AU730779B2 - Composition for the oxidation dyeing of keratin fibres and dyeing process using this composition - Google Patents

Abstract

The invention concerns an oxidation dyeing composition for keratinous fibres, and in particular human keratinous fibres such as hair comprising, in a suitable dyeing medium, at least an oxidation base, at least a 3-aminopyridine derivative as direct colouring agent, and at least a substituted meta-aminophenol as coupling agent, as well as a dyeing method using said composition.

Description

COMPOSITION FOR THE OXIDATION DYEING OF KERATIN FIBRES AND DYEING PROCESS USING THIS COMPOSITION The invention relates to a composition for the oxidation dyeing of keratin fibres, and in particular human keratin fibres such as the hair, comprising, in a medium which is suitable for dyeing, at least one oxidation base, at least one 3-aminopyridine derivative as direct dye, and at least one substituted meta-aminophenol as coupler, as well as to the dyeing process using this composition.

It is known practice to dye keratin fibres, and in particular human hair, with dye compositions containing oxidation dye precursors, in particular ortho- or para-phenylenediamines, ortho- or paraaminophenols and heterocyclic bases, which are generally referred to as oxidation bases. Oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds which, when combined with oxidizing products, can give rise to coloured compounds and dyes 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.

The variety of molecules used as regards the oxidation bases and couplers allows a wide range of colours to be obtained.

It is also known that, in order to vary the shades obtained even more and to give them glints, it is possible to use, in combination with the oxidation dye precursors and couplers, direct dyes, i.e. coloured substances which provide a coloration in the absence of an oxidizing agent.

The great majority of these direct dyes belong to the family of nitrobenzene compounds and have the drawback, when they are incorporated into dye compositions, of leading to colorations that are not sufficiently fast, in particular with respect to shampoos.

The so-called "permanent" coloration obtained by means of these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be able to give shades of the desired intensity and it must be able to withstand external agents (light, bad weather, washing, permanent-waving, perspiration and rubbing).

The dyes must also make it possible to cover white hair, and, finally, they must be as unselective as possible, i.e. they must give the smallest possible differences in colour all the way along the same keratin fibre, which may indeed be differently sensitized damaged) between its tip and its root.

Compositions for the oxidation dyeing of keratin fibres containing a combination of a benzenic oxidation base, a direct dye of the 3-aminopyridine family and an unsubstituted meta-aminophenol as coupler have already been proposed, in particular in patent application FR-A-2,285,851. However, the colorations obtained using such compositions are not entirely satisfactory, in particular from the point of view of their chromaticity and their fastness.

The Applicant has now discovered that it is possible to obtain novel dyes which are capable of giving intense and chromatic colorations, which show little selectivity and which satisfactorily withstand the various attacking factors to which the fibres may be subjected, by combining at least one oxidation base, at least one suitably selected 3-aminopyridine derivative as direct dye, and at least one suitably selected meta-aminophenol derivative.

This discovery forms the basis of the present invention.

A first subject of the invention is thus a composition for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, characterized in that it comprises, in a medium which is suitable for dyeing: at least one oxidation base, as direct dye, at least one 3-aminopyridine derivative chosen from the compounds of formula (I) below: R2 N=N A (I) R B R4 R, in which: B represents a group of formula (Ia) or (Ib) below: I I X (Ib) 0-

R

R represents a CI-C 4 alkyl radical; RI represents a hydrogen or halogen atom such as chlorine, bromine or fluorine, or a Ci-C 4 alkyl or

C

1

-C

4 alkoxy radical;

R

2 represents a hydrogen atom or a Ci-C 4 alkyl or Ci-C 4 alkoxy radical;

R

4 represents a hydrogen or halogen atom such as chlorine, bromine or fluorine, or a Ci-C 4 alkyl, nitro, amino or (C 1

-C

4 )acylamino radical;

R

3 represents a hydrogen atom or else R 4 and R 3 together form a 6-membered unsaturated ring bearing a hydroxyl substituent chelated with one of the nitrogen atoms of the azo double bond; A represents a residue -NRsR 6 in which R 5 represents a hydrogen atom or a C 1

-C

4 alkyl, CI-C 4 monohydroxyalkyl or C 2

-C

4 polyhydroxyalkyl radical; R 6 represents a hydrogen atom, a C 1

-C

4 alkyl, Ci-C 4 monohydroxyalkyl or

C

2

-C

4 polyhydroxyalkyl radical, a phenyl ring or a

-CH

2

-SO

3 Na radical; X represents a monovalent or divalent anion and is preferably chosen from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogen sulphate or a (C 1

-C

6 )alkyl sulphate such as, for example, a methyl sulphate or an ethyl sulphate, and at least one coupler chosen from the meta-aminophenol derivatives of formula (II) below, and the addition salts thereof with an acid:

OH

R

J R')

NHR,

R,

in which:

R

7 represents a hydrogen atom or a C 1

-C

4 alkyl, C 1

-C

4 monohydroxyalkyl, C 2

-C

4 polyhydroxyalkyl or C 1

-C

4 monoaminoalkyl radical;

R

8 represents a hydrogen atom, a C 1

-C

4 alkyl or C 1

-C

4 alkoxy radical or a halogen atom chosen from chlorine, bromine and fluorine,

R

9 and R' 9 which may be identical or different, represent a hydrogen or halogen atom or a C 1

-C

4 alkyl,

C

1

-C

4 alkoxy, Ci-C 4 monohydroxyalkyl, C 2

-C

4 polyhydroxyalkyl, Ci-C 4 monohydroxyalkoxy or C 2

-C

4 polyhydroxyalkoxy radical; it being understood that at least one of the radicals

R

7

R

8

R

9 and R' 9 is other than a hydrogen atom.

The dye composition in accordance with the invention gives intense, chromatic colorations which show little selectivity and excellent properties of resistance both with respect to atmospheric agents such as light and bad weather, and with respect to perspiration and the various treatments to which the hair may be subjected. These properties are particularly noteworthy as regards the chromaticity.

A subject of the invention is also a process for the oxidation dyeing of keratin fibres using this dye composition.

The nature of the oxidation base(s) used in the ready-to-use dye composition is not critical. They can 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 dye compositions in accordance with the invention, mention may be made in particular of the compounds of formula (III) below, and the addition salts thereof with an acid: N R, 0R,

NR

10

R

11 rR 1 2

R

13

NH

z in which:

R

0 o represents a hydrogen atom or a C 1

-C

4 alkyl radical, C 1

-C

4 monohydroxyalkyl radical, C 2

-C

4 polyhydroxyalkyl radical, (C 1

-C

4 )alkoxy(C 1

-C

4 )alkyl radical, Ci-C 4 alkyl radical substituted with a nitrogenous group, phenyl or 4'-aminophenyl;

R

11 represents a hydrogen atom or a C 1

-C

4 alkyl radical, Ci-C 4 monohydroxyalkyl radical, C 2

-C

4 polyhydroxyalkyl radical, (C 1

-C

4 )alkoxy(C 1

-C

4 )alkyl radical or Ci-C 4 alkyl radical substituted with a nitrogenous group;

R

12 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, or a Ci-C 4 alkyl radical, C 1

-C

4 monohydroxyalkyl radical,

C

1

-C

4 hydroxyalkoxy radical, acetylamino(C 1

-C

4 )alkoxy, mesylamino (C 1

-C

4 alkoxy or carbamoylamino(C 1

-C

4 alkoxy radical,

R

13 represents a hydrogen or halogen atom or a Ci-C 4 alkyl radical.

Among the nitrogenous groups of formula (III) above, mention may be made in particular of amino, mono(C 1

-C

4 )alkylamino, di (C-C 4 )alkylamino, tri (Cl-C 4 alkylamino, monohydroxy (C C 4 alkyl amino, imidazolinium and ammonium radicals.

Among the para-phenylenediamines of formula (III) above, mention may be made more particularly of para-phenylenediamine, para-tolylenediamine, 2 -chloropara-phenylenediamine, 2, 3-dimethyl-paraphenylenediamine, 2, 6-dimethyl -para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 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 (P-hydroxyethyl) -para-phenylenediamine, 4-N,Nbis (P-hydroxyethyl) amino-2-methylaniline, 4-N,N-bis hydroxyethyl) amino-2-chloroaniiine, 2-p-hydroxyethylpara-phenylenediamine, 2-f luoro-para-phenylenediamine, 2 -isopropyl-para-phenylenediamine, N- (P-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-paraphenylenediamine, N,N-dimethyl-3-methyl-paraphenylenediamine, N-ethyl-N- (1-hydroxyethyl) -paraphenylenediamine, N- (f,y-dihydroxypropyl) -paraphenylenediamine, N- -aminophenyl) -paraphenylenediamine, N-phenyl -para-phenylenediamine, 24hydroxyethyloxy-para-phenylenediamine, 2acetylaminoethyloxy-para-phenylenediamine and N- (Imethoxyethyl)-para-phenylenediamine, and the addition salts thereof with an acid.

Among the para-phenylenediamines of formula (III) above, the ones most particularly preferred are para-phenylenediamine, para-tolylenediamine, 2 -isopropyl -para-phenylenediamine, 2 -p-hydroxyethyl= para-phenylenediamine, 2 -f-hydroxyethyloxy-paraphenylenediamine, 2, G-dimethyl-para-phenylenediamine, 2 ,6-diethyl-para-phenylenediamine, 2,3-dimethyl-paraphenylenediamine, N,N-bis (f-hydroxyethvl) -paraphenylenediamine, 2 -chioro-para-phenylenediamine and 2-p-acetyaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid.

According to the invention, the term "double bases" means compounds comprising at least two aromatic nuclei on which amino and/or hydroxyl groups are borne.

0 Among the double bases which can be used as S...oxidation bases in the dyie compositions in accordance a0 0 06* 15 with the invention, mention may be made in particular of the compounds corresponding to the formula (IV) below, and the addition salts thereof with an acid: 0 z 2 1-4 Y

(IV)

a* *a 0 0:0 in which: 0 Z, and Z 2 which may be identical or different, represent a hydroxyl or -NH{ 2 radical which can be substituted with a CI-C 4 alkyl radical or with a linker arm y; the linker arm Y represents a linear or branched alkylene chain comprising from 1 to 14 carbon atoms, which can be interrupted or terminated with one or more nitrogenous groups and/or with one or more hetero atoms such as oxygen, sulphur or nitrogen atoms, and optionally substituted with one or more hydroxyl or Ci-C 6 alkoxy radicals;

R

14 and R 15 represent a hydrogen or halogen atom, a

C

1

-C

4 alkyl radical, Ci-C 4 monohydroxyalkyl radical,

C

2

-C

4 polyhydroxyalkyl radical or Ci-C 4 aminoalkyl radical or a linker arm Y;

R

16

R

17

R

18

R

19

R

20 and R 21 which may be identical or different, represent a hydrogen atom, a linker arm Y or a C 1

-C

4 alkyl radical; it being understood that the compounds of formula (IV) comprise only one linker arm Y per molecule.

Among the nitrogenous groups of formula (IV) above, mention may be made in particular of amino, mono(C 1

-C

4 )alkylamino, di (C 1

-C

4 )alkylamino, tri (C 1

-C

4 )alkylamino, monohydroxy(C 1

-C

4 )alkylamino, imidazolinium and ammonium radicals.

Among the double bases of formula (IV) above, mention may be made more particularly of N,N'-bis(Phydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3diaminopropanol, N,N'-bis(f-hydroxyethyl)-N,N'-bis(4'aminophenyl)ethylenediamine, N,N'-bis(4aminophenyl)tetramethylenediamine, N,N'-bis(p- IN hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4methylaminophenyl)tetramethylenediamine,

N,N'-

bis(ethyl)-N,N'-bis(4'-amino-3'methylphenyl)ethylenediamine and 1,8-bis(2,5diaminophenoxy)-3,5-dioxaoctane, and the addition salts thereof with an acid.

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

Among the para-aminophenols which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made in particular of the compounds of formula below, and the addition salts thereof with an acid:

OH

NH

2 in which:

R

22 represents a hydrogen or halogen atom or a CI-C 4 alkyl, C 1

-C

4 monohydroxyalkyl,

(C

1

-C

4 )alkoxy(C 1

-C

4 )alkyl, C 1

-C

4 aminoalkyl or hydroxy(C 1

-C

4 )alkylamino(C 1

-C

4 )alkyl radical,

R

23 represents a hydrogen or halogen atom or a CI-C 4 alkyl, Ci-C 4 monohydroxyalkyl,

C

2

-C

4 polyhydroxyalkyl,

C

1

-C

4 aminoalkyl, 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

22 and R 23 represents a hydrogen atom.

Among the para-aminophenols of formula (V) above, mention may be made more particularly of 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, 4amino-2-(p-hydroxyethylaminomethyl)phenol and 4-amino- 2-fluorophenol, and the addition salts thereof with an acid.

Among the ortho-aminophenols which can be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made more particularly of 2-aminophenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.

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

Among the pyridine derivatives, mention may be made more particularly of the compounds described, for example, in GB patents 1,026,978 and 1,153,196, such as 2-5-diaminopyridine, 2- (4-rethoxyphenyl) amino- 3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2- (fmethoxyethyl) amino-3-amino-6-methoxypyridine and 3,4diaminopyridine, and the addition salts thereof 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 patents JP 88-169,.571 and JP 91-333,495 or patent applications WO 96/15765, such as 2,4,5,6tetraaminopyrimidine, 4-hydroxy-2, 5,6triaminopyrimidine, 2-hydroxy-4 6-triaminopyrimidine, 2 ,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6traminopyrimidine, and pyrazolopyrimidine derivatives, such as those mentioned in patent application FR-A-2,750,048 and among which mention may be made of pyrazolo[l,5-alpyrimidine-3,7-diamine; dimethylpyrazoloil, 5-alpyrimidine-3,7-diamine; pyrazolo[1,5-alpyrimidine-3,5-diamine; 2,7dimethylpyrazolo[l, 5-alpyrimidine-3,5-diamine; 3aminopyrazoloEl, 5-allpyrimidin-7-ol; 3aminopyrazolo[1,5-alpyrimidin-5-ol; 2-(3aminopyrazololl,-apyrimidin7ylamino)ethanol, 2- (7aminopyrazolo [1,5-alpyrirnidin-3-ylamino)ethanol, 2- \\aminopyrazoloI1,5apyrimidin7yl) hydroxyethyl) amino] ethanol, 2- [(7-aminopyrazolo alpyrimidin-3-yl) -(2-hydroxyethyl) aminolethanol, 5,6dimethylpyrazolo[1,5-alpyrimidine-3,7-diamine, 2,6dimethylpyrazolo 5-alpyrimidine-3,7-diamine and

N

7

,N

7 -tetramethylpyrazolo[1,5-alpyrimidine-3,7-diamine, and the addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists, and the addition salts thereof with an acid.

Among the pyrazole derivatives, mention may be made more particularly of the compounds described in patents DE 3,843,892 and 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 methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-l- chlorobenzyl)pyrazole, 4,5-diamino-l,3dimethylpyrazole, 4,5-diamino-3-methyl-lphenylpyrazole, 4, 5-diamino-1-methyl-3-phenylpyrazole, 4 -amino-i,3-dimethyl-5-hydrazinopyrazole, diamino-3-methylpyrazole, 4, 5-diamino-3-tert-butyl-lmethylpyrazole, 4,5-diamino-1-tert-butyl-3methylpyrazole, 4,5-diamino-l- (f-hydroxyethyl) -3methylpyrazole, 4, 5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3- -methoxyphenyl)pyrazole, diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3hydroxymethyl-l-methylpyrazole, 4,5-diamino-3hydroxymethyl-l-isopropylpyrazole, 4, 5-diamino-3methyl-l-isopropylpyrazole, 4-amino-5- aminoethyl) amino-i, 3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5triaminopyrazole, 3,5-diamino-l-methyl-4methylaminopyrazole and 3,5-diamino-4-(3hydroxyethyl)amino-1-methylpyrazole, and the addition salts thereof with an acid.

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

The 3-aminopyridine derivative(s) of formula in accordance with the invention is (are) preferably chosen from: 4'-dimethylaminobenzene-1'-azo-l-methyl-3-pyridinium methosulphate of formula: CH3

CH

3 CH 3

SO

4

N

I

CH

3 4'-bis(p-hydroxyethyl)aminobenzene-1'-azo-l-methyl-3pyridinium methosulphate of formula:

CH

2

CH

2

OH

NN.

CH

2

CH

2 0H

CH

3

SO

4 N. N

I-

CH 3 -4'-amino-B' -hydroxynaphthalene-i' -azo-l-methyl-3pyridinium methosuiphate of formula: KJN.I CH 3 S0 4 N HO

O

3 5-4' -dimethylamino-2'-nitrobenzene-1' -azo-l-methyl-3pyridinium methosuiphate of formula: I -C3 ,CH 3

SO

4

N"

N2

UNH

3 -dimethylaminobenzene-1' -azo-1,6-dimethyl-3pyridinium methosuiphate of formula: CH3

~CH

3 CH 3 S0 4

H

3 C N'

CH

3 4'-aminobenzenle-1'-azo-3-pyridiLne N-oxide of formula: 4' -dimethylaminobenzene-l' -azo-3-pyridine N-oxide of formula: 41 -N,N-bis(fbhydroxyethyl)aminobenzeie-1' -azo-3pyridine N-oxide of formula: 4' -dimethylamino-2' -methylbenzene-l' -azo-1-ethyl-3pyridinium ethosuiphate of formula: ,c 2

H

5 so 4 -dimethylamino-2' -methylbenzeie-1' -azo-1-butyl-3pyridinium bromide of formula:

CH

3

~CH

3 ,Br'

OH

3

N

CAH

-dimethylamino-2' -chlorobenzene-i' -azo-l-methyl-3pyridinium methosuiphate of formula: k3, CH- SO

N

CH 3 ,4'-diamino-5' -methylbenzene-1' -azo-l-methyl-3pyridinium methosuiphate of formula:

CH

3 ri y NH 2 CH 3 S0 4 4' -phenylaminobenzene-1' -azo-1-methyl-3-pyridinium methosuiphate of formula:

,CH

3

SO

4 2' -acetylamino-4' -dimethylaminobenzene-l' -azo-lethyl-3-pyridinium ethosuiphate of formula:

C

2

H

5 S0 4 2' ,4'-diamino-5' -methoxybenzene-1'-azo-l-methyl-3pyridinium methosuiphate of formula:

OCH

3

NH

2 Y CH 3 S0 4 and -amino-4' -dimethylaminobenzene-1' -azo-l-methyl-3pyridinium methosuiphate of formula:

CH

3

CH

3 ,CH 3 S0 4

N

N~

NH

2

CH

3 The 3-aminopyridine derivative(s) of formula 0O used according to the invention preferably represent(s) from 0.001 to 10% by weight approximately relative to the total weight of the dye composition, and even more preferably from 0.01 to 5% by weight approximately relative to this weight.

Among the meta-aminophenols of formula (II) above, mention may be made more particularly of amino-2-methoxyphenol, 5-amino-2-(phydroxyethyloxy)phenol, 5-amino-2-methylphenol, 5-N-(3hydroxyethyl)amino-2-methylphenol, hydroxyethyl)amino-4-methoxy-2-methylphenol, 5-amino-4methoxy-2-methylphenol, 5-amino-4-chloro-2methylphenol, 5-amino-2,4-dimethoxyphenol, hydroxypropylamino)-2-methylphenol, 3-amino-2-chloro-6methylphenol, 3-amino-6-chlorophenol and 3-(Paminoethyl)amino-6-chlorophenol, and the addition salts thereof with an acid.

The meta-aminophenol derivative(s) of formula (II) in accordance with the invention preferably represent(s) from 0.0001 to 10% by weight approximately relative to the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately relative to this weight.

The dye composition in accordance with the invention can also contain one or more couplers other than the meta-aminophenol derivatives of formula (II) and/or one or more direct dyes other than the 3-aminopyridine derivatives of formula in particular to modify the shades or to enrich them with glints.

Among the couplers which may also be present in the dye composition in accordance with the invention, mention may be made in particular of metaphenylenediamines, meta-diphenols and heterocyclic couplers, and the addition salts thereof with an acid.

When they are present, these additional couplers preferably represent from 0.0001 to 10% by weight approximately relative to the total weight of the dye composition and even more preferably from 0.005 to 5% by weight approximately relative to this weight.

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

The medium which is suitable for dyeing (or support) for the dye composition in accordance with the invention generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in water. Organic solvents which may be mentioned, for example, are C 1

-C

4 alkanols, such as ethanol and isopropanol.

The solvents can be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The pH of the dye composition in accordance with the invention is generally between 3 and 12 approximately, and preferably between 5 and 12 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratin fibres.

Among the acidifying agents which may be mentioned, for example, are inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or lactic acid, and sulphonic acids.

Among the basifying agents which may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine, 2-methyl-2-aminopropanol and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (VI) below:

/R

26 N-W-N (VI) 7 in which W is a propylene residue optionally substituted with a hydroxyl group or a Cz-C 4 alkyl radical; R 24

R

2 s, R 26 and R 27 which may be identical or different, represent a hydrogen atom or a Cl-C 4 alkyl or Cl-C 4 hydroxyalkyl radical.

The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair.

Needless to say, a person skilled in the art will take care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the dye composition in accordance with the invention are not, or are not substantially, adversely affected by the addition or additions envisaged.

The dye composition in accordance with the invention can be in various forms, such as in the form of liquids, creams or gels, which are optionally pressurized, or in any other form which is suitable for dyeing keratin fibres, and in particular human hair.

A subject of the invention is also a process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, using the dye composition as defined above.

According to this process, the dye composition as defined above is applied to the fibres, the colour being developed at acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added to the dye composition only at the time of use, or which is present in an oxidizing composition that is applied simultaneously or sequentially in a separate manner.

According to a particularly preferred embodiment of the dyeing process according to the invention, the dye composition described above is mixed, at the time of use, with an oxidizing composition containing, in a medium which is suitable for dyeing, at least one oxidizing agent present in an amount which is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres and is left on them for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which the fibres are rinsed, washed with shampoo, rinsed again and dried.

The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibres, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates, percarbonates and persulphates, peracids, enzymes such as 2-electron oxidoreductases, peroxidases and lactases. Hydrogen peroxide is particularly preferred.

The pH of the oxidizing composition containing the oxidizing agent as defined above is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibres preferably ranges between 3 and 12 approximately and even more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratin fibres and are as defined above.

The oxidizing composition as defined above can also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.

The composition which is finally applied to the keratin fibres can be in various forms, such as in the form of liquids, creams or gels or in any other form which is suitable for dyeing keratin fibres, and in particular human hair.

Another subject of the invention is a multicompartment dyeing device or multi-compartment dyeing "kit", or any other multi-compartment packaging system, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition as defined above. These devices may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR-2,586,913 in the name of the Applicant.

The examples which follow are intended to illustrate the invention without thereby limiting its scope.

EXAMPLES

COMPARATIVE DYEING EXAMPLES 1 TO 4 The dye compositions below were prepared (contents in grams): EXAMPLE 1 3 4' -Dimethylaminobenzene-1'- 0.5 0.5 azo- 3-pyridine N-oxide (compound of formula MI) 2'-Acetylamino-4'-dimethyl- 0.6 0.6 aminobenzene-1' -azo-l-ethyl- 3 -pyridinium ethosuiphate (compound of formula para--Phenylenediamine 0.324 0.324 0.324 0.324 (oxidation base) 5-Amino-2-methylphenol 0.369 0.369 (coupler of formula meta-Aminophenol (coupler) 0.327 0.327 Common dye support Demineralized water qs 100 g ,100 g ,100 g 100 g Comparative example not forming part of the invent ion Common dye support: -Oleyl alcohol polyglycerolated with 2 mol of glycerol -Oleyl alcohol polyglycerolated with 4 mol of glycerol, containing 78% active material -Oleic acid -Oleylamine containing 2 mol of ethylene oxide, sold under the trade name Ethomeen 012® by the company Akzo -Diethylaminopropyl laurylaminosuccinamate, sodium salt, containing 55% A.M.

-Oleyl alcohol -Oleic acid diethanolamide -Propylene glycol -Ethyl alcohol -Dipropylene glycol -Propylene glycol monomethyl ether -Sodium metabisulphite as an aqueous solution containing 35% A.M.

-Ammonium acetate -Antioxidant, sequestering agent -Fragrance, preserving agent -Aqueous ammonia containing 20% NH 3 4.0 g 5.69 g A.M.

3.0 g 7.0 g 3.0 5.0 12.0 3.5 7.0 0.5 9.0 0.455 0.8 qs qs 10.0 g A.M.

g g g g g g g A.M.

g g Each of the dye compositions described above was mixed, at the time of use, with an equivalent weight-amount of 20-volumes hydrogen peroxide by weight) having a pH of about 3.

Each resulting mixture had a pH of about 10+0.2 and was applied for 30 minutes to locks of permanent-waved grey hair containing 90% white hairs.

The hair was then rinsed with water, washed with a standard shampoo, rinsed again and then dried.

The colour of the locks was evaluated before and after dyeing, in the Munsell system, using a Minolta CM 20020 spectrophotometer.

According to the Munsell notation, a colour is defined by the formula: HV C in which the three parameters denote, respectively, the "Hue" or shade the "Value" or intensity and the "Chroma" or saturation the oblique line simply being a convention and not denoting a ratio.

The increase in the coloration AE can be calculated by applying the Nickerson equation: AE 0.4CodH 6dV 3dC as described, for example, in "Journal of the Optical Society of America", vol. 34, No. 9, Sept 1944, pages 550-570.

In this equation, AE represents the difference in colour between two locks (in the present case the increase in the coloration), dH, dV and dC represent the variation in absolute value of the three parameters H, V and C, Co representing the saturation of the lock relative to which it is desired to evaluate the difference in colour.

The greater the value of AE, the greater the difference in colour between the two locks, and, in the present case, the greater the increase in the coloration (or intensity of the coloration).

The results are given in the table below: Example Colour of the Colour of Increase in lock the lock coloration before dyeing after dyeing dH dV dC AE 1 3.3 Y 5.8/1.6 6.5 R 2..7/3.8 16.8 3.1 2.2 36.0 3.3 Y 5.8/1.6 1.2 YR 2.4/2.1 12.1 3.4 0.5 29.6 3 3.3 Y 5.8/1.6 5.1 R 2.5/3.0 18.2 3.3 1.4 35.6 3.3 Y 5.8/1.6 8.7 R 2.2/1.5 14.6 3.6 0.1 31.2 Comparative example not forming part of the invention It is found that the dye compositions of Examples 1 and 3 in accordance with the invention, i.e.

compositions containing a combination of a direct dye of formula an oxidation base and a coupler of formula lead to more intense colorations than the 0 dye compositions of Examples 2 and 4 not forming part of the invention since they Contain an unsubstituted coupler of meta-aminophenol type and as described, for example, in patent application FR-A-2.285,851.

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

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Claims (12)

1. Composition for the oxidation dyeing of keratin fibres, and in particular of human keratin fibres such as the hair, characterized in that it comprises, in a medium which is suitable for dyeing: at least one oxidation base, as direct dye, at least one 3-aminopyridine derivative chosen from the compounds of formula (I) below: R 2 N=N A (I) RR R RI B R4 F in which: B represents a group of formula (Ia) or (Ib) below: I (la) I X (Ib) 0 R R represents a C 1 -C 4 alkyl radical; R 1 represents a hydrogen or halogen atom such as chlorine, bromine or fluorine, or a C 1 -C 4 alkyl or Cz-C 4 alkoxy radical; R 2 represents a hydrogen atom or a C 1 -C 4 alkyl or Ci-C 4 alkoxy radical; R 4 represents a hydrogen or halogen atom such as chlorine, bromine or fluorine, or a CI-C 4 alkyl, nitro, amino or (C 1 -C 4 )acylamino radical; R 3 represents a hydrogen atom or else R 4 and R 3 together form a 6-membered unsaturated ring bearing a hydroxyl substituent chelated with one of the nitrogen atoms of the azo double bond; A represents a residue -NRsR 6 in which Rs represents a hydrogen atom or a Ci-C 4 alkyl, Ci-C 4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl radical; Rg represents a hydrogen atom, a C 1 -C 4 alkyl, Ci-C 4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl radical, a phenyl ring or a -CH 2 -SO 3 Na radical; X- represents a monovalent or divalent anion and is preferably chosen from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogen sulphate or a (C 1 -C 6 )alkyl sulphate such as, for example, a methyl sulphate or an ethyl sulphate, and at least one coupler chosen from the meta-aminophenol derivatives of formula (II) below, and the addition salts thereof with an acid: OH R9 R', (II) NHR, R8 in which: R 7 represents a hydrogen atom or a Cz-C 4 alkyl, C 1 -C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl or C 1 -C 4 monoaminoalkyl radical; Re represents a hydrogen atom, a C 1 -C 4 alkyl or C 1 -C 4 alkoxy radical or a halogen atom chosen from chlorine, bromine and fluorine, R 9 and R' 9 which may be identical or different, represent a hydrogen or halogen atom or a Cz-C 4 alkyl, C 1 -C 4 alkoxy, Cz-C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, Cz-C 4 monohydroxyalkoxy or C 2 -C 4 polyhydroxyalkoxy radical; it being understood that at least one of the radicals R 7 R 8 R 9 and R' 9 is other than a hydrogen atom.

2. Composition according to Claim 1, characterized in that the oxidation base(s) is (are) chosen from para-phenylenediamines, double bases, para- aminophenols, ortho-aminophenols and heterocyclic oxidation bases.

3. Composition according to Claim 2, characterized in that the para-phenylenediamines are chosen from the compounds of formula (III) below, and the addition salts thereof with an acid: NRioR R12 R (111) 13 (III) NH, in which: R 10 represents a hydrogen atom or a Ci-C 4 alkyl radical, Ci-C 4 monohydroxyalkyl radical, C 2 -C 4 polyhydroxyalkyl radical, (Ci-C 4 alkoxy(C 1 -C 4 alkyl radical, Ci-C 4 alkyl radical substituted with a nitrogenous group, phenyl or 4'-aminophenyl; R 11 represents a hydrogen atom or a Ci-C 4 alkyl radical, Ci-C 4 monohydroxyalkyl radical, C 2 -C 4 polyhydroxyalkyl radical, (C 1 -C 4 alkoxy(Ci-C 4 alkyl radical or Ci-C 4 alkyl radical substituted with a nitrogenous group; R 1 2 represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, or a C 1 -C 4 alkyl radical, Ci-C 4 monohydroxyalkyl radical, Ci-C 4 hydroxyalkoxy radical, acetylamino(Ci-C 4 alkoxy, mesylamino(Ci-C 4 )alkoxy or carbamoylamino(C 1 -C 4 alkoxy radical, R 13 represents a hydrogen or halogen atom or a Ci-C 4 alkyl radical.

4. Composition according to Claim 3, characterized in that the para-phenylenediamines of formula (III) 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, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N- diethyl-3-methylaniline, N,N-bis (P-hydroxyethyl)-para- phenylenediamine, 4-N,N-bis(13-hydroxyethyl)amino-2- methylaniline, 4-N,N-bis(P3-hydroxyethyl) amino-2- chloroaniline, 2- 3 -hydroxyethyl-para-phenylenediamine, 2 -fluoro-para-phenylenediamine, 2-isopropyl-para- phenylenediamine, N- (1-hydroxypropyl) -para- phenylenedianine, 2 -hydroxymethyl -para- phenylenediamine, N, N-dimethyl-3-methyl-para- phenylenediamine, N-ethyl-N- (f-hydroxyethyl) -para- pheriylenediamine, N- (1 3 y-dihydroxypropyl) -para- phenvlenediamine, N-(4'-aminovhenyl) -para- phenylenediamine, N-pheriyl -para-phenylenediamine,- 2 -1-hydroxyethyloxy-para-phenylened iamine, C 2-1-acetylaminoethyloxy-para.-phenylenediamine and N- (P- C methoxyethyl) -para-phenylenediamine, and the addition salts thereof with an acid. S. Composition according to Claim 2, characterized in that the double bases are chosen from the compounds of formula (IV) below, and the addition salts thereof with an acid:

17.' R1 (IV) N 1 9 NR-QR 21 in which: and Z 2 which may be identical or different, P RA4/represent a hydroxyl or -NH 2 radical which can be substituted with a C 1 -C 4 alkyl radical or with a linker arm Y; the linker arm Y represents a linear or branched alkylene chain comprising from 1 to 14 carbon atoms, which can be interrupted or terminated with one or more nitrogenous groups and/or with one or more hetero atoms such as oxygen, sulphur or nitrogen atoms, and optionally substituted with one or more hydroxyl or Ci-C6 alkoxy radicals; R 14 and R 15 represent a hydrogen or halogen atom, a C 1 -C 4 alkyl radical, C 1 -C 4 monohydroxyalkyl radical, C 2 -C 4 polyhydroxyalkyl radical or Ci-C 4 aminoalkyl radical or a linker arm Y; R 1 6 R1 7 R 1 8 R 1 9 R 2 0 and R 2 1 which may be identical or different, represent a hydrogen atom, a linker arm Y or a C 1 -C 4 alkyl radical; it being understood that the compounds of formula (IV) comprise only one linker arm Y per molecule. 6. Composition according to Claim characterized in that the double bases of formula (IV) 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'- N bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine and 1,8-bis(2,5- and the addition salts thereof with an acid. 7. Composition according to Claim 2, characterized in that para-aminophenols are chosen from the compounds of formula below, and the addition salts thereof with an acid: OH (V) 1 v NH 2 in which: R 22 represents a hydrogen or halogen atom or a C 1 -C 4 alkyl, C 1 -C 4 monohydroxyalkyl, (Cl-C 4 )alkoxy(C 1 -C 4 )alkyl, C 1 -C 4 aminoalkyl or hydroxy(C 1 -C 4 alkylamino (C 1 -C 4 alkyl radical, R 23 represents a hydrogen or halogen atom or a CI-C 4 alkyl, CI-C 4 monohydroxyalkyl, C 2 -C 4 polyhydroxyalkyl, C 1 -C 4 aminoalkyl, 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 22 and R 23 represents a hydrogen atom. 8. Composition according to Claim 7, characterized in that the para-aminophenols of formula 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 and 4-amino-2- fluorophenol, and the addition salts thereof with an acid. 9. Composition according to Claim 2, characterized in that the ortho-aminophenols are chosen from 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6- methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid. 10. Composition according to Claim 2, characterized in that the heterocyclic oxidation bases are chosen from pyridine derivatives, pyrimidine derivatives and pyrazole derivatives, and the addition salts thereof with an acid. 11. Composition according to any one of the preceding claims, characterized in that the oxidation base(s) represent(s) from 0.0005 to 12% by weight relative to the total weight of the dye composition. 12. Composition according to Claim 11, characterized in that the oxidation base(s) represent(s) from 0.005 to 6% by weight relative to the total weight of the dye composition. 13. Composition according to any one of the preceding claims, characterized in that the 3- aminopyridine derivative(s) of formula is (are) chosen from: 4'-dimethylaminobenzene-1'-azo-1-methyl-3-pyridinium methosulphate of formula: CH 3 CH 3 ,CH 3 S0 4 N N CH 3 -bis(f-hydroxyethyl)arinobenzene-' -azo-l-methyl-3- pyridinium. methosuiphate of formula: CH 2 CH 2 0H 'CHCHOH CH3SO4 4' -amino-B' -hydroxynaphthalene-l' -azo-1-methyl-3- pyridinium methosuiphate of formula: ,CH 3 S0 4 N HO CH 3 4' -dimethylamino-2' -nitrobenzene-l' -azo-l-methyl-3- pyridinium methosuiphate of formula: CH CH 3 CH 3 S0 4 N CH 3 -dimethylamiriobenzene-l' -azo-l,6-dimethyl-3- pyridirijum methosuiphate of formula: CH 3 N ~CH 3 CH 3 SO 4 4'-amirlobenzene-1'-azo-3-pyridine N-oxide of formula: NNH 2 N N N 4' -dimethylaminobenzene-i' -azo-3-pyridine N-oxide of formula: CH 3 CH 3 -N,N-bislj3-hydroxyethyl)aminobenzeie-1'-azo-3- pyridine N-oxide of formula: -dimethylamino-2' -methylbenzene-1' -azo-1-ethyl-3- pyridirijum ethosuiphate of formula: OH 3 CH 3 ,C 2 HSS0 4 Nip C 2 HH3 -dimethylamino-2' -methylbenzeie-1' -azo-1-butyl-3- pyridinium bromide of formula: ic N N+ CH 3 4' -dimethylamino-2' -chlorobenzene-l' -azo-l-methyl-3- pyridinium methosuiphate of formula: CH OH 3 CH 3 so 4 2' 14' -diamino-5' -methylberizene-1' -azo-1-methyl-3- pyridinium methosuiphate of formula: CH- 3 NH 2 rll~r CH 3 S0 4 4' -phenylaminobenzene-1' -azo-1-methyl-3-pyridinium methosuiphate of formula: CH 3 S0 4 -acetylamino-4' -dimethylaminobexzene-l' -azo-1- ethyl-3-pyridiriium ethosuiphate of formula: CH 3 N H3 C C 2 H 5 S0 4 N~ NHCOCH 3 -2'1,4'-diamino-5' -methoxybenzene-l' -azo-l-methyl-3- pyridirijum methosuiphate of formula: OCH 3 NH CH3 3 O arnd -amino-4' -dimethylaminobeizene-1' -azo-l-methyl-3- pyridinium methosuiphate of formula: CH 3 3 cH3, CHzSO 4 NH2 N 2 N CH 3 14. Composition according to any one of the preceding claims, characterized in that the 3-amino- pyridine derivative(s) of formula represent(s) from 0.001 to 10% by weight relative to the total weight of the dye composition. Composition according to Claim 14, characterized in that the 3-aminopyridine derivative(s) of formula represent(s) from 0.01 to 5% by weight relative to the total weight of the dye composition. 16. Composition according to any one of the preceding claims, characterized in that the meta- aminophenol derivatives of formula (II) are chosen from 5-amino-2-methoxyphenol, 5-amino-2-(P- hydroxyethyloxy)phenol, 5-amino-2-methylphenol, hydroxyethyl)amino-2-methylphenol, hydroxyethyl)amino-4-methoxy-2-methylphenol, 5-amino-4- methoxy-2-methylphenol, 5-amino-4-chloro-2- methylphenol, 5-amino-2,4-dimethoxyphenol, hydroxypropylamino)-2-methylphenol, 3-amino-2-chloro-6- methylphenol, 3-amino-6-chlorophenol and 3-(P- aminoethyl)amino-6-chlorophenol, and the addition salts thereof with an acid. 17. Composition according to any one of the preceding claims, characterized in that the meta- aminophenol derivative(s) of formula (II) represent(s) from 0.0001 to 10% by weight relative to the total weight of the dye composition.

18. Composition according to Claim 17, characterized in that the meta-aminophenol derivative(s) of formula (II) represent(s) from 0.005 to 5% by weight relative to the total weight of the dye composition.

19. Composition according to any one of the preceding claims, characterized in that it contains one or more couplers other than the meta-aminophenol derivatives of formula (II) as defined in Claim 1 and/or one or more direct dyes other than the 3-aminopyridine derivatives of formula as defined in Claim 1. Composition according to any one of the preceding claims, characterized in that the addition salts with an acid are chosen from the hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.

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

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

23. Process for dyeing keratin fibres, and in particular human keratin fibres such as the hair, characterized in that at least one dye composition as defined in any one of Claims 1 to 22 is applied to the said fibres, the colour being developed at acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added to the dye composition only at the time of use, or which is present in an oxidizing S. composition that is applied simultaneously or sequentially.

24. Process according to Claim 23, 15 characterized in that the oxidizing agent present in the oxidizing composition is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates, percarbonates and persulphates, peracids O and enzymes.

25. A multi-compartment dyeing kit when used to perform the process of claim 23, wherein the kit comprises a first compartment which contains a dye composition as defined in any one of claims 1 to 22-and a second compartment which contains an oxidising composition. Dated this 2nd day of January 2001 L'OREAL By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia