S.P.

- (4) copolymers of methacrylates or of C * ι-C ₆ alkyl acrylates and of amphiphilic monomers comprising at least one fatty chain, such as for example the methyl acrylate / oxyethylenated stearyl acrylate sold by the company GOLDSCHMIDT under the name ANTIL 208. - (5) copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers comprising at least one fatty chain such as for example the polyethylene glycol methacrylate / lauryl methacrylate copolymer.

- (6) polyether polyurethanes comprising in their chain, both hydrophilic sequences of a nature most often polyoxyethylenated and hydrophobic sequences which can be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences.

- (7) polymers with an aminoplast ether skeleton having at least one fatty chain, such as the PURE THIX compounds offered by the company SUD-CHEMIE.

Preferably, the polyether polyurethanes comprise at least two lipophilic hydrocarbon chains, having from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon chains being able to be pendant chains or chains at the end of hydrophilic block. In particular, it is possible that one or more hanging chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block.

The polyether polyurethanes can be multiblock in particular in the form of a triblock. The hydrophobic blocks can be at each end of the chain (for example: triblock copolymer with hydrophilic central block) or distributed both at the ends and in the chain (multiblock copolymer for example). These same polymers can also be in grafts or in a star.

The nonionic fatty chain polyurethane polyethers can be triblock copolymers whose hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylenated groups. Non-ionic polyether polyurethanes contain a urethane bond between the hydrophilic sequences, hence the origin of the name.

By extension, also included among the nonionic fatty-chain polyurethane polyethers, those whose hydrophilic sequences are linked to the lipophilic sequences by other chemical bonds. As examples of non-ionic polyether polyurethanes with a fatty chain which can be used in the invention, it is also possible to use Rheolate 205 with urea function sold by the company RHEOX or Rheolates 208, 204 or 212, as well as Acrysol RM 184, PAculyn 44 and Aculyn 46 from the company ROHM & HAAS [ACULYN 46 is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene bis (4- cyclohexylisocyanate) (SMDl), 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44 is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDl), at 35% by weight in a mixture of propylene glycol (39 %) and water (26%)].

We may also mention the product Elfacos T210 alkyl chain Cι ₂ -ι ₄ and the product Elfacos T212 containing a alkyl chain in C ₁₈ from Akzo. The product DW 1206B from ROHM & HAAS with a C ₂₀ alkyl chain and a urethane bond, offered at 20% dry matter in water, can also be used. It is also possible to use solutions or dispersions of these polymers, especially in water or in an alcoholic medium. By way of example, such polymers that may be mentioned are Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company RHEOX. One can also use the product DW 1206F and the DW 1206J offered by the company ROHM & HAAS.

The polyether polyurethanes which can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380.389 (1993 ;.

The fatty chain thickening polymers of cationic type used according to the present invention are preferably chosen from quaternized cellulose derivatives and polyacrylates with non-cyclic amino side groups.

The quaternized cellulose derivatives are, in particular,

- quaternized celluloses modified by groups comprising at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof, - quaternized hydroxyethylcelluloses modified by groups comprising at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the celluloses or hydroxyethylcelluloses quaternized above preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote the phenyl, benzyl, naphthyl or anthryl groups. As examples of quaternized C ₈ -C ₃₀ fatty chain alkyl hydroxyethyl celluloses, the products QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C ₁₂ alkyl) and QUATRISOFT LM-X 529-8 (Cι. ₈ alkyl) sold by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (C ₁₂ alkyl) and CRODACEL QS (C18 alkyl) sold by the company CRODA.

Polyacrylates with amino side groups, quaternized or not, for example have hydrophobic groups of the steareth 20 type (polyoxyethylenated stearyl alcohol (20)). As examples of polyacrylates with amino side chains, mention may be made of polymers 8781-121 B or 9492-103 offered by the company National Starch.

The amphoteric type fatty chain thickening polymers used according to the present invention are preferably chosen from acrylic acid / (meth) acrylamidopropyl trimethyl ammonium chloride / stearyl methacrylate terpolymers.

The fatty chain thickening polymers of anionic, nonionic, cationic or amphoteric type are preferably used in an amount which can vary from approximately 0.01 to 10% by weight of the total weight of the dye composition. More preferably, this amount varies from about 0.1 to 5% by weight.

The ready-to-use composition according to the invention may also preferably further comprise, in the composition containing the derivative (s) in position-4 5-halo-ortho-amino-phenols of formula (I), at least one cationic or amphoteric polymer.

Cationic polymers Within the meaning of the present invention, the expression “cationic polymer” designates any polymer containing cationic groups and / or groups which can be ionized into cationic groups.

The cationic polymers which can be used in accordance with the present invention can be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in patent application EP-A-337 354 and in French patents FR- 2,270,846, 2,383,660, 2,598,611, 2,470,596 and 2,519,863.

The preferred cationic polymers are chosen from those which contain units comprising primary, secondary, tertiary and / or quaternary amine groups which can either be part of the main polymer chain or be carried by a lateral substituent directly connected thereto.

The cationic polymers used generally have a number average molecular mass of between 500 and 5.10 ⁶ approximately, and preferably between 10 ³ and 3.10 ⁶ approximately.

Among the cationic polymers, mention may more particularly be made of polymers of the polyamine, polyaminoamide and quaternary polyammonium type. These are known products. They are described in particular in French patents 2,505,348 or 2,542,997. Among the said polymers, there may be mentioned:

(1) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of formulas (I), (11), (III) or (IV):

in which:

R3, identical or different, denote a hydrogen atom or a CH3 radical;

A, identical or different, represent an alkyl group, linear or branched, from 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group from 1 to 4 carbon atoms; R4, R5, R6, identical or different, represent an alkyl group having from 1 to

18 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms;

R * 1 and R2, identical or different, represent hydrogen or an alkyl group having from 1 to 6 carbon atoms and preferably methyl or ethyl;

X denotes an anion derived from a mineral or organic acid such as a methosulfate anion or a halide such as chloride or bromide.

The polymers of family (1) can also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls (C1-C4), acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters. Thus, among these polymers of family (1), there may be mentioned:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl hologenide, such as that sold under the name HERCOFLOC by the company HERCULES,

the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described for example in patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY,

- the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulfate sold under the name RETEN by the company HERCULES, vinylpyrrolidone / acrylate or dialkylaminoalkyl methacrylate quaternized or not, such as the products sold under the name "GAFQUAT" ISP such as "GAFQUAT 734" or "GAFQUAT 755" or the products called "COPOLYMER 845, 958 and 937". These polymers are described in detail in French patents 2,077,143 and 2,393,573,

- dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers such as the product sold under the name GAFFIX VC 713 by the company ISP,

- the vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymer sold in particular under the name STYLEZE CC 10 by ISP,

- and vinylpyrrolidone / methacrylamide dimethylaminopropyl quaternized copolymers such as the product sold under the name "GAFQUAT HS 100" by the company ISP.

(2) Derivatives of cellulose ethers comprising quaternary ammonium groups described in French patent 1,492,597, and in particular the polymers marketed under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by the Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammonium hydroxyethylcellulose having reacted with an epoxide substituted by a trimethylammonium group.

(3) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer, and described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl- , hydroxyethyl- or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyl trimethylammonium, of methacrylmidopropyl trimethylammonium, of dimethyl-diallylammonium.

The marketed products meeting this definition are more particularly the products sold under the name "Celquat L 200" and "Celquat H 100" by the National Starch Company.

(4) The cationic polysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups. Guar gums modified with a salt (eg chloride) of 2,3-epoxypropyl trimethylammonium are used, for example. Such products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company MEYHALL.

(5) Polymers consisting of piperazinyl units and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, optionally interrupted by oxygen, sulfur, nitrogen atoms or by aromatic or heterocyclic rings, as well as the products of oxidation and / or quaternization of these polymers. Such polymers are described in particular in French patents 2,162,025 and 2,280,361.

(6) Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis- halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide or also by an oligomer resulting from the reaction of a bifunctional compound reactive with respect to a bis-halohydrin, of a bis -azetidinium, a bis-haloacyldiamine, an alkyl bis-halide, an epilhalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amino group of the polyaminoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary, quaternized amine functions. Such polymers are described in particular in French patents 2,252,840 and 2,368,508.

(7) Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation by bifunctional agents. Mention may be made, for example, of the adipic acid-diacoylaminohydroxyalkoyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl, propyl. Such polymers are described in particular in French patent 1,583,363.

Among these derivatives, there may be mentioned more particularly the adipic acid / dimethylaminohydroxypropyl / diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz.

(8) The polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polylamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the resulting polyaminoamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are described in particular in the patents American 3,227,615 and 2,961,347.

Polymers of this type are in particular sold under the name "Hercosett 57" by the company Hercules Inc. or else under the name name of "PD 170" or "Delsette 101" by the company Hercules in the case of the copolymer of adipic acid / epoxypropyl / diethylene-triamine.

(9) Cyclopolymers of alkyl diallyl amine or dialkyl diallyl ammonium such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (V) or (VI):

formulas in which k and t are equal to 0 or 1, the sum k + t being equal to 1; Rg denotes a hydrogen atom or a methyl radical; R ₇ and R ₈ , independently of one another, denote an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (C1-C4), or R7 and Rg may denote jointly with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R ₇ and R ₈ independently of one another preferably denote an alkyl group having from 1 to 4 carbon atoms; Y ^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are described in particular in French patent 2,080,759 and in its certificate of addition 2,190,406. Among the polymers defined above, there may be mentioned more particularly the homopolymer of dimethyldiallylammonium chloride sold under the name "Merquat 100" by the company Calgon (and its counterparts of low weight average molecular weight) and the copolymers of diallyldimethylammonium chloride and of acrylamide sold under the name "MERQUAT 550".

(10) The quaternary diammonium polymer containing recurring units corresponding to the formula:

formula (Vil) in which:

^R 10 _> ^R 11 _> ^R 12 and 13 _> identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or else R- [-Q. Ru,

R-12 and R 3, together or separately, constitute with the nitrogen atoms to which they are attached heterocycles possibly containing a second heteroatom other than nitrogen or else R * ιo, Ru, R- | 2 t R-13 represent a linear or branched C- | -C6- alkyl radical substituted by a nitrile, ester, acyl, amide or -CO-O- R14-D or -CO-NH- group

where R-14 is alkylene and D is a quaternary ammonium group;

A1 and B1 represent polymethylenic groups containing from 2 to 20 carbon atoms which may be 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 atoms of oxygen, 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; A1, R-io t 12 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 can also denote a group - (CH2) n-CO- D-OC- (CH2) n- in which D denotes: a) a glycol residue of formula: -OZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas:

- (CH2-CH2-0) x-CH ₂ -CH ₂ - - [CH2-CH (CH3) -0] y-CH ₂ -CH (CH ₃ ) - where x and y denote an integer from 1 to 4 , representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative; c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or else the bivalent radical -CH2-CH2-SS-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 molecular weight generally between 1000 and 100,000.

Polymers of this type are described in particular in French patents 2,320,330, 2,270,846, 2,316,271, 2,336,434 and 2,413,907 and US patents 2,273,780, 2,375,853, 2,388,614, 2,454,547 , 3.206.462, 2.261.002, 2.271.378, 3.874.870, 4.001.432, 3.929.990, 3.966.904, 4.005.193, 4.025.617, 4.025.627, 4.025.653, 4.026.945 and 4.027 .020.

It is possible to use more particularly the polymers which consist of recurring units corresponding to the following formula (VIII):

in which RJ Q. ^R 1 1. 12 and R 3 _ι identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms approximately, n and p are whole numbers varying from 2 to 20 approximately and, X - is an anion derived from a mineral or organic acid. (11) Quaternary polyammonium polymers consisting of recurring units of formula (IX):

- O - (CH ₂ ) ₂ ^• (IX)

in which p denotes an integer varying from 1 to 6 approximately, D may be zero or may represent a group - (CH2) r -CO- in which r denotes a number equal to 4 or 7, X- is an anion;

Such polymers can be prepared according to the methods described in U.S. Pat. Nos. 4,157,388, 4,390,689, 4,702,906, 4,719,282. They are described in particular in patent application EP-A-122 324.

Among them, there may be mentioned, for example, the products "Mirapol A 15", "Mirapol AD1", "Mirapol AZ1" and "Mirapol 175" sold by the company Miranol.

(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as for example the products marketed under the names Luviquat

FC 905, FC 550 and FC 370 by B.A.S.F.

(13) Polyamines such as Polyquart H sold by HENKEL, referenced under the name of "POLYETHYLENEGLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary.

(14) Crosslinked polymers of methacryloyloxyalkyl (C- | -C4) trialkyl (C- _| -) salts

C4) ammonium such as the polymers obtained by homopolymerization of dimethylaminoethylmethacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethylmethacrylate quaternized with methyl chloride, homo or copolymerization being followed by crosslinking with a olefinically unsaturated compound, in particular methylene bis acrylamide. It is more particularly possible to use a crosslinked acrylamide / methacryloyloxyethyl trimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is marketed under the name of "SALCARE® SC 92" by the company ALLIED COLLOIDS. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyl trimethylammonium chloride containing approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are marketed under the names of "SALCARE® SC 95" and "SALCARE® SC 96" by the company ALLIED COLLOIDS.

Other cationic polymers which can be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, polyamine and epichlorohydrin condensates, quaternary polyureylenes and chitin derivatives.

Among all the cationic polymers capable of being used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10) (11) and (14) and even more preferably the polymers of formulas (W) and (U) below:

t- (W)

CH ₃ CH and in particular those whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900;

CH ₃ C ₂ H ₅ and in particular those whose molecular weight, determined by gel permeation chromatography, is approximately 1200.

The concentration of cationic polymer in the compositions according to the present invention can vary from 0.01 to 10% by weight relative to the total weight of the composition, preferably from 0.05 to 5% and even more preferably from 0.1 to 3%.

Amphoteric polymers The amphoteric polymers which can be used in accordance with the present invention can be chosen from polymers comprising K and M units distributed statistically in the polymer chain, where K denotes a unit derived from a monomer comprising at least one basic nitrogen atom and M denotes a unit deriving from an acid monomer comprising one or more carboxylic or sulphonic groups, or else K and M can denote groups deriving from zwitterionic monomers of carboxybetaines or sulphobetaines; K and M can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical, or although K and M form part of a chain of a polymer with an α, β-dicarboxylic ethylene unit, one of the carboxyl groups of which has been reacted with a polyamine comprising one or more primary or secondary amine groups.

The amphoteric polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:

(1) The polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and of a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, the diaikylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US Pat. No. 3,836,537. Mention may also be made of the sodium acrylate / acrylamide propyl trimethyl ammonium chloride copolymer sold under the name POLYQUART KE 3033 by the company HENKEL.

The vinyl compound can also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. The copolymers of acrylic acid and of the latter monomer are offered under the names MERQUAT 280, MERQUAT 295 and MERQUAT PLUS 3330 by the company CALGON.

(2) Polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reactants, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. The N-substituted acrylamides or methacrylamides more particularly preferred according to the invention are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl-acrylamide, N-tertiooctyl-acrylamide , N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides. The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides. The preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.

Copolymers are particularly used whose name CTFA (4th Ed., 1991) is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.

(3) Crosslinked and alkylated polyaminoamides partially or totally derived from polyaminoamides of general formula:

- j- co - R ₁₉ - co - z— î— (X)

in which R-] g represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or of a radical derived from the addition of any one of said acids with a primary bis or secondary bis amino, and Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents : a) in the proportions of 60 to 100 mol%, the radical

where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this radical deriving from diethylene triamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol% the radical (XI) above, in which x = 2 and p = 1 and which derives from ethylenediamine, or the radical deriving from piperazine:

\ / c) in the proportions of 0 to 20 mole% the radical -NH- (CH2) 6-NH- deriving from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides , dianhydrides, bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent by amino group of polyaminoamide and alkylated by the action of acrylic acid, chloracetic acid or an alkane sultone or their salts . The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids. The alkane sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

(4) Polymers comprising zwitterionic units of formula:

in which R20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, R21 and R22 represent a hydrogen, methyl, ethyl or propyl atom, R23 and R24 represent a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.

The polymers comprising such units may also contain units derived from non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate. By way of example, there may be mentioned the copolymer of butyl methacrylate / dimethylcarboxymethylammonioethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.

(5) polymers derived from chitosan comprising monomer units corresponding to formulas (XIII), (XIV), (XV) below:

the motif (XIII) being present in proportions of between 0 and 30%, the motif (XIV) in proportions of between 5 and 50% and the motif (XV) in proportions of between 30 and 90%, it being understood that in this motif (XV), R ₂₅ represents a radical of formula:

in which q denotes zero or 1; if q = 0, R26. 27 ^{and R} 28 _> identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkoyiamine residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted by one or more amino, hydroxyl, carboxyl, alkylthio, sulfonic groups, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R26, R27 and R28 being in this case a hydrogen atom; or if q = 1, R26. ^R 27 and R28 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(6) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by the company JAN DEKKER.

(7) The polymers corresponding to the general formula (XI) such as those described for example in French patent 1,400,366:

in which R29 represents a hydrogen atom, a CH3O, CH3CH2O, phenyl radical, R30 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R31 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R32 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R33-N (R3- |) 2, R33 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2 -CH (CH3) -, R31 having the meanings mentioned above, as well as the higher homologs of these radicals and containing up to 6 carbon atoms,

r is such that the molecular weight is between 500 and 6,000,000 and preferably between 1,000 and 1,000,000.

(8) Amphoteric polymers of the type -D-X-D-X- chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloroacetate on the compounds comprising at least one unit of formula:

-DXDXD- (XVII) where D denotes a radical _-V ^~~ V_

\ / and X denotes the symbol E or E ', E or E', which are identical or different, denote a bivalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups and which may also contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane; b) polymers of formula:

-D-X-D-X- (XVIII) where D denotes a radical

\ / and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, whether or not substituted by one or more hydroxyl radicals and comprising a or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloracetate.

The amphoteric polymers which are particularly preferred according to the invention are those of the family (1).

According to the invention, the amphoteric polymer (s) can represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and even more preferably from 0.1% to 3% by weight , of the total weight of the composition. The ready-to-use composition according to the invention also preferably comprises, in the composition containing the derivative (s) in position-4 of the 5-halo-ortho-amino-phenols of formula (I), at least one surfactant.

Surfactants

The surfactant (s) may be chosen, alone or in mixtures, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants. They are more particularly chosen from nonionic surfactants.

The surfactants which are suitable for carrying out the present invention are in particular the following:

(i) Anionic surfactant (s):

By way of example of anionic surfactants which can be used, alone or as mixtures, in the context of the present invention, there may be mentioned in particular (non-limiting list) the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts) of the following compounds: alkylsulphates, alkylethersulphates, alkylamidoethersulphates, alkylarylpolyethersulphates, monoglycerides sulphates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin-sulfonates, paraffin-rsulfonates; (C ₆ -C ₂₄ ) alkyl sulfosuccinates, (C ₆ -C ₂ ) alkyl ethersulfosuccinates, (C ₆ -C ₂ ) alkyl amidesulfosuccinates; (C ₆ -C ₂ ) alkyl sulfoacetates; acyl (C ₆ -C ₂₄ ) sarcosinates and acyl (C ₆ -C ₂₄ ) glutamates. It is also possible to use the alkyl esters (C ₆ -C ₂ 4) carboxylic polyglycosides such as the alkylglucoside citrates, the alkylpolyglycoside tartrate and the alkylpolyglycoside sulfosuccinates., The alkylsulfosuccinamates; acylisethionates and N-acyltau splees, the alkyl or acyl radical of all these different compounds preferably containing from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants which can still be used, mention may also be made of the salts fatty acids such as the oleic, ricinoleic, palmitic, stearic acid salts, coconut oil acids or hydrogenated coconut oil; acyl lactylates whose acyl radical contains 8 to 20 carbon atoms. It is also possible to use the alkyl D galactoside uronic acids and their salts, the polyoxyalkylenated (C ₆ -C ₂₄ ) alkyl ether carboxylic acids, the polyoxyalkylenated (C ₆ -C ₂₄ ) aryl ether carboxylic acids, the alkyl (C ₆ -C ₂ 4) polyoxyalkylenated carboxylic amido ether and their salts, in particular those comprising from 2 to 50 alkylene oxide groups, in particular ethylene, and their mixtures.

(ii) Non-ionic surfactant (s)

Non-ionic surfactants are also well known compounds per se (see in particular in this regard "Handbook of Surfactants" by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178) and their nature is not, in the context of the present invention, critical. Thus, they can in particular be chosen from (nonlimiting list) alcohols, alpha-diols, alkylphenols or polyethoxylated, polypropoxylated fatty acids, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of oxide groups ethylene or propylene oxide which may range in particular from 2 to 50. Mention may also be made of copolymers of ethylene oxide and of propylene, condensates of ethylene oxide and of propylene on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1, 5 to 4; polyethoxylated fatty amines preferably having 2 to 30 moles of ethylene oxide; esters of oxyethylenated sorbitan fatty acids having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkyl glucamine derivatives, amine oxides such as amino (C1Q-C14) alkyl oxides or oxides of N-acylaminopropylmorpholine. It will be noted that the alkylpolyglycosides constitute nonionic surfactants which are particularly well within the scope of the present invention just like the ethoxylated fatty alcohols. (iii) Amphoteric or zwitterionic surfactants:

Amphoteric or zwitterionic surfactants, the nature of which is not critical in the context of the present invention, may in particular be (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a chain linear or branched having 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulfonate, sulfate, phosphate or phosphonate); mention may also be made of (C8-C20) alkyl betaines, sulfobetaines, (C8-C20) alkyl amidoalkyl (C-i-Cβ) betaines or {CQ-C20) amidoalkyl (C-j-C) sulfobetaines alkyls.

Among the amine derivatives, mention may be made of the products sold under the name Miranol, as described in patents US-2,528,378 and US-2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates of respective structures:

R34 -CONHCH ₂ CH ₂ -N (R ₃ 5) (R3 ₆ ) (CH ₂ COO-) in which: R34 denotes an alkyl radical of an acid R34-COOH present in hydrolyzed coconut oil, a heptyl radical , nonyl or undecyl, R35 denotes a beta-hydroxyethyl group and R36 denotes a carboxymethyl group; and R34'-CONHCH ₂ CH2-N (B) (C) in which:

B represents -CH2CH2OX ', C represents - (CH2) _Z -Y', with z = 1 or 2,

X 'denotes the group -CH2CH2-COOH or a hydrogen atom

Y 'denotes -COOH or the radical -CH2 - CHOH - SO3H

R34 ′ denotes an alkyl radical of an acid R37 -COOH present in coconut oil or in hydrolysed linseed oil, an alkyl radical, in particular C7, Cg,

Ci 1 or C13, a C-17 alkyl radical and its iso form, an unsaturated C17 radical. These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroampho- diacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionatepropodopropodampropodopropionampropodampropodampropylamphodipropionate . By way of example, mention may be made of the cocoamphodiacetate sold under the trade name MIRANOL® C2M concentrated by the company RHODIA CHIMIE.

(iv) Cationic surfactants:

Among the cationic surfactants that may be mentioned in particular (non-limiting list): the salts of primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated; quaternary ammonium salts such as chlorides or bromides of tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium; imidazoline derivatives; or cationic amine oxides.

The amounts of surfactants present in the composition according to the invention can vary from 0.01 to 40% and preferably from 0.1 to 30% of the total weight of the composition.

The ready-to-use dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic or nonionic or zwitterionic polymers other than those already mentioned, or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or unmodified, or those described in French patent application 2,773,474, the content of which is an integral part of the invention, film-forming agents, ceramides, preserving agents and reducing agents, opacifying agents.

Among the reducing or antioxidant agents used to preserve the oxidation dyes and usable in the proportion of 0.05 to 1.5% by weight of the total weight of the composition, there may be mentioned in particular sodium sulfite, thioglycolic acid , thiolactic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2-methyl-hydroquinone, ter-butyl-hydroquinone, homogentisic acid, N-acetyl-L-cysteine described in Applicant's patent application FR-9903829 or a ketose and preferably a ketohexose such as fructose as described in the applicant's patent application FR-9904338.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the ready-to-use dye composition in accordance with the invention are not, or not substantially, altered by the planned addition (s).

The ready-to-use dye composition in accordance with the invention can be in various forms, such as in the form of liquids, creams, gels, optionally pressurized, or in any other form suitable for dyeing keratin fibers. , and in particular human hair. In this case, the compound or compounds of formula (I) according to the invention and the oxidoreductase (s) with 2 electrons or with 4 electrons or the peroxidase (s) are present within the same composition, and therefore said composition must be free of gaseous oxygen, so as to avoid any premature oxidation of the compound or compounds of formula (I).

The subject of the invention is also a process for dyeing keratin fibers and in particular human keratin fibers such as the hair using the ready-to-use dye composition as defined above. According to this method, at least one ready-to-use dye composition as defined above is applied to the fibers, at an application temperature between room temperature and 80 ° C., for a time sufficient to develop the desired coloration . Preferably, the fibers are then rinsed, or optionally washed with shampoo, then dried. The application temperature is preferably between room temperature and 60 ° C and even more preferably between 35 ° C and 50 ° C. The time sufficient for the development of the coloration on the keratin fibers is generally between 1 and 60 minutes and even more precisely between 5 and 30 minutes.

According to a particular embodiment of the invention, the method comprises a preliminary step consisting in storing in separate form, on the one hand, a composition comprising, in a medium suitable for dyeing, at least one derivative in position-4 of 5-halo-ortho-amino-phenols of formula (I) as defined above, and on the other hand, a composition containing, in a medium suitable for dyeing, at least one enzyme of the 2-electron oxidoreductase type or with 4 electrons, or peroxidase, then mix them at the time of use before applying this mixture to the keratin fibers.

Another object of the invention is a dyeing device with several compartments or dyeing "kit" or any other packaging system with several compartments of which at least one first compartment contains the composition (A) as defined above and at at least one second compartment contains the composition (B) as defined above. These devices can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.

The example which follows is intended to illustrate the invention without however limiting its scope. EXAMPLE 1

The following ready-to-use dye composition was prepared:

denotes Active Material The composition was applied to locks of natural gray hair containing 90% white. After a 30-minute break at room temperature, the locks of hair were rinsed, washed with a shampoo, and then dried. They have been dyed dark ash blonde and the coloration obtained has good tenacity in the light.

EXAMPLE 2

The following ready-to-use dye composition was prepared

gen at re ct ve

At the time of use, the composition described above was mixed weight for weight with a 20 volume hydrogen peroxide solution (6% by weight). The ready-to-use composition thus obtained was applied to locks of natural or permanent hair containing 90% white hairs, and left to stand for 30 minutes.

The locks were then rinsed, washed with a shampoo, rinsed again and then dried.

They have been dyed in a tenacious natural brown shade.

Claims

1. Ready-to-use composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, comprising in a medium suitable for dyeing, at least one derivative in position-4 of 5- halo-ortho-amino-phenols of formula (I) defined below, and at least one oxidizing agent:

in which,

R denotes a hydrogen atom or a C- | -C6 alkyl radical,

X denotes a halogen atom, and their addition salts with an acid.

2. Composition according to claim 1, characterized in that in formula (I), R denotes a methyl radical and X denotes a chlorine atom.

3. Composition according to any one of the preceding claims, characterized in that the acid addition salts of the compounds of formula (I) are chosen from hydrochlorides, hydrobromides, sulfates, tartrates, lactates and acetates.

4. Composition according to any one of the preceding claims, characterized in that the compound or compounds of formula (I) and their addition salts with an acid represent from 0.001 to 10% by weight of the total weight of the composition.

5. Composition according to Claim 4, characterized in that the compound or compounds of formula (I) and their addition salts with an acid represent from 0.01 to 8% by weight of the total weight of the composition.

6. Composition according to any one of the preceding claims, characterized in that it contains at least one oxidation dye precursor chosen from paraphenylenediamines, double bases, paraaminophenols, ortho-aminophenols different from those of formula (I) and heterocyclic oxidation bases and their addition salts with an acid.

7. Composition according to claim 6, characterized in that the oxidation dye precursor (s) represent from 0.0005 to 12% by weight of the total weight of the composition.

8. Composition according to any one of the preceding claims, characterized in that the oxidizing agent is a solution of hydrogen peroxide titrating 1 to 40 volumes.

9. Composition according to any one of claims 1 to 7, characterized in that the oxidizing agent comprises at least one enzyme chosen from 2-electron oxidoreductases, 4-electron oxidoreductases, or peroxidases.

10. Composition according to Claim 9, characterized in that the 2-electron oxidoreductases are used with a donor for the said enzyme (s) and are chosen from pyranose oxidases, glucose oxidases, glycerol oxidases, lactate oxidases, pyruvate oxidases, uricases, choline oxidases, sarcosine oxidases, bilirubin oxidases and amino acid oxidases.

11. Composition according to claim 9, characterized in that the oxidoreductases with 4 electrons are chosen from laccases, tyrosinases, catechol oxidases and polyphenol oxidases.

12. Composition according to Claim 11, characterized in that the oxidoreductases with 4 electrons are chosen from laccases of plant origin, animal origin, fungal origin or bacterial origin and from the laccases obtained by biotechnology.

13. Composition according to claim 12, characterized in that characterized in that the laccase is of plant origin and chosen from the laccases present in the extracts of Anacardiaceae; Podocarpaceae; of Rosmarinus off. ; Solanum tuberosum; Iris sp. ; from Coffea sp. ; Daucus carrota; of Vinca minor; Persea americana; Catharenthus roseus; from Musa sp. ; Malus pumila; Gingko biloba; Monotropa hypopithys (sucepin), Aesculus sp. ; Acer pseudoplatanus; of Prunus persica and Pistacia palaestina.

14. Composition according to claim 11 or 12, characterized in that the laccase is of fungal origin or obtained by biotechnology.

15. Composition according to claim 14, characterized in that the laccase is chosen from laccases derived from Polyporus versicolor, Rhizoctonia pratola, Rhus vemicifera, Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyricularia orizae, Trametes versicolor, Fomes fomentarius, Thermophilic Chaetomium, Neurospora crassa, Coriolus versicolor, Botrytis cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus ostreatus, Aspergiilus nidulans, Podospgarus anser bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum, Thelephora terrestris, Cladosporium cladosporioides, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsis subvermisa subvermisa , Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and their variants.

16. Composition according to claim 9, characterized in that the peroxidases are simplex peroxidases.

17. Composition according to claim 9, characterized in that the peroxidase (s) are catalases.

18. Composition according to Claim 9, characterized in that the peroxidase (s) are used with a donor for the said enzyme (s) and are chosen from NADH peroxidases, fatty acids peroxidases, NADPH peroxidases, cytochrome-c peroxidases, iodides peroxidases, chlorides peroxidases, L. ascorbates peroxidases, glutathione peroxidases.

19. Composition according to any one of claims 9 and 16 to 18, characterized in that the peroxidase (s) are of animal, plant, fungal, bacterial or obtained by biotechnology.

20. Composition according to Claim 19, characterized in that the peroxidase (s) come from apple, apricot, barley, black radish, beetroot, cabbage, carrot, corn , cotton, garlic, grapes, mint, rhubarb, soy, spinach, coprin, bovine milk, microorganisms like Acetobacter peroxidans, Staphylococcus faecalis, Arthromyces ramosus.

21. Composition according to any one of claims 1 to 7 and 9 to 20, characterized in that the oxidoreductases with 2 electrons or with 4 electrons represent from 0.01 to 20% by weight of the total weight of the composition .

22. Composition according to Claim 21, characterized in that the oxidoreductases with 2 electrons or with 4 electrons represent from 0.1 to 5% by weight of the total weight of the composition.

23. Composition according to any one of claims 9, 16 to 19, characterized in that the peroxidase (s) represent from 0.0001 to 20% by weight of the total weight of the composition.

24. Composition according to Claim 23, characterized in that the peroxidase (s) represent from 0.001 to 10% by weight of the total weight of the composition.

25. Composition according to any one of the preceding claims, characterized in that it contains at least one additional coupler.

26. Composition according to Claim 25, characterized in that the additional couplers are chosen from metaphenylenediamines, metaaminophenols, metadiphenols, naphthols, heterocyclic couplers, and the addition salts of these compounds with an acid.

27. Composition according to any one of claims 25 or 26, characterized in that the additional couplers are present in concentrations ranging from 0.0001 to 15% by weight relative to the total weight of the composition.

28. Composition according to any one of the preceding claims, characterized in that the addition salts with an acid of the oxidation dye precursors and additional couplers are chosen from hydrochlorides, hydrobromides, sulfates, tartrates , lactates and acetates.

29. Composition according to any one of the preceding claims, characterized in that it contains at least one direct dye chosen from nitro, azo or anthraquinone, neutral, cationic or anionic in the proportion by weight of 0.001 to 20% and of preferably from 0.01 to 10% of the total weight of the composition.

30. Composition according to any one of the preceding claims, characterized in that the medium suitable for dyeing consists of water or a mixture of water and at least one organic solvent.

31. Composition according to claim 30, characterized in that the solvents are present in proportions of between 0.5 and 20% by weight relative to the total weight of the composition.

32. Composition according to any one of the preceding claims, characterized in that it contains at least one surfactant in the proportion ranging from 0.01% to 40% by weight of the total weight of the composition.

33. Composition according to claim 32, characterized in that the surfactant is nonionic.

34. Composition according to any one of the preceding claims, characterized in that it contains at least one thickening polymer of anionic, nonionic, cationic or amphoteric type and comprising at least one fatty chain in the proportion ranging from 0.01 % to 10% by weight of the total weight of the composition.

35. Composition according to any one of the preceding claims, characterized in that it contains at least one cationic or amphoteric polymer in the proportion ranging from 0.01% to 10% by weight of the total weight of the composition.

36. Composition according to any one of the preceding claims, characterized in that it has a pH of between 3 and 12, and preferably between 5 and 11.

37. Composition according to any one of the preceding claims, characterized in that it is in the form of a liquid, cream, gel, optionally pressurized, or in any other form suitable for dyeing keratin fibers.

38. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it is applied to said fibers, at an application temperature between at room temperature and 80 ° C, at least one ready-to-use dye composition as defined in any one of Claims 1 to 36, for a time sufficient to develop the desired coloration.

39. The method of claim 38, characterized in that the application temperature is between room temperature and 60 ° C.

40. Method according to claim 38, characterized in that the time sufficient for the development of the coloring is between 1 and 60 minutes.

41. Method according to claim 40, characterized in that the time sufficient for the development of the coloring is between 5 and 30 minutes.

42. Method according to any one of claims 38 to 41, characterized in that it comprises a preliminary stage consisting in storing, in separate form, on the one hand, a composition comprising, in a medium suitable for dyeing, at at least one compound of formula (I) as defined in any one of claims 1 to 5, and on the other hand, a composition containing, in a medium suitable for dyeing, at least one enzyme of the oxidoreductase type to 2 or 4 electrons or peroxidase, then mix them at the time of use before applying this mixture to the keratin fibers.

43. Dyeing device with several compartments, characterized in that it comprises at least one first compartment containing a composition comprising, in a medium suitable for dyeing, at least one compound of formula (I) as defined in any one of claims 1 to 5, and at least one second compartment containing a composition containing, in a medium suitable for dyeing, at least one enzyme of the 2- or 4-electron oxidoreductase type or peroxidase.