AU739945B2 - Keratinous fibre oxidation dyeing composition containing a laccase and dyeing method using same - Google Patents

Abstract

The invention concerns a ready-to-use composition for oxidation dyeing of keratinous fibres, and in particular human keratinous fibres such as hair comprising, in a suitable dyeing medium, 2-amino 4-N-( beta -hydroxyethyl)amino anisole as coupling agent, and at least an enzyme such as laccase, as well as the dyeing method using said composition.

Description

'1

I

WO 99/36042 1 PCT/FR98/02834 COMPOSITION FOR THE OXIDATION DYEING OF KERATINOUS FIBRES CONTAINING A LACCASE AND DYEING METHOD USING THIS COMPOSITION The subject of the invention is a composition for the oxidation dyeing of keratinous fibres, and in particular of human keratinous fibres such as hair, comprising, in a medium appropriate for dyeing, at least one oxidation base, 2-amino-4-N-(P-hydroxyethyl)aminoanisole as coupler, and at least one enzyme of the laccase type, as well as the dyeing method using this composition.

It is known to dye keratinous fibres, and in particular human hair, with dyeing compositions containing oxidation dye precursors, in particular ortho- and para-phenylenediamines, ortho- or paraaminophenols, heterocyclic bases generally called oxidation bases. The oxidation dye precursors, (oxidation bases), are colourless or weakly coloured compounds which, combined with oxidizing products, can give rise to dye and coloured compounds by a process of oxidative condensation.

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

0' I 2 The variety of molecules used in oxidation bases and couplers allows a rich palette of colours to be obtained.

The so-called "permanent" colour obtained by means of these oxidation dyes should moreover satisfy a number of requirements. Thus, it should have no drawbacks from the toxicological point of view, it should make it possible to obtain shades of the desired intensity and it should exhibit good resistance towards external agents (light, adverse weather conditions, washing, permanent waving, perspiration, rubbing).

The dyes should also make it possible to cover grey hair, and thus should be the least selective possible, that is to say they should make it possible to obtain the smallest possible differences in colour all along the same keratinous fibre, which may indeed be differently sensitized damaged) between its tip and its root.

The oxidation dyeing of keratinous fibres is generally carried out in an alkaline medium, in the presence of hydrogen peroxide. However, the use of alkaline media in the presence of hydrogen peroxide has the disadvantage of causing substantial degradation of the fibres, as well as decolouring of the keratinous fibres which is not always desirable.

The oxidation dyeing of keratinous fibres can also be carried out with the aid of oxidizing systems different from hydrogen peroxide such as enzymatic systems. Thus, it has already been proposed in Patent US 3,251,742, Patent Applications FR-A-2,112,549, FR-A-2,694,018, EP-A-0,504,005, W095/07988, W095/33836, W095/33837, W096/00290, W097/19998 and W097/19999 to dye keratinous fibres with compositions comprising at least one oxidation dye, or at least one melanin precursor, in combination with enzymes of the laccase type, the said compositions being brought into contact with atmospheric oxygen. These dyeing formulations, although used under conditions which do not cause degradation of the keratinous fibres comparable to that caused by dyeings carried out in the presence of hydrogen peroxide, lead to colours which are still inadequate both from the point of view of homogeneity of the colour distributed along the fibre (unison), from the point of view of chromaticity (luminosity) and of the dyeing power.

Now, the applicant has now just discovered that it is possible to obtain novel dyes which are capable of giving intense and chromatic colours, without causing significant degradation of the keratinous fibres, which are not very selective and which are quite resistant to various attacks to which the fibres may be subjected, by combining at least one oxidation base, 2-amino-4-N-(P-hydroxyethyl)aminoanisole as coupler, and at least one enzyme of the laccase type.

This discovery forms the basis of the present invention.

The first subject of the invention is therefore a ready-to-use composition for the oxidation dyeing of keratinous fibres, and in particular human keratinous fibres such as hair, characterized in that it comprises, in a medium appropriate for dyeing: at least one oxidation base, 2-amino-4-N-(p-hydroxyethyl)aminoanisole and/or at least one of its addition salts with an acid as coupler, at least one enzyme of the laccase type.

The ready-to-use dyeing composition in accordance with the invention gives intense colours which exhibit low selectivity and excellent properties of resistance both to atmospheric agents such as light and adverse weather conditions and to perspiration and various treatments to which the hair may be subjected (washing, permanent deformation).

The subject of the invention is also a method for the oxidation dyeing of keratinous fibres using this ready-to-use dyeing composition.

The laccase(s) used in the ready-to-use dye composition in accordance with the invention may be chosen in particular from laccases of plant origin, animal origin, fungal origin (yeasts, moulds, fungi) or bacterial origin, organisms which may be of mono- or /-xpluricellular origin. The laccase(s) used in the readyto-use dyeing composition in accordance with the invention can also be obtained by biotechnology.

Among the laccases of plant origin which can be used according to the invention, there may be mentioned the laccases produced by plants which perform chlorophyll synthesis such as those indicated in Patent Application FR-A-2,694,018.

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

Among the laccases of fungal origin, optionally obtained by biotechnology, which can be used according to the invention, there may be mentioned the laccase(s) derived from Polyporus versicolor, Rhizoctonia practicola and Rhus vernicifera as described for examples in Patent Applications FR-A-2,112,549 and EP-A-504005, the laccases described in Patent Applications W095/07988, W095/33836, W095/33837, W096/00290, W097/19998 and W097/19999, whose content is an integral part of the present description, such as for example the laccase(s) derived from Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyricularia orizae, and variants thereof. There may also be mentioned the laccase(s) derived from Trametes versicolor, Fomes fomentarius, Chaetomium thermophile, Neurospora crassa, Colorius versicol, 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 cladosporiodes, Cerrena unicolor, Coriolus hirsutus, Ceriporiopsis subvermispora, Coprinus cinereus, Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and variants thereof.

The laccases of fungal origin optionally obtained by biotechnology will be preferably chosen.

The enzymatic activity of the laccases used in accordance with the invention and which have syringaldazine among their substrates can be defined from the oxidation of syringaldazine under aerobic conditions. The Lacu unit corresponds to the quantity of enzyme catalysing the conversion of 1 mmol of syringaldazine per minute at a pH of 5.5 and at a temperature of 300C. The unit U corresponds to the quantity of enzyme producing a delta absorbance of I-\0.001 per minute, at a wavelength of 530 nm, using syringaldazine as substrate, at 30 0 C and at a pH of The enzymatic activity of the laccases of the invention can also be defined from the oxidation of para-phenylenediamine. The lacu unit corresponds to the quantity of enzyme producing a delta absorbance of 0.001 per minute, at a wavelength of 496.5 nm, using para-phenylenediamine as substrate (64 mM), at 30 0 C and at a pH of According to the invention, it is preferable to determine the enzymatic activity in lacu units.

The quantity of laccase(s) present in the ready-to-use dyeing composition in accordance with the invention will vary according to the nature of the laccase(s) used. Preferably, the quantity of laccase(s) is between 0.5 and 200 Lacu approximately that is to say between 10,000 and 4x106 U units approximately or that is to say between 20 and 2x10 6 lacu units, per 100 g of dyeing composition.

The nature of the oxidation base(s) used in the ready-to-use dyeing composition is not critical.

They may be chosen in particular from paraphenylenediamines, double bases, para-aminophenols, ortho-aminophenols and heterocyclic oxidation bases.

Among the para-phenylenediamines which can be used as oxidation base in the dyeing composition in accordance with the invention, there may be mentioned in particular the compounds of the following formula jt\ and their addition salts with an acid:

(I)

NH

2 in which: Ri represents a hydrogen atom, a C 1

-C

4 alkyl radical, a monohydroxy(Ci-C 4 alkyl) radical, a polyhydroxy-

(C

2

-C

4 alkyl) radical, a (C 1

-C

4 )alkoxy(C 1

-C

4 )alkyl radical, a C 1

-C

4 alkyl radical substituted with a nitrogen-containing group, a phenyl radical or a 4'-aminophenyl radical;

R

2 represents a hydrogen atom, a C 1

-C

4 alkyl radical, a monohydroxy(C 1

-C

4 alkyl) radical, a polyhydroxy(C 2

-C

4 alkyl) radical, a

(C

1

-C

4 )alkoxy(C 1

-C

4 )alkyl radical or a C 1

-C

4 alkyl radical substituted with a nitrogen-containing group;

R

3 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a Ci-C 4 alkyl radical, a monohydroxy(C-C 4 alkyl) radical, a hydroxy(C 1

-C

4 alkoxy) radical, an acetylamino(C 1

-C

4 alkoxy) radical, a mesylamino(Ci-C 4 alkoxy) radical or a carbamoylamino(Ci-C 4 alkoxy) radical,

R

4 represents a hydrogen or halogen atom or a C 1

-C

4 alkyl radical.

Among the nitrogen-containing groups of formula above, there may be mentioned in particular the amino, mono(C 1

-C

4 )alkylamino, (C 1

-C

4 )dialkylamino, I I 9 (C C 4 trialkyl amino, monohydroxy (C C 4 alkyl amino, imidazolinium and ammonium radicals.

Among the para-phenylenediamines of formula above, there may be mentioned more particularly para-phenylenediamine, para-tolylenediamine, 2-chloropara-phenylenediamine, 2,3 -dimethyl-para-phenylenediamine, 2, 6-dimethyl-para-phenylenediamine, 2, 6-diethyl-para-phenylenediamine, 2, phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-paraphenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis (1-hydroxyethyl) -para-phenylenediamine, 4-N,Nbis(f3-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(3hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethylpara-phenylenediamine, 2-f luoro-para-phenylenediamine, 2 -isopropyl-para-phenylenediamine, N- (P-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N- (ethyl-p3-hydroxyethyl) -para-phenylenediamine, N- (f,y-dihydroxypropyl) -para-phenylenediamine, N- aminophenyl) -para-phenylenediamine, N-phenyl-paraphenylenediamine, 2-1-hydroxyethyloxy-paraphenylenediamine, 2-p-acetylaminoethyloxy-paraphenylenediamine, N- (f-methoxyethy1) -paraphenylenediamine, and their addition salts with an acid.

Among the para-phenylenediamines of formula above, there are most particularly preferred paraphenylenediamine, para-tolylenediamine, 2-isopropylpara-phenylenediamine, 2-p-hydroxyethyl-paraphenylenediamine, 2-p-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-paraphenylenediamine, N,N-bis(p-hydroxyethyl)-paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-Pacetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid.

According to the invention, "double bases" is understood to mean the compounds containing at least two aromatic rings on which amino and/or hydroxyl groups are carried.

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

Z.

R. R R I Y 11)

NR

9 Ro

NRR

12 in which:

Z

1 and Z 2 which are identical or different, represent a hydroxyl or -NH 2 radical which may be substituted with a C 1

-C

4 alkyl radical or with a linking arm Y; the linking arm Y represents a linear or branched alkylene chain comprising from 1 to 14 carbon atoms, which may be interrupted by or which may end with one or more nitrogen-containing groups and/or one or more heteroatoms such as oxygen, sulphur or nitrogen atoms, and optionally substituted with one or more hydroxyl or

C

1

-C

6 alkoxy radicals; Rs and Re represent a hydrogen or halogen atom, a C 1

-C

4 alkyl radical, a monohydroxy(C 1

-C

4 alkyl) radical, a polyhydroxy(C 2

-C

4 alkyl) radical, an amino(C 1

-C

4 alkyl) radical or a linking arm Y;

R

7 Re, R 9

R

1 o, R 11 and R 12 which are identical or different, represent a hydrogen atom, a linking arm Y or a C 1

-C

4 alkyl radical; it being understood that the compounds of formula (II) contain only one linking arm Y per molecule.

Among the nitrogen-containing groups of formula (II) above, there may be mentioned in particular the amino, mono(C 1

-C

4 alkylamino, (C -C 4 dialkylamino, (C 1

-C

4 trialkylamino, monohydroxy (C 1

-C

4 alkylamino, imidazolinium and ammonium radicals.

Among the double bases of formulae (II) above, there may be mentioned more particularly N,N'-bis(p-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3diaminopropanol, N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(P-hydroxyethyl)-N,N'bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4methylaminophenyl)tetramethylenediamine, N,N'bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid.

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

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

OH

R 1 R14

NH

2 in which:

R

13 represents a hydrogen or halogen atom, a Ci-C 4 alkyl, monohydroxy(Ci-C 4 alkyl) (C 1

-C

4 )alkoxy(C 1

-C

4 alkyl, amino(C 1

-C

4 alkyl) or hydroxy(C 1

-C

4 )alkylamino- (Ci-C 4 alkyl) radical,

R

14 represents a hydrogen or halogen atom, a Ci-C 4 alkyl, monohydroxy(C 1

-C

4 alkyl), polyhydroxy(C 2

-C

4 alkyl), amino(C 1

-C

4 alkyl), cyano(C 1

-C

4 alkyl) or (Ci-C 4 )alkoxy(C 1

-C

4 alkyl radical, it being understood that at least one of the radicals

R

13 or R 14 represents a hydrogen atom.

Among the para-aminophenols of formula (III) above, there may be mentioned more particularly paraaminophenol, 4-amino-3-methylphenol, 4-amino-3fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(p-hydroxyethylaminomethyl)phenol, 4-amino-2fluorophenol, and their addition salts with an acid.

Among the ortho-aminophenols which can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned more particularly 2-aminophenol, methylphenol, 2-amino-6-methylphenol, 5-acetamido-2aminophenol, and their addition salts with an acid.

Among the heterocyclic bases which can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned more particularly pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives, and their addition salts with an acid.

Among the pyridine derivatives, there may be mentioned more particularly the compounds described for example in Patents GB 1,026,978 and GB 1,153,196, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(Pmethoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their addition salts with an acid.

Among the pyrimidine derivatives, there may be mentioned more particularly the compounds described for example in German Patent DE 2,359,399 or Japanese Patents JP 88-169,571 and JP 91-333,495 or Patent Application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6diaminopyrimidine, 2,5,6-triaminopyrimidine, and their addition salts with an acid.

Among the pyrazole derivatives, there may be mentioned more particularly the compounds described in Patents DE 3,843,892, DE 4,133,957 and Patent Applications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE 195 43 988 such as 3,4-diaminopyrazole, 4,5-diamino-l-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5hydrazinopyrazole, l-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-l-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 1-(P-hydroxyethyl) -3-methylpyrazole, ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3- methoxyphenyl)pyrazole, 4,5-diamino-l-ethyl-3hydroxymethylpyrazole, 4, 5-diamino-3 -hydroxymethyl-lrethylpyrazole, 4, 5-diamino-3-hydroxymethyl-lisopropylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5- -aminoethyl) amino-l,3-dimethylpyrazole, 3,4,5-triaminopyrazole, l-methyl-3,4,5triaminopyrazole, 3, 5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4- (J-hydroxyethyl)amino-lmethylpyrazole, and their addition salts with an acid.

Among the pyrazolopyrirnidine derivatives, there may be mentioned more particularly the compounds described in Patent Application FR-A-2,750,048, among which there may be mentioned: pyrazololll,5-alpyrimidine-3,7-dianine; 2,5-dimethylpyrazolo[1,5-alpyrimidine-3,7-diamine; pyrazolo[l,5-alpyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[l,5-alpyrimidine-3,5-diamine; 3-aminopyrazolo 5-alpyrimidin-7-ol; 3-aminopyrazolo[1,5-alpyrimidin-5-ol; 2- (3-aminopyrazolo[l,5-a]pyrirnidin-7-ylamino)ethanol; 2- (7-aminopyrazolo pyrimidin-3-ylamino) ethanol; 2- [(3-aminopyrazolo pyrimidin-7-yl) (2-hydroxyethyl) amino] ethanol; 2- [(7-aminopyrazolo[l,5-a]pyrimidin-3-yl) (2-hydroxyethyl) amino] ethanol; 5,6-dimethylpyrazolo pyrimidine-3,7-diamine; N- 2,6-dimethylpyrazolo[l,S-alpyrinidine-3,7-diamine; 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7diamine; and their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.

The oxidation base(s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition in accordance with the invention, and still more preferably from 0.005 to 6% by weight approximately of this weight.

The 2-amino-4-N-(P-hydroxyethyl)aminoanisole and/or the or its addition salts with an acid preferably represent from 0.0001 to 8% by weight approximately of the total weight of the dyeing composition, and still more preferably from 0.005 to by weight approximately of this weight.

The dyeing composition in accordance with the invention may contain one or more other couplers different from 2-amino-4-N-(P-hydroxyethyl)aminoanisole and/or direct dyes in particular in order to modify the shades or to increase their shimmer.

Among the couplers which can additionally be present in the ready-to-use dyeing composition in accordance with the invention, there may be mentioned in particular meta-phenylenediamines, metaaminophenols, meta-diphenols, and their addition salts with an acid.

When they are present these additional couplers preferably represent from 0.0001 to 10% by

II

17 weight approximately of the total weight of the readyto-use dyeing composition, and more preferably from 0.005 to 5% by weight approximately of this weight.

In general, the addition salts with an acid which can be used in the context of the dyeing compositions of the invention (oxidation bases and couplers) are in particular chosen from hydrochlorides, hydrobromides, sulphates and tartrates, lactates and acetates.

The medium appropriate for dyeing (or carrier) of the ready-to-use dyeing composition in accordance with the invention generally consists of water or of a mixture of water and of at least one organic solvent in order to solubilize the compounds which might not be sufficiently soluble in water.

The pH of the ready-to-use composition in accordance with the invention is chosen such that the enzymatic activity of the laccase is sufficient. It is generally between 4 and 11 approximately, and preferably between 6 and 9 approximately. It may be adjusted to the desired value using acidifying or alkalinizing agents normally used in dyeing keratinous fibres.

The ready-to-use dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, Samphoteric or zwitterionic surfactants or mixtures thereof, polymers, antioxidants, enzymes different from the laccases used in accordance with the invention, such as for examples peroxidases or oxidoreductases containing 2 electrons, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, thickening agents, film-forming agents, preservatives, opacifying agents or vitamins.

Of course, persons skilled in the art will be careful to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the ready-to-use dyeing composition in accordance with the invention are not, or substantially not, impaired by the addition(s) envisaged.

The ready-to-use dyeing composition in accordance with the invention can be provided in various forms, such as in the form of liquids, creams, gels, optionally pressurized, or in any other form appropriate for dyeing keratinous fibres, in particular human hair. In this case, the oxidation dyes and the enzyme(s) of laccase type are present in the same ready-to-use composition, and consequently the said composition should be free of gaseous oxygen, so as to avoid any premature oxidation of the oxidation dye(s) The subject of the invention is also a method of dyeing keratinous fibres, and in particular human keratinous fibres such as hair, using the ready-to-use dyeing composition as defined above.

According to this method, at least one readyto-use dyeing composition as defined above is applied to the fibres for a sufficient time to develop the desired colour, after which they are rinsed, optionally washed with shampoo, rinsed again and dried.

The time necessary for the development of the colour on the keratinous fibres is generally between 3 and 60 minutes and still more precisely 5 and minutes.

According to one particular embodiment of the invention, the method comprises a preliminary step consisting in storing in a separate form, on the one hand, a composition comprising, in a medium appropriate for dyeing, at least one oxidation base and 2-amino-4-N-(P-hydroxyethyl)aminoanisole and/or at least one of its addition salts with an acid, on the other hand, a composition containing, in a medium appropriate for dyeing, at least one enzyme of the laccase type, and then in mixing them at the time of use before applying this mixture to the keratinous fibres.

Another subject of the invention is a multicompartment device or dyeing (kit) or any other multicompartment packaging system in which a first comparment contains the composition as defined above and a second compartment contains a composition as defined above. These devices may be equipped with a means which makes it possible to deliver the desired mixture to the hair, such as the devices described in Patent FR-2,586,913 in the name of the applicant.

The example which follows is intended to illustrate the invention without limiting the scope as a result.

DYEING EXAMPLE The following dyeing composition was prepared: para-Phenylenediamine 0.2 g 2-Amino-4-N-(p-hydroxyethyl)aminoanisole 0.25 g dihydrochloride Laccase derived from Rhus vernicifera 1.8 g containing 180 units/mg sold by the company Sigma -(Cs-Cio)Alkyl polyglucoside in aqueous 8.0 g solution containing 60% of active substance (AS) sold under the name ORAMIX CG110® by the company SEPPIC Ethanol 20 g pH agent qs pH Demineralized water qs 100 g The ready-to-use dyeing composition described above was applied to locks of natural grey hair which is 90% white for 40 minutes, at a temperature of 30 0

C.

1 7he hair was then rinsed, and then dried.

The hair was dyed in a blue grey shade.

In the dyeing composition described above, Rhus vernicifera laccase at 180 units/mg, sold by the company Sigma can be replaced by 1.0 g of Pyricularia 5 orizae laccase at 100 units/mg sold by the company ICN.

Throughout this specification and the claims, the words "comprise", "comprises" and "comprising" are used in a non-exclusive sense".

0ioe o .0.-0 o..

Claims (27)

1. Ready-to-use composition for the oxidation dyeing of keratinous fibres, and in particular human keratinous fibres such as hair, characterized in that it comprises, in a medium appropriate for dyeing: at least one oxidation base,

2-amino-4-N- (-hydroxyethyl)aminoanisole and/or at least one of its addition salts with an acid as coupler, at least one enzyme of the laccase type. 2. Composition according to Claim 1, characterized in that the laccase is chosen from laccases of plant origin, animal origin, fungal origin or bacterial origin and from the laccases obtained by biotechnology.

3. Composition according to either of Claims 1 and 2, characterized in that the laccase is of plant origin and chosen from the laccases present in the extracts of Anacardiaceae, Podocarpaceae, Rosmarinus off., Solanum tuberosum, Iris sp., Coffea sp., Daucus carrota, Vinca minor, Persea americana, Catharenthus roseus, Musa sp., Malus pumila, Gingko biloba, Monotropa hypopithys (Indian pipe), Aesculus sp., Acer pseudoplatanus, Prunus persica and Pistacia palaestina. 23

4. Composition according to Claim 1 or 2, characterized in that the laccase is of fungal origin or obtained by biotechnology.

Composition according to Claim 4, characterized in that the laccase is chosen from the laccases derived from Polyporus versicolor, Rhizoctonia praticola, Rhus vernicifera, Scytalidium, Polyporus pinsitus, Myceliophtora thermophila, Rhizoctonia solani, Pyricularia orizae, Trametes versicolor, Fomes fomentarius, Chaetomium thermophile, Neurospora crassa, Colorius versicol, 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, Ceriporiopsis subvermispora, Coprinus cinereus, Panaeolus papilionaceus, Panaeolus sphinctrinus, Schizophyllum commune, Dichomitius squalens, and of variants thereof.

6. Composition according to any one of the preceding claims, characterized in that the quantity of laccase(s) is between 0.5 and 200 Lacu per 100 g of dyeing composition.

7. Composition according to any one of the preceding claims, characterized in that the oxidation base(s) are chosen from para-phenylenediamines, double f 24 bases, para-aminophenols, ortho-aminophenols and heterocyclic oxidation bases.

8. Composition according to Claim 7, characterized in that the para-phenylenediamines are chosen from the compounds of formula and their addition salts with an acid: NR 1 R 2 R 3 R, J (I) NH 2 in which: RI represents a hydrogen atom, a C 1 -C 4 alkyl radical, a monohydroxy(C 1 -C 4 alkyl) radical, a polyhydroxy- (C 2 -C 4 alkyl) radical, a (C 1 -C 4 )alkoxy(C 1 -C 4 )alkyl radical, a C 1 -C 4 alkyl radical substituted with a nitrogen-containing group, a phenyl radical or a 4'-aminophenyl radical; R 2 represents a hydrogen atom, a CI-C 4 alkyl radical, a monohydroxy(Ci-C 4 alkyl) radical, a polyhydroxy(C 2 -C 4 alkyl) radical, a (Cl-C 4 )alkoxy(C 1 -C 4 )alkyl radical or a C 1 -C 4 alkyl radical substituted with a nitrogen-containing group; R 3 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C 1 -C 4 alkyl radical, a monohydroxy(C 1 -C 4 alkyl) radical, a hydroxy(C 1 -C 4 alkoxy) radical, an acetylamino(Ci-C 4 alkoxy) radical, a mesylamino(Cl-C 4 alkoxy) radical or a carbamoyl amino (C C 4 alkoxy) radical, R 4 represents a hydrogen or halogen atom or a Cl-C 4 alkyl radical.

9. Composition according to Claim 8, characterized in that the para-phenylenediamines of formula are chosen from para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2, 3-dimethyl-para-phenylenediamine, 2, 6-dimethyl-para- phenylenediamine, 2, 6-diethyl-para-phenylenediamine, 2, 5-dimethyl-para-phenylenediamine, N,N-dimethyl-para- phenylenediamine, N, N-diethyl-para-phenylenediamine, NN-dipropyl-para-phenylenediamine, 4-amino-N,N- diethyl-3-methylaniline, N,N-bis (f-hydroxyethyl) -para- phenylenediamine, 4-N,N-bis (1-hydroxyethyl)amino-2- methylaniline, 4-N,N-bis (1-hydroxyethyl) amino-2- chloroaniline, 2-p-hydroxyethyl-para-phenylenediamine, 2-f luoro-para-phenylenediamine, 2-isopropyl-para- phenylenediamine, N- (P-hydroxypropyl) -para- phenylenediamine, 2-hydroxymethyl -para-phenylene- diamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N- (ethyl-13-hydroxyethyl) -para-phenylenediamine, N- (1,y-dihydroxypropyl) -para-phenylenediamine, N- aminophenyl) -para-phenylenediamine, N-phenyl-para- phenylenediamine, 2 -p-hydroxyethyloxy-para- phenylenediamine, 2-f-acetylaminoethyloxy-para- phenylenediamine, N- (J-methoxyethyl) -para- p 26 phenylenediamine, and their addition salts with an acid. Composition according to Claim 7, characterized in that the double bases are chosen from the compounds of formula and their addition salts with an acid: R R 7 Y (II) NRRio NR,,R, 1 j L in which: Zi and Z 2 which are identical or different, represent a hydroxyl or -NH 2 radical which may be substituted with a Ci-C 4 alkyl radical or with a linking arm Y; the linking arm Y represents a linear or branched alkylene chain comprising from 1 to 14 carbon atoms, which may be interrupted by or which may end with one or more nitrogen-containing groups and/or one or more heteroatoms such as oxygen, sulphur or nitrogen atoms, and optionally substituted with one or more hydroxyl or C 1 -C 6 alkoxy radicals; Rs and R 6 represent a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, a monohydroxy(C 1 -C 4 alkyl) radical, a polyhydroxy(C 2 -C 4 alkyl) radical, an amino(C 1 -C 4 alkyl) radical or a linking arm Y; R 7 R 8 Rs, R

10 R 11 and R 12 which are identical or different, represent a hydrogen atom, a linking arm Y or a C 1 -C 4 alkyl radical; it being understood that the compounds of formula (II) contain only one linking arm Y per molecule.

11. Composition according to Claim characterized in that the double bases of formula (II) are chosen from N,N'-bis(P-hydroxyethyl)-N,N'-bis(4'- aminophenyl)-1,3-diaminopropanol, N,N'-bis(p- hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'- bis(P-hydroxyethyl)-N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis(4- methylaminophenyl)tetramethylenediamine, N,N'- bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylene- diamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid.

12. Composition according to Claim 7, characterized in that the para-aminophenols are chosen from the compounds of formula (III), and their addition salts with an acid: OH I 11 1 SR14 NH 2 in which: R 13 represents a hydrogen or halogen atom, a C 1 -C 4 Salkyl, monohydroxy(C 1 -C 4 alkyl), (C 1 -C 4 )alkoxy(C 1 -C 4 I 28 alkyl, amino(C 1 -C 4 alkyl) or hydroxy(C 1 -C 4 )alkylamino- (C 1 -C 4 alkyl) radical, R 14 represents a hydrogen or halogen atom, a C 1 -C 4 alkyl, monohydroxy(C 1 -C 4 alkyl), polyhydroxy(C 2 -C 4 alkyl), amino(C 1 -C 4 alkyl), cyano(C 1 -C 4 alkyl) or (C 1 -C 4 )alkoxy(C 1 -C 4 )alkyl radical, it being understood that at least one of the radicals R 13 or R 14 represents a hydrogen atom.

13. Composition according to Claim 12, characterized in that the para-aminophenols of formula (III) are chosen from para-aminophenol, 4-amino-3- methylphenol, 4-amino-3-fluorophenol, 4-amino-3- hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-(P- hydroxyethylaminomethyl)phenol, 4-amino-2-fluoro- phenol, and their addition salts with an acid.

14. Composition according to Claim 7, characterized in that the ortho-aminophenols are chosen from 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6- methylphenol, 5-acetamido-2-aminophenol, and their addition salts with an acid.

Composition according to Claim 7, characterized in that the heterocyclic bases are chosen from pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives, and their addition salts with an acid. <-4S

16. Composition according to any one of the preceding claims, characterized in that the oxidation base(s) represent from 0.0005 to 12% by weight of the total weight of the dyeing composition.

17. Composition according to Claim 16, characterized in that the oxidation base(s) represent from 0.005 to 6% by weight of the total weight of the dyeing composition.

18. Composition according to any one of the preceding claims, characterized in that the 2-amino-4- N-(p-hydroxyethyl)aminoanisole and/or the or its addition salts with an acid represent from 0.0001 to 8% by weight of the total weight of the dyeing composition.

19. Composition according to Claim 18, characterized in that the 2-amino-4-N-(p-hydroxy- ethyl)aminoanisole and/or the or its addition salts with an acid represent from 0.005 to 5% by weight of the total weight of the dyeing composition.

20. Composition according to any one of the preceding claims, characterized in that it contains one or more other couplers different from 2-amino-4-N-(P- hydroxyethyl)aminoanisole and/or direct dyes.

21. Composition according to any one of the preceding claims, characterized in that the addition salts with an acid are chosen from hydrochlorides, hydrobromides, sulphates and tartrates, lactates and acetates. _L

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

23. Composition according to any one of the preceding claims, characterized in that it has a pH of between 4 and 11.

24. Method of dyeing keratinous fibres, and in particular human keratinous fibres such as hair, characterized in that at least one ready-to-use dyeing composition as defined in any one of the preceding claims is applied to the said fibres for a sufficient time to develop the desired colour.

Method according to Claim 24, characterized in that it comprises a preliminary step consisting in storing in a separate form, on the one hand, a composition comprising, in a medium appropriate for dyeing, at least one oxidation base and 2-amino-4-N-(P-hydroxyethyl)aminoanisole and/or at least one of its addition salts with an acid and, on the other hand, a composition containing, in a medium appropriate for dyeing, at least one enzyme of laccase [lacuna], and then in mixing them at the time of use before applying this mixture to the keratinous fibres.

26. Multicompartment device or dyeing "kit", characterized in that it comprises a first compartment containing the composition as defined in Claim 31 and a second compartment containing the composition as defined in Claim

27. Ready-to-use compositions or method of dyeing 5 keratinous fibres involving them, substantially as :I hereinbefore described with reference to the example. Dated this 30th day of August 2001 10 L'OREAL By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia o* H:\Leanne\Keep\18816-99.doc 29/08/01