FR2814069A1 - KERATIN FIBER OXIDATION DYEING COMPOSITION COMPRISING A 5-HALOGENO-ORTHO-AMINO-PHENOLS POSITION-4 DERIVATIVE - Google Patents

Abstract

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 selected from derivatives in position-4 of 5-halo-ortho-amino-phenols, and at least one oxidizing agent, as well as the oxidation dyeing process using this composition.

Description

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KERATIN FIBER OXIDATION DYEING COMPOSITION
COMPRISING A 5-HALOGENO-ORTHO-4-POSITION DERIVATIVE
The subject of the invention is a ready-to-use composition for the oxidation dyeing of keratinous fibers, and in particular human keratinous fibers such as the hair comprising, in a medium which is suitable for dyeing, at least one oxidation dye chosen from derivatives at the 4-position of the 5-halo-ortho-amino-phenols, and at least one oxidizing agent, as well as the oxidation dyeing method using this composition.

It is known to dye keratinous fibers and in particular human hair with dyeing compositions containing oxidation dyes and in particular oxidation dye precursors, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, heterocyclic bases, generally called oxidation bases. The oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored and coloring compounds.

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

The variety of molecules involved in oxidation dyes (oxidation bases and couplers) makes it possible to obtain a rich palette of colors The so-called "permanent" coloration obtained with these oxidation dyes must in addition satisfy a number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to the agents.

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 external (light, bad weather, washing, permanent waving, perspiration, friction) The oxidation dyeing of keratinous 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 keratinous fibers, in particular in the 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 at 2. electrons, such as pyranose oxidase, glucose oxidase or uricase, in the presence of a donor for said enzymes.

It has already been proposed, in particular in patent applications FR-A-2112549, FR-A-2694018, EP-A-504005, WO 95/07988, WO95 / 33836, WO95 / 33837, WO96 / 00290, WO97 / 19998, WO97 / 19999, WO97 / 37633, WO / 98/40471 and US-3251742, dyeing keratinous 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, for dyeing keratin fibers, peroxidase in the presence of small amounts of hydrogen peroxide, as described in patents EP-548620, BE-775110 and US-3893803. .

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

The Applicant has now discovered that it is possible to obtain new dyes, capable of leading to stubborn stains, especially to light, whose shades are natural, by combining at least one oxidation dye chosen from 4-position derivatives of the 5-haloortho-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 peroxidase.

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This discovery is the basis of the present invention.

dans laquelle, R désigne un atome d'hydrogène ou un radical alkyle en C1-C6, X désigne un atome d'halogène choisi parmi le fluor, le brome, l'iode ou le chlore, et leurs sels d'addition avec un acide. The subject of the invention is therefore a ready-to-use composition for the oxidation dyeing of keratinous fibers and in particular human keratinous fibers such as the hair, comprising in a medium suitable for dyeing, at least one derivative in the 4-position of the 5-halo-ortho-amino-phenols of formula (I) below defined, and at least one oxidizing agent.

in which, R denotes a hydrogen atom or a C1-C6 alkyl radical, X denotes a halogen atom chosen from fluorine, bromine, iodine or chlorine, and their addition salts with an acid .

The acid addition salts of the oxidation dyes of formula (I) are chosen in particular from hydrochlorides, phosphates, hydrobromides, sulphates 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 dyeing of keratinous fibers.

According to the present invention, among the 4-position derivatives of the 5-haloorthoamino phenols of formula (1), it is particularly preferred to use the compound

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 of formula (I) for which R denotes a methyl radical and X denotes a chlorine atom.

The oxidation dye (s) of formula (1) used according to the invention preferably represent from 0.001 to 10% by weight of the total weight of the composition and even more preferably from 0.01 to 8% of this weight. .

Oxidizing agent In the ready-to-use composition according to the invention, the oxidizing agent may 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 is advantageously constituted by a solution of hydrogen peroxide whose content may vary, more particularly, from about 1 to 40 volumes, and even more preferably from about 5 to 40.

It is also possible to use as oxidizing agent one or more 2-electron or 4-electron or peroxidase-type xydo-reductase enzymes. A particularly preferred ready-to-use composition according to the present invention is a ready-to-use composition. use for the oxidation dyeing of keratinous fibers and in particular human keratinous fibers such as the hair, comprising in a medium suitable for dyeing, at least one derivative at the 4-position of the 5-halogeno-ortho-amino-phenols of formula (1) defined above, and at least one enzyme selected from 2-electron oxidoreductases, 4-electron oxidoreductases or peroxidases.

The 2-electron oxido-reductase (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.

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 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 wild boar liver, uricase from Arthrobacter globiformis, and uricase from Aspergillus flavus.

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

The one or more 2-electron oxidoreductases according to the invention preferably represent from 0.01 to 20% by weight of the total weight of the composition, and still more preferably from 0.1 to 5% by weight approximately of this composition. weight.

The amount of enzyme can also be defined according to its activity.

The enzymatic activity of the 2-electron oxidoreductases according to the invention can be defined from the oxidation of the donor under aerobic conditions.

A unit U corresponds to the amount of enzyme leading to the generation of one mol of H 2 O 2 per minute at a pH of 8.5 and at a temperature of 25 ° C. Preferably, the amount of oxidoreductase at 2 ° C. electrons according to the invention is between 10 and 108 units U about per 100g of dye composition.

According to the invention, the term "donor" is understood to mean the different 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 that is used. For example, as a donor for pyranose oxidases, there may be mentioned D-glucose, L-sorbose and D-xylose; as a donor for glucose oxidases, mention may be made of D-glucose; as a donor for glycerol oxidases, mention may be made of glycerol and dihydroxyacetone; as a donor for lactate oxidases, mention may be made of

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 lactic acid and its salts; as a donor for pyruvate oxidases, mention may be made of pyruvic acid and its salts; as a donor for uricases, there may be mentioned uric acid and its salts; as a donor for choline oxidases, there may be mentioned choline and its addition salts with an acid such as choline hydrochloride, and betaine aldehyde; as a donor for sarcosine oxidases include sarcosine, N-methyl-L-leucine, N-methyl-DL-alanine, and N-methyl-DL-valine; and finally, as a donor for bilirubin oxidases, there may be mentioned bilirubin.

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

The one or more 4-electron oxidoreductases used in the ready-to-use dye composition according to the invention may be chosen in particular from laccases, tyrosinases, catechol oxidases and polyphenol oxidases.

According to a particular and preferred embodiment of the invention, the one or more 4-electron oxidoreductases are chosen from laccases.

These laccases may 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 possibly being mono- or pluricellular. Laccases can also be obtained by biotechnology.

Among the laccases of plant origin that 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 the patent application FR-A-2 694 018.

These include laccases present in extracts of Anacardiaceae such as, for example, extracts of Magnifera indica, Schinus molle or Pleiogynium timoriense; in extracts of Podocarpaceae; Rosmarinus off.

; Solanum tuberosum; of Iris sp. ; from Coffea sp. ; Daucus carrota; Vinca

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 minor; Persea americana; Catharenthus roseus; Musa sp. ; de Malus pumila; Gingko biloba; of 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) derived from Polyporus versicolor, Rhizoctonia praticola and Rhus vernicifera, as described for example in the French patent applications. A-2,112,549 and EP-A-504005; the laccases described in the patent applications WO95 / 07988, WO95 / 33836, WO95 / 33837, WO96 / 00290, WO97 / 19998 and WO97 / 19999, the content of which forms an integral part of the present description, such as, for example, the laccase (s) resulting from of Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyricularia orizae, and variants thereof. We may also mention the laccase (s) derived from Trametes versicolor, Fomes fomentarius, Chaetomium thermophilus, Neurospora crassa, Coriolus versicolor, Botrytis cinerea, Rigidoporus lignosus, Phellinus noxius, Pleurotus ostreatus, Aspergillus nidulans, Podospora anserina, Agancus bisporus, Ganoderma lucidum, Glomerella cingulata, Lactarius piperatus, Russula delica, Heterobasidion annosum, Thelephora terrestris, Cladosporium cladosporioides, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsis subvermispora, of 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 according to the invention and having syringaldazine among their substrates can be defined from the oxidation of syringaldazine under aerobic conditions. The Lacu unit corresponds to the amount 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. The unit U corresponds to the amount of enzyme producing a delta absorbance of 0.001 per minute, at a wavelength of 530 nm, using syringaldazine as a substrate, at 30 C and at a

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 pH of 6.5. The enzymatic activity of the laccases used according to the invention can also be defined from the oxidation of para-phenylenediamine. The ulac unit corresponds to the amount of enzyme producing an absorbance delta of 0.001 per minute, at a wavelength of 496.5 nm, using paraphenylenediamine as a substrate (64 mM), at 30 ° C. a pH of 5.

In general, the one or more 4-electron oxidoreductases in accordance with the invention preferably represent from 0.01 to 20% by weight of the total weight of the ready-to-use dye composition, and still more preferably from About 1 to 5% by weight 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 according to the invention will vary according to the nature of the laccase (s) used. Preferably, the amount of laccase (s) is between about 0.5 and 2000 Lacu (or between about 10000 and 40.106 U units or between 20 and 20. 10 ulac units) per 100 g of dye composition ready for use. 'employment.

The peroxidase or peroxidases used in the ready-to-use dye composition according to the invention may in particular be chosen from the enzymes belonging to subclass 1. 11.1 described in the book Enzyme Nomenclature, Academic Press Inc., 1984 Some of them require the presence of a donor to function. This is the case, in particular NADH peroxidases (1.11.1) [donor = NADH], peroxidase fatty acids (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], peroxidase iodides (1. 11.1.8) [donor = iodide], peroxidase chlorides (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, the peroxidases simplex (1.11.1.7) are preferably used.

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All peroxidases function in the presence of hydrogen peroxide which is supplied as such or generated in situ enzymatically [2-electron oxidase (s) and donor (s) presence of air].

The peroxidases used may be of plant, animal, fungal or bacterial origin. They can also be obtained by biotechnology.

Thus, the peroxidases may for example be derived from apple, apricot, barley, black radish, beetroot, cabbage, carrot, corn, cotton, garlic, grapes, mint, rhubarb, soybean, spinach, cinnamon, bovine milk, microorganisms of the type Acetobacter peroxidans, Staphylococcus faecalis, Arthromyces ramosus.

The unit of activity of peroxidase simplex (1.11.1.7) can be defined as the amount of simplex enzyme forming 1 mg of purpurogallin from pyrogallol in 20s at pH6 and at 20 C. For example, SIGMA black radish peroxidase P6782 has an activity of about 250 units per mg.

The concentration of use of this type of enzyme thus varies between 25 and 5 × 10 6 units per 100 g of composition.

The peroxidase (s) according to the invention preferably represent from 0.0001 to 20% by weight approximately of the total weight of the composition, and still 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 para-phenylenediamines, double bases, para-aminophenols, ortho-aminophenols different from those of formula (1) and heterocyclic oxidation bases.

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dans laquelle : Ri représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, polyhydroxyalkyle en C2-C4, alcoxy(C1-
C4)alkyle(C1-C4), alkyle en C1-C4 substitué par un groupement azoté, phényle ou
4'-aminophényle ; R2 représente un atome d'hydrogène, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4 ou polyhydroxyalkyle en C2-C4, alcoxy(C1-
C4)alkyle(C1-C4) ou alkyle en C1-C4 substitué par un groupement azoté ,
Ri et R2 peuvent également former avec l'atome d'azote qui les porte un hétérocycle azoté éventuellement substitué ; R3 représente un atome d'hydrogène, un atome d'halogène tel qu'un atome de chlore, un radical alkyle en C1-C4, sulfo, carboxy, monohydroxyalkyle en C1-C4 ou hydroxyalcoxy en C1-C4, acétylaminoalcoxy en C1-C4, mésylaminoalcoxy en
C1-C4 ou carbamoylaminoalcoxy en C1-C4. Among the para-phenylenediamines which can be used as oxidation base in the dyeing compositions in accordance with the invention, mention may in particular be made of the compounds of the following formula (II) and their addition salts with an acid:

in which: R 1 represents a hydrogen atom, a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 alkoxy radical;
C4) (C1-C4) alkyl, C1-C4 alkyl substituted by a nitrogen group, phenyl or
4'-aminophenyl; R2 represents a hydrogen atom, a C1-C4 alkyl, C1-C4 monohydroxyalkyl or C2-C4 polyhydroxyalkyl radical, C1-C4 alkoxy radical;
C4) (C1-C4) alkyl or C1-C4 alkyl substituted with a nitrogen group,
R 1 and R 2 may also form, with the nitrogen atom carrying them, an optionally substituted nitrogenous heterocycle; R3 represents a hydrogen atom, a halogen atom such as a chlorine atom, a C1-C4 alkyl, sulfo, carboxy, C1-C4 monohydroxyalkyl or C1-C4 hydroxyalkoxy, C1-C4 acetylaminoalkoxy radical; mesylaminoalkoxy
C1-C4 or carbamoylaminoalkoxy C1-C4.

trialkyl(Cl-C4)amino, monohydroxyalkyl(CI-C4)amîno, imidazolinium et ammonium Parmi les paraphénylènediamines de formule (1) ci-dessus, on peut plus particulièrement citer la paraphénylènediamine, la paratoluylènediamine, la 2-chloro-paraphénylènediamine, la 2,3-diméthyl-paraphénylènediamine, la 2,6-diméthyl-paraphénylènediamine, la 2,6-diéthyl-paraphénylènediamine, la R4 represents a hydrogen atom, a halogen atom or a C1-C4 alkyl radical. Among the nitrogen groups of formula (I) above, mention may be made especially of amino, monoalkyl (C 1 -C 4) amino and dialkyl radicals. (C1-C4) alkylamino,

trialkyl (C1-C4) amino, monohydroxyalkyl (C1-C4) amino, imidazolinium and ammonium Among the paraphenylenediamines of formula (1) above, there may be mentioned more particularly paraphenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,

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paraphénylènediamine, la 4-amino-N,N-bis-(p-hydroxyéthyl)-3-méthyl-aniline, la 4-amino-3-chloro-N,N-bis-(P-hydroxyéthyl)-aniline, la 2-p-hydroxyéthylparaphénylènediamine, la 2-fluoro-paraphénylènediamine, la 2-isopropylparaphénylènediamine, la N-(-hydroxypropyl)-paraphénylènediamine, la 2-hydroxyméthyl-paraphénylènediamine, la N,N-diméthyl-3-méthylparaphénylènediamine, la N,N-(éthyl, ss-hydroxyéthyl)-paraphénylènediamine, la N-(ss,[gamma]-dihydroxypropyl)paraphénylènediamine, la N-(4'-aminophényl)paraphénylènediamine, la N-phényl-paraphénylènediamine, la 2-p-hydroxyéthyloxy-paraphénylènediamine, et leurs sels d'addition avec un acide. 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methyl- aniline, N, N-bis - ((3-hydroxyethyl) -

paraphenylenediamine, 4-amino-N, N-bis- (p-hydroxyethyl) -3-methyl-aniline, 4-amino-3-chloro-N, N-bis- (P-hydroxyethyl) -aniline, 2 p-hydroxyethylparapenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - (- hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (N- (ss, [gamma] -dihydroxypropyl) paraphenylenediamine, N- (ss, [gamma] dihydroxypropyl), N- (4'-aminophenyl) paraphenylenediamine, N-phenyl-para-phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine and their addition salts with an acid.

Among the para-phenylenediamines of formula (1) above, para-phenylenediamine, paratoluylenediamine, 2-isopropyl-para-phenylenediamine, 2-p-hydroxyethyl-para-phenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2,6-isopropyl-para-phenylenediamine are particularly preferred. dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (ss-hydroxyethyl) -paraphenylenediamine, 2-chloro-para-phenylenediamine, and their addition salts with a acid.

According to the invention, the term "double bases" is intended to mean compounds comprising at least two aromatic rings bearing amino and / or hydroxyl groups.

Among the double bases that can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned the compounds corresponding to the following formula (III), and their addition salts with an acid:

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dans laquelle : - Z1 et Z2, identiques ou différents, représentent un radical hydroxyle ou-NH2 pouvant être substitué par un radical alkyle en C1-C4 ou par un bras de liaison Y ; - le bras de liaison Y représente une chaîne alkylène comportant de 1 à 14 atomes de carbone, linéaire ou ramifiée pouvant être interrompue ou terminée par un ou plusieurs groupements azotés et/ou par un ou plusieurs hétéroatomes tels que des atomes d'oxygène, de soufre ou d'azote, et éventuellement substituée par un ou plusieurs radicaux hydroxyle ou alcoxy en Ci-Ce ; - R5 et Re représentent un atome d'hydrogène ou d'halogène, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4 polyhydroxyalkyle en C2-C4, aminoalkyle en C1-C4 ou un bras de liaison Y ; - R7, R8, Rg, Rio, R11 et R12, identiques ou différents, représentent un atome d'hydrogène, un bras de liaison Y ou un radical alkyle en C1-C4 ; étant entendu que les composés de formule (III) ne comportent qu'un seul bras de liaison Y par molécule.

in which: Z1 and Z2, which may be identical or different, represent a hydroxyl or -NH2 radical which may be substituted with a C1-C4 alkyl radical or with a Y linker arm; the linking arm Y represents an alkylene chain comprising from 1 to 14 carbon atoms, linear or branched, which may be interrupted or terminated by one or more nitrogenous groups and / or by one or more heteroatoms such as oxygen atoms, sulfur or nitrogen, and optionally substituted by one or more hydroxyl or alkoxy radicals Ci-Ce; R5 and R6 represent a hydrogen or halogen atom, a C1-C4 alkyl radical, a C1-C4 polyhydroxyalkyl C1-C4 monohydroxyalkyl radical, a C1-C4 aminoalkyl radical or a Y-linkage arm; - R7, R8, Rg, Rio, R11 and R12, which are identical or different, represent a hydrogen atom, a linker Y or a C1-C4 alkyl radical; it being understood that the compounds of formula (III) have only one Y linker per molecule.

Among the nitrogen groups of the formula (III) above, mention may be made especially of amino, monoalkyl (C 1 -C 4) amino, dialkyl (C 1 -C 4) amino, trialkyl (C 1 -C 4) amino, monohydroxyalkyl (C 1 -C 4) radicals. C4) amino, imidazolinium and ammonium.

Among the double bases of formulas (III) above, mention may be made more particularly of N, N'-bis (ss-hydroxyethyl) N, N'-bis (4'-aminophenyl) 1,3-diamino propanol. N, N'-bis (hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (N-N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N ' -bis- (4'-amino,

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 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxane, and their addition salts with an acid.

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

dans laquelle : R13 représente un atome d'hydrogène,un atome d'halogène tel que le fluor, un radical alkyle en C1-C4, monohydroxyalkyle en C1-C4, alcoxy(C1-C4)alkyle(C1-C4) ou aminoalkyle en Ci-C4, ou hydroxyalkyl(C1-C4)aminoalkyle en Ci-C4. Among the para-aminophenols that can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned the compounds corresponding to the following formula (IV), and their addition salts with an acid:

in which: R13 represents a hydrogen atom, a halogen atom such as fluorine, a C1-C4 alkyl, C1-C4 monohydroxyalkyl, C1-C4 alkoxy (C1-C4) alkyl or aminoalkyl radical; C1-C4, or C1-C4 hydroxyalkyl (C1-C4) aminoalkyl.

R 14 represents a hydrogen atom or a halogen atom such as fluorine, a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 aminoalkyl, C 1 -C 4 cyanoalkyl or alkoxy (C1-C4) alkyl (C1-C4).

Among the para-aminophenols of formula (IV) above, mention may be made more particularly of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol and 4-amino. 3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol 4-amino-2- (p-hydroxyethylaminomethyl) phenol, and their addition salts with an acid.

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 Among the ortho-aminophenols that can be used as oxidation bases in the dyeing 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-aminophenol, and their addition salts with an acid.

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

Among the pyridine derivatives, mention may be made more particularly 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- (ss-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 Patent DE 2,359,399 or Japanese JP 88-169,571 and JP 91-10659 or patent applications WO 96/15765, such as 2,4, 5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2, 5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the 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; pyrazolo [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-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl-pyrazolo [1,5-a] -pyrimidine-3,7-diamine , 2,6-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine,

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 2,5, N7, N7-tetramethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine, and their addition salts and tautomeric forms, when tautomeric equilibrium and their salts exist. addition with an acid.

Among the pyrazole derivatives, mention may be made more particularly 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. Such as 4,5-diamino-1-methyl-pyrazole, 4,5-diamino-1-hydroxyethyl-pyrazole, 3,4-diaminopyrazole, 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- (s-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-pyrazole, 4 , 5-diamino-3-methyl-1-isopropyl-pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl-pyrazole, 3,4,5-triamino-pyrazole, methyl-3,4,5-triamino-pyrazole, 3,5-diamino-1-methyl-4-methylamino-pyrazole, 3,5-diamino-4- (ss-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 para-phenylenediamines.

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

Additional couplers The ready-to-use dyeing composition according to the invention may also contain one or more additional couplers other than those of formula (1)

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 according to the invention and usually used in oxidation dyeing chosen from meta-aminophenols, meta-phenylenediamines, meta-diphenols, naphthols and heterocyclic couplers such as, for example, indole derivatives, indoline 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-aminophenol, 5-N- (ss-hydroxyethyl) -amino-2-methyl-phenol, 3-amino-phenol, 1,3-dihydroxy- benzene, 1,3-dihydroxy-2-methyl-benzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (ss-hydroxyethyloxy) -benzene, 2-amino- 4- (α-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino-benzene, 1,3-bis (2,4-diaminophenoxy) -propane, sesamol, α-naphthol, acetoxy-2-methylnaphthalene, 6-hydroxy-indole, 4-hydroxy-indole, 4-hydroxy-N-methyl-indole, 3- (4-hydroxy-1-methyl-1H-indol) 5-yl-methyl) -1-methyl-pyridinium, 6-hydroxy-indoline, 2,6-dihydroxy-4-methyl-pyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-H-3 methyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, and their addition salts with an acid.

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

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

Direct Dyestuffs The ready-to-use dye composition according to the invention may also contain one or more direct dyes, in particular to modify the shades by enriching them with reflections. These direct dyes can in particular be

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 chosen from nitro, azo or anthraquinone dyes, neutral, cationic or anionic in the weight proportion of about 0.001 to 20% and preferably from 0.01 to 10% of the total weight of the composition.

Dyeing medium The medium suitable for dyeing (or supporting) the ready-to-use dye composition according to the invention generally consists of water or a mixture of water and at least one organic solvent to solubilize compounds that are not sufficiently soluble in water. As an organic solvent, mention may be made, for example, of C1-C4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, those described in French Patent Application 2,773,475, the content of which forms an integral part of the invention, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, like products and mixtures thereof.

The solvents, when present in the medium, may represent about 0.5 to 20% and preferably about 2 to 10% by weight of the total weight of the ready-to-use dye composition.

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

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 for dyeing keratinous fibers.

Among the acidifying agents, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid,

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 sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en Ci-C4 ; R15 R16, R17 et R18, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C4 ou hydroxyalkyle en C1-C4. Among the alkalinizing agents that may be mentioned, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines, 2-methyl-2-amino-1-propanol and their derivatives, the hydroxides of sodium or potassium and the compounds of formula (V) below:

wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; R15 R16, R17 and R18, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

The ready-to-use composition according to the invention also preferably comprises, in the composition containing the derivative (s) at the 4-position, 5-haloortho-amino-phenols of formula (1), at least one anionic-type thickening polymer. , nonionic, cationic, or amphoteric having at least one fatty chain.

Among the thickening polymers comprising at least one fatty chain and anionic type. mention may be made of: - (I) those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly those whose hydrophilic unit is constituted by an ethylenic unsaturated anionic monomer, more particularly by a vinyl carboxylic acid and especially with acrylic acid or methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (1)
In which R 'denotes H or CH 3, B denotes the ethyleneoxy radical, n denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl radicals, arylalkyl, aryl, alkylaryl, cycloalkyl, comprising from 8 to 30 carbon atoms, preferably 10 to 24, and more particularly

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 from 12 to 18 carbon atoms. A more particularly preferred unit of formula (I) is a unit in which R 'denotes H, n is equal to 10, and R denotes a stearyl (C18) radical.

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

Among these anionic fatty-chain thickening polymers, polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of ( lower alkyl meth) acrylates, from 2 to 50% by weight of fatty-chain allyl ether of formula (1), and from 0 to 1% by weight of a crosslinking agent which is a copolymerizable polyethylenic unsaturated monomer well known, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

Among these, the crosslinked terpolymers of methacrylic acid, ethyl acrylate, polyethylene glycol (10 EO) and stearyl alcohol (Steareth 10) are particularly preferred, 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).

(II) those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of the (C 10 -C 30) alkyl ester of unsaturated carboxylic acid type.

dans laquelle, Ri désigne H ou CH3 ou C2H5, c'est-à-dire des motifs acide acrylique, acide méthacrylique ou acide éthacrylique, et dont le motif hydrophobe de type ester d'alkyl (C10-C30) d'acide carboxylique insaturé correspond au monomère de formule (III) suivante : Preferably, these polymers are chosen from those whose hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the following monomer of formula (II):

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

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dans laquelle, R2 désigne H ou CH3 ou C2H5 (c'est-à-dire des motifs acrylates, méthacrylates ou éthacrylates) et de préférence H (motifs acrylates) ou CH3 (motifs méthacrylates), R3 désignant un radical alkyle en C10-C30, et de préférence en C12-C22.

in which, R2 denotes H or CH3 or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units), R3 denotes a C10-C30 alkyl radical; and preferably C12-C22.

Alkyl (C 10 -C 30) 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 fatty-chain anionic thickening polymers, polymers formed from a monomer mixture comprising: (i) essentially acrylic acid, (ii) an ester of formula (III) described herein above and in which R2 designates H or
CH 3, R 3 denoting an alkyl radical having from 12 to 22 carbon atoms, (iii) and a crosslinking agent, which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide.

Among this type of fatty-chain anionic thickening polymers, 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 C 10 -C 30 alkyl acrylate ( hydrophobic unit), and 0 to 6% by weight of polymerizable crosslinking monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C10 alkyl acrylate -C30 (hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among said polymers above, the products sold by the company GOODRICH under the

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 trade names PEMULEN TR1, PEMULEN TR2, CARBOPOL 1382, and even more preferentially PEMULEN TR1, and the product sold by the company S.E.P.P.I.C. under the name COATEX SX.

(III) terpolymers of maleic anhydride / α-olefin C30-C38 / alkyl maleate such as the product (maleic anhydride copolymer / C3o-C38 α-olefin / isopropyl maleate) sold under the name PERFORMA V 1608 by the company NEWPHASE TECHNOLOGIES.

(IV) acrylic terpolymers comprising: (a) about 20% to 70% by weight of a [alpha], ss-monoethylenically unsaturated carboxylic acid, (b) about 20 to 80% by weight of a monomer to unsaturation [alpha], ss-monoethylenic non-surfactant other than (a), (c) about 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a surfactant monohydric active agent with a monoethylenically unsaturated monoisocyanate, such as those described in the patent application EP-A-0173109 and more particularly that described in Example 3, namely, a terpolymer methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl ethoxylated behenyl alcohol isocyanate (400E) in a 25% aqueous dispersion.

(V) copolymers comprising among their monomers an α, mon-monoethylenically unsaturated carboxylic acid and a [α], s-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise, as monomer, a carboxylic acid ester with [alpha], ss-monoethylenic unsaturation and C1-C4 alcohol.

By way of example of this type of compound, mention may be made of Aculyn 22 sold by Rohm and Haas, which is a methacrylic acid / ethyl acrylate / stearyl methacrylate oxyalkylenated terpolymer.

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Thick-chain thickening polymers of the nonionic type. used according to the invention are preferably chosen from: - (1) celluloses modified with groups comprising at least one fatty chain; mention may be made, for example, of: hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, such as the product NATROSOL PLUS GRADE 330 CS (alkyls in C16) sold by AQUALON, or the product BERMOCOLL EHM 100 sold by BEROL NOBEL, - those modified with polyalkylene glycol ether alkylphenol groups, such as the product AMERCELL POLYMER HM-1500 (polyethylene glycol (15) nonyl phenol ether) sold by the company Amerchol - (2) hydroxypropyl guars modified with groups comprising at least one fatty chain such as the product ESAFLOR HM 22 (C22 alkyl chain) sold by LAMBERTI, the products RE210-18 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by RHONE POULENC.

(3) copolymers of vinyl pyrrolidone and hydrophobic fatty-chain monomers; by way of example, mention may be made of: the products ANTARON V216 or GANEX V216 (vinylpyrrolidone / hexadecene copolymer) sold by the company I.S.P.

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

(4) copolymers of C 1 -C 6 alkyl methacrylates or acrylates and amphiphilic monomers comprising at least one fatty chain, such as, for example, the oxyethylenated methyl acrylate / stearyl acrylate copolymer sold by GOLDSCHMIDT under the name denomination ANTIL 208.

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(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer.

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

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

Preferably, the polyether polyurethanes comprise at least two hydrocarbon-based lipophilic chains having from 6 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant 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 may be multiblocked, in particular in the form of a triblock. The hydrophobic sequences may be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These same polymers may also be graft or star.

The nonionic polyurethane polyethers with a fatty chain may be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain containing from 50 to 1000 oxyethylenated groups. Nonionic polyurethane polyethers have a urethane bond between the hydrophilic blocks, hence the origin of the name.

By extension are also included among the nonionic fatty-chain polyurethane polyethers, those whose hydrophilic sequences are linked to the lipophilic blocks by other chemical bonds.

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By way of examples of nonionic polyurethane polyethers with a fatty chain which can be used in the invention, it is also possible to use also the urea-functional Rheolate 205 sold by the company Rheox or else the Rheolates 208, 204 or 212, as well as the Acrysol RM 184, Aculyn 44 and Aculyn 46 from 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) (SMDI) at 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 methylenebis (4cyclohexylisocyanate) (SMDI), at 35% by weight in a propylene glycol mixture (39%) and water (26%)].

Mention may also be made of the product ELFACOS T210 with a C12-14 alkyl chain and the product ELFACOS T212 with a C18 alkyl chain from AKZO.

The product DW 1206B from Rohm & Haas containing a C20 alkyl chain and a urethane linkage, proposed at 20% solids content in water, may also be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example, such polymers include, for example, Rheolate 255, Rheolate 278 and Rheolate 244 sold by Rheox. It is also possible to use the product DW 1206F and the DW 1206J proposed by the company Rohm & Haas.

The polyether polyurethanes that 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 cationic type fatty-chain thickening polymers used according to the present invention are preferably chosen from quaternized cellulose derivatives and polyacrylates with non-cyclic amine side groups. The quaternized cellulose derivatives are, in particular, quaternized cellulose modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups having at least 8 carbon atoms, or mixtures thereof,

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 quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures of these.

The alkyl radicals borne by the above-quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms.

The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.

Examples of C8-C30 fatty chain quaternized alkylhydroxyethylcelluloses are QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C12 alkyl) and QUATRISOFT LM products. -X 529-8 (C18 alkyl) marketed by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (C12 alkyl) and CRODACEL QS (C18 alkyl) marketed by the company CRODA.

The polyacrylates with amino side groups, quaternized or otherwise, have, for example, steareth type water-repellent groups (polyoxyethylenated stearyl alcohol (20)).

Examples of aminated side chain polyacrylates include polymers 8781-121 B or 9492-103 proposed by the company National Starch.

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

The fatty-chain thickening polymers of the anionic, nonionic, cationic or amphoteric type are preferably used in an amount ranging from about 0.01 to 10% by weight of the total weight of the dyeing 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 furthermore preferably comprise in the composition containing the 4-position derivative (s).

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 5-halo-ortho-amino-phenols of formula (1), at least one cationic or amphoteric polymer.

Cationic Polymers For the purposes of the present invention, the expression "cationic polymer" denotes any polymer containing cationic groups and / or ionizable groups in cationic groups.

The cationic polymers that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in the patent application EP-A-337 354 and in the French patents 2 270 846.2 383 660.2 598 611, 2 470 596 and 2 519 863.

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

The cationic polymers used generally have a number-average molecular weight of between about 500 and 5 × 10 6, and preferably between about 103 and 3 × 10 6.

Among the cationic polymers, mention may be made more particularly of the polyamine, polyaminoamide and quaternary polyammonium type polymers.

These are known products. They are especially described in French patents Nos. 2,505,348 or 2,542,997. Among said polymers, mention may be made of: (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulas (1), (II), (III) or (IV):

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dans lesquelles: R3 , identiques ou différents, désignent un atome d'hydrogène ou un radical CH3; A, identiques ou différents, représentent un groupe alkyle, linéaire ou ramifié, de 1 à 6 atomes de carbone, de préférence 2 ou 3 atomes de carbone ou un groupe hydroxyalkyle de 1 à 4 atomes de carbone ; R4, R5, R6, identiques ou différents, représentent un groupe alkyle ayant de 1 à 18 atomes de carbone ou un radical benzyle et de préférence un groupe alkyle ayant de 1 à 6 atomes de carbone; R1 et R2 , identiques ou différents, représentent hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone et de préférence méthyle ou éthyle; X désigne un anion dérivé d'un acide minéral ou organique tel qu'un anion méthosulfate ou un halogénure tel que chlorure ou bromure.

in which: R3, which may be identical or different, denote a hydrogen atom or a CH3 radical; A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R4, R5, R6, which may be 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; R1 and R2, identical or different, represent hydrogen or an alkyl group having 1 to 6 carbon atoms and preferably methyl or ethyl; X denotes an anion derived from a mineral or organic acid such as a methosulphate anion or a halide such as chloride or bromide.

The polymers of family (1) may also contain one or more comonomer-derived units that may be chosen from the family of acrylamides, methacrylamides, acrylamide diacetones, acrylamides and methacrylamides.

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 substituted on the 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), mention may be made of: copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl holognide, such as that sold under the name HERCOFLOC by the company HERCULES the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described, for example, in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY, the copolymer of acrylamide and methosulphate of methacryloyloxyethyltrimethylammonium sold under the name RETEN by the company HERCULES, - vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers quaternized or otherwise, such as the products sold under the name "GAFQUAT" by the company ISP such as "GAFQUAT 734" or "GAFQUAT 755 "or the products referred to as" COPOLYMER 845, 958 and 937 ". These polymers are described in detail in French patents Nos. 2,077,143 and 2,393,573, dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP, vinylpyrrolidone copolymers. and methacrylamidopropyl dimethylamine sold in particular under the name STYLEZE CC 10 by ISP, and quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymers such as the product sold under the name "GAFQUAT HS 100" by the company ISP.

(2) The cellulose ether derivatives comprising quaternary ammonium groups described in French Patent 1,492,597, and in particular the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as

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 quaternary ammonium hydroxylcellulose reacted with an epoxide substituted with 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 cellulose grafted in particular with a salt of methacryloylethyl trimethylammonium, methacrylmidopropyl trimethylammonium, dimethyldiallylammonium salt.

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

(4) The cationic polysaccharides described more particularly in US Pat. Nos. 3,589,578 and 4,031,307, such as guar gums containing cationic trialkylammonium groups. For example, guar gums modified with a salt (eg chloride) of 2,3-epoxypropyltrimethylammonium are used.

Such products are marketed in particular under the trade names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company MEYHALL.

(5) Polymers consisting of piperazinyl units and straight or branched chain alkylene or hydroxyalkylene divalent radicals, optionally interrupted by oxygen, sulfur, nitrogen or aromatic or heterocyclic rings, as well as oxidation and / or quaternization of these polymers. Such polymers are especially described 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 may be crosslinked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative,

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 halohydrin, a bis-azetidinium, a bis-haloacyldiamine, an alkyl bis-halide or an oligomer resulting from the reaction of a bifunctional compound reactive with a bis-halohydrin, 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 moles per amine group of the polyaminoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary amine functional groups, quaternized. Such polymers are in particular described in French Patents 2 252 840 and 2 368 508.

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

Among these derivatives, mention may be made more particularly of 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 polyaminoamide resulting therefrom being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the amme group; secondary polyaminoamide between 0.5: 1 and 1.8: 1. Such polymers are described in particular in US Patents 3,227,615 and 2,961,347.

Polymers of this type are in particular marketed under the name "Hercosett 57" by the company Hercules Inc. or else under the name "Hercosett 57".

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 denomination of "PD 170" or "Delsette 101" by the company Hercules in the case of the adipic acid / epoxypropyl / diethylene-triamine copolymer.

formules dans lesquelles k et t sont égaux à 0 ou 1, la somme k + t étant égale à 1 ; Rg désigne un atome d'hydrogène ou un radical méthyle ; R7 et R8, indépendamment l'un de l'autre, désignent un groupement alkyle ayant de 1 à 22 atomes de carbone, un groupement hydroxyalkyle dans lequel le groupement alkyle a de préférence 1 à 5 atomes de carbone, un groupement amidoalkyle inférieur (C1-C4), ou R7 et R8 peuvent désigner conjointement avec l'atome d'azote auquel ils sont rattachés, des groupement hétérocycliques, tels que pipéridinyle ou morpholinyle ; R7 et R8 indépendamment l'un de l'autre désignent de préférence un groupement alkyle ayant de 1 à 4 atomes de carbone ; Y- est un anion tel que bromure, chlorure, acétate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. Ces polymères sont notamment décrits dans le brevet français 2. 080.759 et dans son certificat d'addition 2.190 406. (9) cyclopolymers of alkyl diallyl amine or of 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 0 or 1, the sum k + t being equal to 1; Rg denotes a hydrogen atom or a methyl radical; R7 and R8, independently of each other, denote an alkyl group having 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 R8 may designate, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R7 and R8, 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, mention may be made more particularly of the homopolymer of dimethyldiallylammonium chloride sold under the name "Merquat 100" by the company Calgon (and its counterparts of weak

<Desc / Clms Page number 32>

 weight average molecular weight) and copolymers of diallyldimethylammonium chloride and acrylamide sold under the name "MERQUAT 550".

formule (VII) dans laquelle : R10, R11, R12 et R13, identiques ou différents, représentent des radicaux aliphatiques, alicycliques, ou arylaliphatiques contenant de 1 à 20 atomes de carbone ou des radicaux hydroxyalkylaliphatiques inférieurs, ou bien R10, R11, R12 et R13, ensemble ou séparément, constituent avec les atomes d'azote auxquels ils sont rattachés des hétérocycles contenant éventuellement un second hétéroatome autre que l'azote ou bien R10, R11, R12 et R13 représentent un radical alkyle en C1-C6 linéaire ou ramifié substitué par un groupement nitnle, ester, acyle, amide ou -CO-O- R14-D ou-CO-NH- R14-D où R14 est un alkylène et D un groupement ammonium quaternaire ; A1 et B1 représentent des groupements polyméthyléniques contenant de 2 à 20 atomes de carbone pouvant être linéaires ou ramifiés, saturés ou insaturés, et pouvant contenir, liés à ou intercalés dans la chaîne principale, un ou plusieurs cycles aromatiques, ou un ou plusieurs atomes d'oxygène, de soufre ou des groupements sulfoxyde, sulfone, disulfure, amino, alkylamino, hydroxyle, ammonium quaternaire, uréido, amide ou ester, et X- désigne un anion dérivé d'un acide minéral ou organique; A1, R10 et R12 peuvent former avec les deux atomes d'azote auxquels ils sont rattachés un cycle pipérazinique ; en outre si A1 désigne un radical alkylène ou hydroxyalkylène linéaire ou ramifié, saturé ou insaturé, B1 peut également désigner un groupement-(CH2)n-CO-D-OC-(CH2)n- dans lequel D désigne : (10) The quaternary diammonium polymer containing recurring units having the formula:

wherein R10, R11, R12 and R13, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or R10, R11, R12 and R13, together or separately, together with the nitrogen atoms to which they are attached, form heterocycles optionally containing a second heteroatom other than nitrogen, or R10, R11, R12 and R13 represent a substituted linear or branched C1-C6 alkyl radical. with a nitro, ester, acyl, amide or -CO-O-R14-D or -CO-NH-R14-D group where R14 is alkylene and D is a quaternary ammonium group; A1 and B1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated, and may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more carbon atoms; 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, R10 and R12 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 may also denote a group - (CH2) n -CO-D-OC- (CH2) n- in which D denotes:

<Desc / Clms Page number 33>

 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: - (CH 2 -CH 2 -O) x -CH 2 -CH 2 - - [ CH 2 -CH (CH 3) -O] y-CH 2 -CH (CH 3) - where x and y denote an integer of 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing a degree medium 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 alternatively the divalent radical -CH 2 -CH 2 -S-S-CH 2 -CH 2 -; d) a ureylene group of formula: -NH-CO-NH-.

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

These polymers have a number average molecular weight generally between 1000 and 100000.

Polymers of this type are especially described 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 and 2,454,547. , 206,462, 2,261,002, 2,271,378, 3,874,870, 4,001,432, 3,989,990, 3,966,904, 4,005,193, 4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027. .020.

dans laquelle R10, R11, R12 et R13, identiques ou différents, désignent un radical alkyle ou hydroxyalkyle ayant de 1 à 4 atomes de carbone environ, n et p sont des nombres entiers variant de 2 à 20 environ et, X- est un anion dérivé d'un acide minéral ou organique. It is more particularly possible to use polymers which consist of recurring units corresponding to the following formula (VIII):

in which R10, R11, R12 and R13, which are identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms, n and p are integers ranging from 2 to approximately 20 and, X- is an anion derived from a mineral or organic acid.

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dans laquelle p désigne un nombre entier variant de 1 à 6 environ, D peut être nul ou peut représenter un groupement-(CH2)r -CO- dans lequel r désigne un nombre égal à 4 ou à 7, X- est un anion ; De tels polymères peuvent être préparés selon les procédés décrits dans les brevets U.S.A. n 4 157 388,4 390 689, 4 702 906, 4 719 282. Ils sont notamment décrits dans la demande de brevet EP-A-122 324. (11) Quaternary polyammonium polymers consisting of repeating units of formula (IX):

wherein p denotes an integer ranging from 1 to about 6, D may be zero or may represent a group-(CH 2) r -CO- wherein r denotes a number equal to 4 or 7, X- is an anion; Such polymers may be prepared according to the processes described in US Pat. Nos. 4,157,388, 4,390,689, 4,702,906 and 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 Miranol.

(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as, for example, the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company B.A.S.F.

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

(14) Crosslinked polymers of methacryloyloxyalkyl (C1-C4) trialkyl (C1-C4) ammonium salts such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized by the methyl chloride, homo or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. It is more particularly possible to use a crosslinked acrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer (20/80

<Desc / Clms Page number 35>

 by weight) as a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is marketed under the name "SALCARE SC 92" by the company ALLIED COLLOIDS. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names "SALCARE SC 95" and "SALCARE SC 96" by the company ALLIED COLLOIDS.

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

et notamment ceux dont le poids moléculaire, déterminé par chromatographie par perméation de gel, est compris entre 9500 et 9900;

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

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

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 and especially those whose molecular weight, determined by gel permeation chromatography, is about 1200.

The concentration of cationic polymer in the compositions according to the present invention may 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 that may be used in accordance with the present invention may be chosen from polymers comprising K and M units statistically distributed 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 derived from an acidic monomer comprising one or more carboxylic or sulphonic groups, or K and M may denote groups derived from zwitterionic monomers of carboxybetaines or sulphobetaines, K and M may also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, wherein at least one of the amine groups carries a carboxylic or sulfonic group connected via a hydrocarbon radical, or K and M are part of a chain of a polymer with an ethylene [alpha], ss-dicarboxylic unit, one of which is gro Carboxylic upgrades were reacted with a polyamine having 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, the acrylic acid, methacrylic acid, maleic acid, alpha-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as, more particularly, dialkylaminoalkylmethacrylate and acrylate, dialkylaminoalkylmethacrylamide; and acrylamide. Such compounds are

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described in US Pat. No. 3,836,537. Mention may also be made of the sodium acrylate / acrylamidopropyltrimethylammonium chloride copolymer sold under the name Polyquart KE 3033 by the
HENKEL company.

The vinyl compound may also be a dialkyldiallylammonium salt such as dimethyldiallylammonium chloride. The copolymers of acrylic acid and of the latter monomer are available 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 the nitrogen with an alkyl radical, b) with at least one acidic comonomer containing one or more carboxylic groups reagents, and c) at least one basic comonomer such as primary, secondary, tertiary and quaternary amine substituent esters of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides which are 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, Ntertiobutyl-acrylamide, N-tert-octyl-acrylamide, N-octylacrylamide, Ndecylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.

Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, and N-tert-butylaminoethyl methacrylates.

The copolymers whose CTFA (4th Ed., 1991) name is octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer are particularly used.

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 such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.

c) dans les proportions de 0 à 20 moles % le radical -NH-(CH2)6-NHdérivant de l'hexaméthylènediamine, ces polyaminoamines étant réticulées par addition d'un agent réticulant bifonctionnel choisi parmi les épihalohydrines, les diépoxydes, les dianhydrides, les dérivés bis insaturés, au moyen de 0,025 à 0,35 mole d'agent réticulant par groupement amine du polyaminoamide et alcoylés par action d'acide acrylique, d'acide chloracétique ou d'une alcane sultone ou de leurs sels. (3) Polyamino amides crosslinked and alkylated partially or totally derived from polyaminoamides of general formula: [CO-R 19 -CO-Z] - (X) in which R 19 represents a divalent radical derived from a saturated dicarboxylic acid, a aliphatic mono or dicarboxylic acid having an ethylenic double bond, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or a radical derived from the addition of any of said acids with a bis amine primary or secondary bis, 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 mole%, the radical -N / H- [ (CH2) xN / H] p- (XI) where x = 2 and p = 2 or 3, or x = 3 and p = 2 this radical derived 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 is derived from ethylenediamine, or the radical derived from piperazine:

c) in the proportions of 0 to 20 mole%, the -NH- (CH 2) 6 -NH radical derived from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis unsaturated derivatives, by means of 0.025 to 0.35 mole of crosslinking agent per amine group of the polyaminoamide and alkylated by the action of acrylic acid, chloroacetic acid or an alkane sultone or their salts.

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 The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic acid, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic acid, terephthalic acid, acids with ethylenic double bond such as acrylic acid, methacrylic acid, itaconic acid.

The alkanesultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

dans laquelle R20 désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou méthacrylamide, y et z représentent un nombre entier de 1 à 3, R21 et R22 représentent un atome d'hydrogène, méthyle, éthyle ou propyle, R23 et R24 représentent un atome d'hydrogène ou un radical alkyle de telle façon que la somme des atomes de carbone dans R23 et R24 ne dépasse pas 10. (4) polymers having zwitterionic units of formula:

in which R 20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer of 1 to 3, R 21 and R 22 represent a hydrogen, methyl, ethyl or propyl atom, R 23 and R24 represents a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.

Polymers comprising such units may also comprise 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, mention may be made of the methyl methacrylate dimethylcarboxymethylammonioethylmethacrylate methyl copolymer, such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.

 (5) polymers derived from chitosan having monomeric units corresponding to the following formulas (XIII), (XIV), (XV):

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le motif (XIII) étant présent dans des proportions comprises entre 0 et 30%, le motif (XIV) dans des proportions comprises entre 5 et 50% et le motif F dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif (XV), R25 représente un radical de formule :

dans laquelle si q=0, R26, R27 et R28, identiques ou différents, représentent chacun un atome d'hydrogène, un reste méthyle, hydroxyle, acétoxy ou amino, un reste monoalcoylamine ou un reste dialcoylamine éventuellement interrompus par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes amine, hydroxyle, carboxyle, alcoylthio, sulfonique, un reste alcoylthio dont le groupe alcoyle porte un reste amino, l'un au moins des radicaux R26, R27 et R28 étant dans ce cas un atome d'hydrogène ; ou si q=1, R26, R27 et R28 représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides.

the unit (XIII) being present in proportions of between 0 and 30%, the unit (XIV) in proportions of between 5 and 50% and the unit F in proportions of between 30 and 90%, it being understood that in this R25 represents a radical of formula

in which if q = 0, R26, R27 and R28, which are identical or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or more carbon atoms. nitrogen and / or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio, sulphonic groups, an alkylthio radical whose 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, R27 and R28 each represents a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

 (6) The polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan 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 the French patent 1,400,366:

<Desc / Clms Page number 41>

dans laquelle R29 représente un atome d'hydrogène, un radical CH3O, CH3CH20, phényle, R30 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R31désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R32 désigne un radical alkyle inférieur tel que méthyle, éthyle ou un radical répondant à la formule : -R33-N(R31)2, R33 représentant un groupement -CH2-CH2- , -CH2-CH2-CH2- , -CH2-CH (CH3)- , R31 ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces radicaux et contenant jusqu'à 6 atomes de carbone.

in which R29 represents a hydrogen atom, a radical CH3O, CH3CH20, phenyl, 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 (R31) 2, R33 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH ( CH3) -, R31 having the meanings mentioned above, as well as the higher homologues of these radicals and containing up to 6 carbon atoms.

et X désigne le symbole E ou E', E ou E' identiques ou différents désignent un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée comportant jusqu'à 7 atomes de carbone dans la chaîne principale non substituée ou (8) amphoteric polymers of the -DXDX- type chosen from: a) the polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula: -DXDXD- (XVII) where D designates a radical

and X denotes the symbol E or E ', E or E', which may be identical or different, denote a divalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the unsubstituted main chain or

<Desc / Clms Page number 42>

et X désigne le symbole E ou E' et au moins une fois E' ; ayant la signification indiquée ci-dessus et E' est un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs radicaux hydroxyle et comportant un ou plusieurs atomes d'azote, l'atome d'azote étant substitué par une chaîne alkyle interrompue éventuellement par un atome d'oxygène et comportant obligatoirement une ou plusieurs fonctions carboxyle ou une ou plusieurs fonctions hydroxyle et bétaïnisées par réaction avec l'acide chloracétique ou du chloracétate de soude. substituted with hydroxyl groups and which may further comprise oxygen, nitrogen, sulfur, 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, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide groups, alcohol, ester and / or urethane; b) polymers of formula: -DXDX- (XVIII) where D denotes a radical

and X denotes the symbol E or E 'and at least once E'; having the meaning indicated above and E 'is a divalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or unsubstituted by one or more hydroxyl radicals and having one or more a plurality of nitrogen atoms, the nitrogen atom being substituted by an optionally interrupted alkyl chain by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betaineized by reaction with chloroacetic acid or chloroacetate of soda.

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

According to the invention, the amphoteric polymer (s) may represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and still more preferably from 0.1% to 3% by weight. , 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) at the 4-position of the 5halo-ortho-amino-phenols of formula (1), at least one surfactant.

<Desc / Clms Page number 43>

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

The surfactants that are suitable for carrying out the present invention are, in particular: (i) Anionic surfactant (s): As an example of anionic surfactants that can be used, alone or as mixtures, in the context of the According to the present invention, mention may be made in particular (non-limiting list) of the salts (in particular alkaline salts, in particular of sodium, ammonium salts, amine salts, aminoalcohol salts or magnesium salts) of the following compounds: alkyl sulphates, alkyl ether sulfates, alkyl amido ether sulfates, alkyl aryl polyether sulphates, monoglyceride sulphates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin-sulfonates, paraffin-sulfonates; (C6-C24) alkylsulphosuccinates, (C6-C24) alkylsulphosuccinates, (C6-C24) alkylamidesulfosuccinates; (C6-C24) alkyl sulphoacetates; acyl (C6-C24) sarcosinates and acyl (C6-C24) glutamates It is also possible to use (C6-C24) alkyl polyglycoside carboxylic esters such as alkylglucoside citrates, alkylpolyglycoside tartrate and alkylpolyglycoside sulfosuccinates., alkylsulfosuccinamates ; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably comprising from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants that can still be used, mention may also be made of fatty acid salts such as the salts of oleic, ricinoleic, palmitic and stearic acids, coconut oil acid or hydrogenated coconut oil acid; acyllactylates whose acyl radical has 8 to 20 carbon atoms. It is also possible to use alkyl D galactoside uronic acids and their salts, polyoxyalkylenated (C6-C24) alkylcarboxylic acids, C

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 C24) polyoxyalkylenated aryl ether carboxylic acids, polyoxyalkylenated (C6-C24) alkyl amido ether carboxylic acids and their salts, in particular those containing from 2 to 50 alkylene oxide groups, in particular ethylene, and mixtures thereof.

 (ii) Nonionic surfactant (s): Nonionic 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 critical in the context of the present invention. Thus, they may be chosen in particular from (not limited to) alcohols, alpha-diols, alkylphenols or polyethoxylated fatty acids, polypropoxylated, having a fatty chain comprising for example 8 to 18 carbon atoms, the number of oxide groups. ethylene or propylene oxide which may range from 2 to 50. Mention may also be made of copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and propylene oxide 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; oxyethylenated sorbitan fatty acid esters having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkylglucamine derivatives, amine oxides such as (C10-C14) alkyl oxides or oxides N-acylaminopropylmorpholine. It will be noted that alkylpolyglycosides constitute nonionic surfactants that are particularly suitable for the purposes of the present invention, as are ethoxylated fatty alcohols.

 (iii) Amphoteric (s) or Zwitterionic Surfactant (s): Amphoteric or zwitterionic surfactants, the nature of which is not within the scope of the present invention of a critical nature, may be

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 in particular (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one anionic water-solubilising group (for example carboxylate, sulphonate, sulphate phosphate or phosphonate); mention may also be made of alkyl (C8-C20) betaines, sulfobetaines, (C8-C20) alkylamido (C1-C6) alkyl betaines or (CgC20) alkylamido (C1-C6) alkyl sulfobetaines.

Among the amine derivatives, mention may be made of the products sold under the name MIRANOL, as described in US Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates of respective structures: R34-CONHCH2CH2 -N (R35) (R36) (CH2COO-) in which: R34 denotes an alkyl radical of an R34-COOH acid present in the hydrolysed coconut oil, a heptyl radical, nonyl or undecyl, R35 denotes a beta-hydroxyethyl group and R36 a carboxymethyl group; and R34'-CONHCH2CH2-N (B) (C) wherein: 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 R37 -COOH acid present in coconut oil or in hydrolysed linseed oil, a radical alkyl, especially C7, Cg, C11 or C13, a C17 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 Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium

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 Caprylamphodipropionate, Disodium Capryloamphodipropionate, Lauroamphodipropionic acid, Cocoamphodipropionic acid.

By way of example, mention may be made of cocoamphodiacetate sold under the trade name MIRANOL C2M concentrated by Rhodia Chimie.

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

The amounts of surfactants present in the composition according to the invention may 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 according to the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic or nonionic or zwitterionic polymers other than those already mentioned, or mixtures thereof, inorganic or organic thickeners, antioxidants, penetrating 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 the French patent application 2,773,474 whose content is an integral part of the invention, film-forming agents, ceramides, preservatives and reducing agents, opacifying agents.

Among the reducing agents or antioxidants used to conserve the oxidation dyes and usable in the proportion of 0.05 to 1.5% by weight of the weight

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 total of the composition, there may be mentioned in particular sodium sulphite, thioglycolic acid, thiolactic acid, sodium bisulfite, dehydroascorbic acid, hydroquinone, 2-methyl-hydroquinone, tert-butylhydroquinone, the homogentisic acid, N-acetyl-L-cysteine described in the patent application FR-9903829 or ketosis and preferably a ketohexose such as fructose as described in the patent application of the applicant FR-9904338 .

Of course, one 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 according to the invention are not, or not substantially, altered by the addition or additions envisaged.

The ready-to-use dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, possibly pressurized, or in any other form suitable for dyeing keratinous fibers. , and in particular human hair. In this case, the compound (s) of formula (I) according to the invention and the 2-electron or 4-electron oxidoreductase (s) or peroxidase (s) are present in the same composition, and consequently said composition must be free from gaseous oxygen, so as to avoid any premature oxidation of the compound (s) of formula (1).

The invention also relates to a process for dyeing keratin fibers and in particular human keratinous 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 of between room temperature and 80.degree. C., for a time sufficient to develop the desired coloration. Preferably, the fibers are then rinsed, or optionally washed with shampoo, and then dried.

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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 keratinous 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 of 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 the 5-halo-ortho-amino-phenols of formula (I) as defined above, and secondly, a composition containing, in a medium suitable for dyeing, at least one oxidoreductase enzyme with 2 electrons or to 4 electrons, or peroxidase, then to proceed to their mixing at the time of use before applying this mixture on keratinous fibers Another object of the invention is a dyeing device with several compartments or "kit" of dyeing or any other multi-compartment packaging system of which at least a first compartment contains the composition (A) as defined above and at least one second compartment contains the composition (B) such as as defined above. These devices may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant.

The following example is intended to illustrate the invention without limiting its scope.

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EXAMPLE The following ready-to-use dyeing composition was prepared:

<Tb>
<tb> 5-chloro-4-methoxy-2-amino-phenol <SEP> ............... <SEP> 0.521 <SEP> g
<tb> Paraphenylenediamine ................................ <SEP> 0.324 <SEP> g
<tb> N-acetyl-L-cysteine ..................................... <SEP> 0.10 <SEP> g
<Tb>

Uricase..................................................... 20.10 unitésU

Uricase ................................................. .... 20.10 unitsU

<Tb>
<tb> Acid <SEP> uric .......................................... .... <SEP> 1 <SEP> 9 <SEP>
<tb> Mono-oleate <SEP> of <SEP> polyglycerol <SEP> to <SEP> 10 <SEP> moles <SEP> of
<Tb>

glycérol................................................... 1 g

glycerol................................................. .. 1 g

<Tb>
<tb> Aculyn <SEP> 22 <SEP> (Rohm <SEP> and <SEP> Haas) ....................... <SEP> 0, 75 <SEP> g <SEP> MA *
<tb> 2-amino-2-methyl-1-propanol ....................... <SEP> qsp <SEP> pH <SEP> 9, 5
<tb> Demineralized <SEP> water <SEP> ........................ qsp ..... <SEP> 100 <SEP> g
<tb> * <SEP> means <SEP> Material <SEP> Active
<Tb>
The composition was applied to gray hair strands natural to 90% white. After 30 minutes of resting at room temperature, the locks of hair were rinsed, washed with shampoo and dried. They have been dyed dark ash and the coloring obtained has good tenacity to light.

Claims (42)

 in which, R denotes a hydrogen atom or a C 1 -C 6 alkyl radical, X denotes a halogen atom, and their addition salts with an acid.

 1. ready-to-use composition, for the oxidation dyeing of keratinous fibers and in particular human keratinous fibers such as the hair, comprising in a medium suitable for dyeing, at least one derivative in position-4 of 5 -halogeno-ortho-amino-phenols of formula (1) defined below, and at least one oxidizing agent: 2. Composition according to Claim 1, characterized in that in formula (1), 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 (1) are chosen from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates. 4. Composition according to any one of the preceding claims, characterized in that the compound (s) of formula (1) and their addition salts with an acid represent from 0.001 to 10% by weight of the total weight of the composition. <Desc / Clms Page number 51>  5. Composition according to Claim 4, characterized in that the compound (s) of formula (1) 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 selected from paraphenylenediamines, double bases, paraaminophenols, ortho-aminophenols different from those of formula (1) and heterocyclic oxidation bases and their addition salts with an acid. 7. Composition according to Claim 6, characterized in that the oxidation dye precursor or precursors 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 comprises at least one enzyme selected from 2-electron oxidoreductases, 4-electron oxidoreductases, or peroxidases. 9. The composition as claimed in claim 8, 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 and pyruvates. oxidases, uricases, choline oxidases, sarcosine oxidases, bilirubin oxidases and amino acid oxidases. 10. The composition as claimed in claim 8, characterized in that the 4-electron oxidoreductases are chosen from laccases, tyrosinases, catechol oxidases and polyphenol oxidases. 11. Composition according to Claim 10, characterized in that the oxidoreductases with 4 electrons are chosen from laccases of plant origin, of animal origin, of fungal origin or of bacterial origin and from laccases obtained by biotechnology. <Desc / Clms Page number 52> 12. Composition according to claim 11, characterized in that characterized in that the laccase is of plant origin and selected from laccases present in extracts of Anacardiaceae; Podocarpaceae, from Rosmarinus off. ; deSolanum tuberosum; of Iris sp. ; from Coffea sp. ; Daucus carrota; of Vinca minor; Persea americana; Catharenthus roseus; Musa sp. ; de Malus pumila; Gingko biloba; of Monotropa hypopithys (sucepin), Aesculus sp. ; Acer pseudoplatanus; of Prunus persica and Pistacia palaestina.  13. Composition according to claim 10 or 11, characterized in that the laccase is of fungal origin or obtained by biotechnology.  14. Composition according to Claim 13, characterized in that the laccase is chosen from laccases derived from Polyporus versicolor, Rhizoctonia praticola, Rhus vernicifera, Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyricularia. Onzae, Trametes versicolor, Fomes fomentarius, Chaetomium thermophilus, 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, Ceriponopsis subvermispora, Coprinus cinereus, of Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and their variants.  15. Composition according to claim 8, characterized in that the peroxidases are simplex peroxidases.  16. Composition according to Claim 8, characterized in that the peroxidase or peroxidases are catalases. <Desc / Clms Page number 53> 17. Composition according to Claim 8, characterized in that the peroxidase (s) are used with a donor for the said enzyme (s) and are chosen from NADH peroxidases, peroxidase fatty acids, NADPH peroxidases and cytochrome-c peroxidases. peroxidase iodides, peroxidase chlorides, L. ascorbates peroxidases, glutathione peroxidases. 18. Composition according to any one of claims 8 and 15 to 17, characterized in that the or peroxidases are of animal, plant, fungal, bacterial or biotechnology. 19. A composition according to claim 18, characterized in that the peroxidase or peroxidases are derived from apple, apricot, barley, black radish, beetroot, cabbage, carrot, corn , cotton, garlic, grapes, mint, rhubarb, soybean, spinach, coprin, bovine milk, microorganisms of the type Acetobacter peroxidans, Staphylococcus faecalis, Arthromyces ramosus. 20. Composition according to any one of the preceding claims, characterized in that the oxidoreductases with 2 electrons or 4 electrons represent from 0.01 to 20% by weight of the total weight of the composition. 21. Composition according to claim 20, characterized in that the oxidoreductases with 2 electrons or 4 electrons represent from 0.1 to 5% by weight of the total weight of the composition. 22. Composition according to any one of claims 8,15 to 18, characterized in that the peroxidase or peroxidase represent from 0.0001 to 20% by weight of the total weight of the composition. 23. A composition according to claim 22, characterized in that the peroxidase or peroxidase represent from 0.001 to 10% by weight of the total weight of the composition. <Desc / Clms Page number 54> 24. Composition according to any one of the preceding claims, characterized in that it contains at least one additional coupler. Composition according to Claim 24, characterized in that the additional couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthols, heterocyclic couplers, and the addition salts of these compounds with an acid. 26. Composition according to any one of claims 24 or 25, 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. 27. Composition according to any one of the preceding claims, characterized in that the acid addition salts of the oxidation dye precursors and additional couplers are chosen from hydrochlorides, hydrobromides, sulphates and tartrates. , lactates and acetates. 28. 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 preferably from 0.01 to 10% of the total weight of the composition. 29. Composition according to any one of the preceding claims, characterized in that the medium suitable for dyeing is constituted by water or a mixture of water and at least one organic solvent. 30. Composition according to Claim 29, 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. <Desc / Clms Page number 55> 31. 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. 32. Composition according to claim 31, characterized in that the surfactant is nonionic. 33. Composition according to any one of the preceding claims, characterized in that it contains at least one anionic, nonionic, cationic or amphoteric thickening polymer and comprising at least one fatty chain in the proportion of 0.01. % to 10% by weight of the total weight of the composition. 34. Composition according to any one of the preceding claims, characterized in that it contains at least one cationic or amphoteric polymer in a 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 has a pH of between 3 and 12, and preferably between 5 and 11. 36. Composition according to any one of the preceding claims, characterized in that it is in the form of liquid, cream, gel, possibly pressurized, or in any other form suitable for dyeing keratinous fibers. 37. A process for the oxidation dyeing of keratinous fibers and in particular human keratin fibers such as the hair, characterized in that it is applied to said fibers at an application temperature of between room temperature and 80.degree. 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 color. <Desc / Clms Page number 56> 38. Method according to claim 37, characterized in that the application temperature is between ambient temperature and 60 C. 39. The method of claim 37, characterized in that the time sufficient for the development of the color is between 1 and 60 minutes. 40. Process according to claim 39, characterized in that the time sufficient for the development of the coloration is between 5 and 30 minutes. 41. A method according to any one of claims 37 to 40, characterized in that it comprises a preliminary step of storing in separate form, on the one hand, a composition comprising, in a medium suitable for dyeing, at less a compound of formula (1) as defined in any one of claims 1 to 5, and secondly, a composition containing, in a medium suitable for dyeing, at least one enzyme oxidoreductase type 2 or to 4 electrons or peroxidase, then to proceed to their mixture at the time of use before applying this mixture on the keratinous fibers. 42. A multi-compartment dyeing device, characterized in that it comprises at least a first compartment containing a composition comprising, in a medium suitable for dyeing, at least one compound of formula (1) as defined in US Pat. 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 oxidoreductase enzyme with 2 or 4 electrons or peroxidase.