GB2224518A

GB2224518A - Dyeing keratin fibres with para-type oxidation base and monohydroxy-indole coupler

Info

Publication number: GB2224518A
Application number: GB8920524A
Authority: GB
Inventors: Alex Junino; Gerard Lang; Jean-Jacques Vandenbossche
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1988-09-12
Filing date: 1989-09-11
Publication date: 1990-05-09
Anticipated expiration: 2009-09-11
Also published as: IT1232920B; ZA896845B; AR245515A1; FR2636236B1; JPH02121912A; FR2636236A1; GR1000461B; NL194230C; NL8902281A; ATA210089A; IT8967751A0; KR900004317A; BE1002235A4; PT91663B; CA1341195C; PT91663A; DE3930473B4; AU4120789A; AT400672B; DE3930473A1

Description

n, i') n Z;-2451 0 TINCTORIAL COMPOSITIONS FOR KERATIN FIBRES The present

invention relates to tinctorial compositions suitable for dyeing keratin fibres, in particular for human hair, containing a precursor of an oxidation colorant and an indole coupler, and to a dyeing 5 process.

It is known to dye keratin fibres, in particular human hair, with tinctorial compositions containing a precursor of an oxidation colorant, in particular a p-phenylenediamine or ortho- or para-aminophenol, generally called "oxidation base".

It is also known that the hues obtained with these oxidation bases can be varied by using, in association with these bases, couplers which are also called colour modifiers, more particularly aromatic meta-diamines, netaaminophenols and neta-diphenols.

In the field of hair dyeing, precursors of oxidation colorants or of couplers are sought which allow a colour having satisfactory resistance to light, to washing, to bad weather and to perspiration to be conferred to the hair in the oxidizing alkaline medium generally used in oxidation dyeing.

We have discovered that the use of certain indole derivatives as couplers, with precursors of oxidation colorants of the para-type, allows dyes having particularly remarkable resistance to light, to washing, to bad weather and to perspiration to be obtained after application on keratin fibres, in particular hair.

The present invention provides a tinctorial composition suitable for dyeing keratin fibres, in particular hair, which comprises, in a medium suitable for dyeing the fibres, at least one para-type precursor of an oxidation colourant and at least one heterocyclic coupler which is a compound of formula (I):

1 1 R3 \L,"", R2 CH 1 R in which OH occupies position 6 or 7 of the aromatic nucleus; R, represents a hydrogen atom or a Cl-C4alkyl radical; and R2 and R3, which may be identical or different, each represents hydrogen atom, a Cl-C4 alkyl radical, a carboxyl radical or Cl-C4 alkoxycarbonyl radical; or a salt thereof.

Particularly preferred compounds of formula (I) are those in which the alkyl radical is methyl or ethyl and the alkoxycarbonyl radical is nethoxy- or ethoxycarbonyl.

Among these compounds, there may be mentioned 6-hydroxyindole, 6-hydroxy-3-methoxycarbonylindole, 6-hydroxy-1-methyl-3-nethoxycarbonylindole, 6-hydroxy-lmethyl-2,3-dimethoxycarbonylindole, 6-hydroxy-1,2- dimethylindole, 6-hydroxy-2-methylindole, 6-hydroxy-2- carboxyindole, 6-hydroxy-2,3-dimethylindole, 6-hydroxy-3- carboxyindole, 6-hydroxy-3-ethoxycarbonylindole, 6-hydroxy- 1.

1 carboxyindole, 6-hydroxy-3-ethoxycarbonylindole, 6-hydroxy2ethoxycarbonylindole, 6-hydroxy-3-methylindole, 6-hydroxy1-methylindole, 7-hydroxyindole and 7-hydroxy-3-methylindole. Among these compounds 6hydroxy-l-methylindole and 7-hydroxy- 3-methylindole are novel and their synthesis is described hereafter.

The colorant precursors of the para type are compounds which are not colorants in themselves, but which form a colorant by an oxidative condensation process, either with themselves, or in the presence of a coupler or modifier.

These compounds contain functional groups, in particular, for example, amino or hydroxyl groups, in the para-position with respect to each other.

These para-type colorant precursors are, in particular, para-phenylenediamine, para-aminophenol or paraheterocyclic precursors such as 2,5-diaminopyridine, 2hydroxy-5-aminopyridine or tetraaminopyrimidine.

As regards para-phenylenediamines, there may be more particularly mentioned the compounds of formula (II):

R7 R4 R 6 R - - 1 \H2 in which R4, R5 and R6, which may be identical or different, each represents a hydrogen or halogen atom, an alkyl radical having 1 to 4 carbon atoms or an alkoxy radical having 1 to 4 carbon atoms; R7 and R8, which may be identical or different, each represents a hydrogen atom or an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbethoxyaminoalkyl, piperidinoalkyl or morpholinoalkyl radical, said alkyl or alkoxy moieties having from 1 to 4 carbon atoms, or R7 and R8, form, together with the nitrogen atom to which they are bonded, a piperidino or morpholino heterocycle, with the proviso that R4 or R6 represents a hydrogen atom when R7 and R8 do not represent a hydrogen atom, or a salt thereof.

Among the compounds of formula (II), there may more particularly be mentioned p-phenylenediamine, p-toluylenediamine, methoxy-paraphenylenediamine, chloropara-phenylenediamine, 2,6-dimethyl-pphenylenediamine, 2,5dimethyl-para-phenylenediamine, 2-methyl-5-methoxyparaphenylenediamine, 2,6-dimethyl-5-methoxy-para- phenylenediamine, W,N-dimethyl-para-phenylenediamine, 3nethyl-4-amino-N,N- diethylaniline, N,N-di(P-hydroxyethyl)para-phenylenediamine, 3-methyl-4amino-N,N-di-(Phydroxyethyl)aniline, 3-chloro-4-amino-N,N-di-(Ahydroxyethyl)aniline, 4-amino-N,N-(ethylcarbamylmethyl)aniline, 3methyl-4amino-N,N-(ethylcarbamylmethyl)aniline, 4-amino-N,N(ethyl-ppiperidinoethyl)aniline, 3-methyl-4-amino-N,N-5(ethyl-,6-piperidinoethyl)aniline, 4-amino-N,N-(ethylpmorpholinoethyl)aniline, 3-methyl-4-amino-N,N-(ethylpraorpholinoethyl)aniline, 4-amino-N,N-(ethyl-pacetylaminoethyl)aniline, 4-amino-N-(0-methoxyethyl)aniline, 5 3-methyl-4-amino-N,N-(ethyl-pacetylaminoethyl)aniline, 4amino-N,N-(ethyl-p-nesylaminoethyl)aniline, 3methyl-4-aminoN,N-(ethyl-p-mesylaminoethyl)aniline. 4-amino-N,N-(ethylpsulphoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-p-sulphoethyl)aniline, N-[(41-amino)phenyl]morpholine and N-[(41- amino)phenyl]piperidine. These para-type precursors of oxidation colorants can be introduced into the tinctorial composition either in the form of the free base, or in the form of salts, such as in the form of a hydrochloride, hydrobromide or sulphate.

Among the p-aminophenols, there may be mentioned p- aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4- aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl4-aminophenol, 3,5dimethyl-4-aminophenol, 2,3-dinethyl-4aminophenol, 2,5-dinethyl-4aminophenol, 2-hydroxymethyl-4- aminophenol, 2-(p-hydroxyethyl)-4-aminophenol, 2-methoxy-4aminophenol and 3-methoxy-4-aminophenol.

The tinctorial compositions according to the invention can contain, in addition, ortho-type precursors of oxidation colorants, such as orthoaminophenols such as 1- amino-2-hydroxybenzene, 6-methyl-l-hydroxy-2-aminobenzene or 4-methyl-l- amino-2-hydroxybenzene; ortho-phenylenediamines or ortho-diphenols.

The tinctorial compositions can also contain, in addition to the heterocyclic coupler of formula (I) or a salt thereof, other couplers such as meta-diphenols, meta- aminophenols, meta-phenylenediamines, meta-acylaminophenols, meta- ureidophenols, meta-carbalkoxyaminophenols, a-naphthol or couplers having an active methylene group such as 0-ketone compounds and pyrazolones.

In particular there may be mentioned as examples 2,4dihydroxyphenoxyethanol, 2,4-dihydroxyanisole, meta-aminophenol, resorcinol monomethylether, 2-methyl-5aminophenol, 2-methyl-N-(phydroxyethyl)-5-aminophenol, 2nethyl-N-(0-mesylaminoethyl)-5-aminophenol, 2,6-dimethyl-3aminophenol, 6-hydroxybenzomorpholine, 2,4-diaminoanisole, 15 2,4-diaminophenoxyethanol, 6-aminobenzonorpholine, [N-(j8hydroxyethyl)-2-amino-4-amino]phenoxyethanol, 2-amino-N-(fi hydroxyethyl)-4-aminoanisole, (2,4-diamino)phenyl-p,y dihydroxypropylether and 2,4-diaminophenoxyethylamine and salts thereof.

There may be added to these compositions, as is well known in the state of the art, direct colorants such as azo colorants, anthraquinone colorants or nitrated derivatives of the benzene series, in particular with a view to shading or enriching with glints the colours afforded by the precursors of oxidation colorants.

All of the para-type precursors of oxidation 1 -7colorants as well as the couplers used in the tinctorial compositions according to the invention preferably represent from 0.3 to 7% by weight with respect to the weight of the said composition. The concentration of compounds of formula (1) or salts thereof is generally from 0.05 to 3.5% by weight of the total weight of the composition.

The solvent medium is generally aqueous, and its pH can, for example, vary from 8 to 11,,preferably from 9 to 11.

It may be adjusted to the desired value with the aid of an alkalinizing agent such as ammonia, or an alkali carbonate or alkanolamine such as mono-, di- or triethanolamine.

The tinctorial compositions according to the invention also contain, in their preferred form of implementation, anionic, cationic, non-ionic or amphoteric surfactants or a mixture thereof. Among these surfactants there may be mentioned the alkylbenzenesulphonates, the alkylnaphthalenesulphonates, the sulphates, the ether sulphates and the sulphonates of fatty alcohols, quaternary ammonium salts such as trimethylcetylammonium bromide and cetylpyridinium bromide; optionally ethoxylated fatty acid ethanolamides; polyethoxylated acids, alcohols or amines, polyglycerolated alcohols or polyethoxylated or polyglycerolated alkylphenols, as well as polyethoxylated alkylsulphates.

These surfactants are generally present in the -8compositions according to the invention in proportions of from 0.5 to 55% by weight, preferably from 2 to 50% by weight, with respect to the total weight of the composition.

These compositions can also contain organic solvents to solubilize the compounds which would not be sufficiently soluble in water. Among these solvents, there may, for example, be mentioned Cl-C4 alkanols such as ethanol and isopropanol; glycerol; glycols or glycol ethers such as 2butoxyethanol, ethylene glycol, propylene glycol and the monoethyl ether and the monomethyl ether of diethyleneglycol, as well as the aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products or mixtures thereof.

The solvents are preferably present in a proportion - in particular from 5 to 30% by of from 1 to 40% by weightf weight, with respect to the total weight of the composition.

The thickening agents which can be added to the compositions according to the invention can be chosen in particular from sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethy1cellulose and carboxymethy1cellulose, acrylic acid polymers and xanthan gum. Inorganic thickening agents, such as bentonite, can also be used. These thickening agents are preferably present in proportions of from 0.1 to 5%, in particular from 0.2 to 3%, by weight with respect to the total weight of the composition.

The antioxidants which can be present in the compositions are chosen in particular from sodium sulphite, thioglycolic acid, sodium bisulphite, ascorbic acid and hydroquinone. These antioxidants are generally present in the composition in proportions of from 0.05 to 1.5% by weight with respect to the total weight of the composition.

These compositions can also contain other cosmetically acceptable additives, such as, for example, penetration agents, sequestering agents, buffers and fra- grances.

The compositions according to the invention can be presented in various forms, such as in the form of liquids, creams, gels, or in any other form which is appropriate for carrying out dyeing of keratin fibres, and in particular human hair. These compositions can be packed in aerosol containers in the presence of a propellant.

The tinctorial compositions according to the invention which contain a para-type precursor of an oxidation colorant and a coupler of formula (I) or a salt thereof are used in processes for dyeing keratin fibres, in particular human hair, using development by means of an oxidizing agent.

According to this process, the tinctorial composition described above is mixed at the time of use with an oxidizing solution in sufficient quantity to develop a coloration, then the mixture obtained is applied on keratin fibres, in particular human hair.

is 2 The oxidizing solution contains oxidizing agents such as hydrogen peroxide, urea peroxide or persalts such as ammonium persulphate. A 20 volume solution of hydrogen peroxide is preferably used.

The mixture obtained is applied to the hair and left in place for from 10 to 40 minutes, preferably from 15 to 30 minutes, after which the hair is rinsed, washed with shampoo, rinsed again and dried.

The heterocyclic coupler of formula (I) or salt thereof can also be used in a process of several stages, consisting in one of its stages in applying the paraprecursor of an oxidation colorant, and in another stage in applying the coupler of formula (I) or salt thereof.

The oxidizing agent can be introduced into the composition applied in the second stage immediately before application, or again may be added onto the keratin fibres themselves in a third stage, the conditions of exposure and of drying or washing being identical.

The following Examples further illustrate the 0 invention without, however, having a limiting character.

-11APPLICATION EXAMPLE 1 The following tinctorial mixture is prepared p-Phenylenediamine - Oleyl alcohol polyglycerolated with 2 moles of glycerol - Oleyl alcohol polyglycerolated with 4 moles of glycerol Ethomeen 0 12 - Armoon Hess Chemical Company Ltd (oleylamine ethoxylated with 12 moles of ethylene oxide) - Comperlan KD - Henkel Company (copra diethanolamide) - Propylene glycol - 2-Butoxyethanol 96% Ethanol Masquol DTPA - Protex Company (pentasodium diethylenetriaminepentacetate) 0.33 g 0.27 g 4.5 g 4.5 g 4.5 g 9.0 g 4.0 g 8. 0 g 6. 0 g 2.0 g - Hydroquinone 0.15 g - 35Be sodium bisulphite solution 1.3 g - 22Be ammonia solution 10.0 g - Water qs 100.0 g - pH = 10.5 g of 20 volume hydrogen peroxide is added at the time of use. The nixture, applied for 20 minutes at 34'C on hair containing 90% naturally white hair, gives it, after shampooing and rinsing, a medium golden brown colour. APPLICATION EXAMPLE 2 The following tinctorial mixture is prepared:

6-Hydroxyindole p-Aminophenol Oleyl alcohol polyglycerolated with 2 moles of glycerol Oleyl alcohol polyglycerolated with 4 moles of glycerol Ethomeen 0 12 - Armoon Hess Chemical Company Ltd. (oleylamine ethoxylated with 12 moles of ethylene oxide) Comperlan KD - Henkel Company (copra diethanolamine) Propylene glycol 2-Butoxyethanol 96% Ethanol - Masquol DTPA - Protex Company (pentasodium diethylenetriaminepentacetate) Hydroquinone - 35OBe sodium bisulphite solution - 22'Be ammonia solution Water pH = 10.5 0.33 g 0.27 g 9 4.5 g 9 9.0 g 4.0 g 8.0 g 6.0 g 2.0 g 0. 15 g 1. 3 g 10. 0 g 100. 0 g qs g of 20 volume hydrogen peroxide is added at the time of use. The mixture, applied for 20 minutes at 340C on bleached hair, gives it, after shampooing and rinsing, a golden beige colour.

APPLICATION EXAMPLE 3 The following tinctorial mixture is prepared: 6-Hydroxy-1-methylindole - Bis-(.-hydroxyethyl)-4-aminoaniline dihydrochloride - Cellosize WP 03 - Union Carbide Company (hydroxyethylcellulose) - Ammonium laurylsulphate - 96% Alcohol - Masquol DTPA - Protex Company (pentasodium diethylenetriaminepent acetate) - Water - pH = 10.5 0.73 g 1.34 g 2.0 g 5.0 g 15. 0 g 5. 0 g 2.0 g qs 100. 0 g 100 g of 20 volume hydrogen peroxide is added at the time of use. The mixture, applied for 20 minutes at 340C on hair containing 90% naturally white hair, gives it, after shampooing and rinsing, a dark purple-grey colour.

-14APPLICATION EXAMPLE 4 The following tinctorial mixture is prepared: 6-Hydroxy-l-methylindole Para-phenylenediamine - Octyldodecanol sold under the name of Eutanol G by the Henkel Company Oleic acid Monoethanolamine laurylethersulphate sold under the name of Sipon IM 35 by the Henkel Company Ethyl alcohol Benzyl alcohol Cetylstearyl alcohol ethoxylated with 33 moles of ethylene oxide, sold under the name of Simulsol GS by the Seppic Company Ethylenediaminetetraacetic acid Cationic polymer consisting of recurrent units:

0.29 g 0.22 g 8. 0 g 20.0 g 3.0 g 10. 0 g 10.0 g 2.4 g 0.2 g I 3 J H 3 (%'-H2)3 - (CH2)6-- CII 3' Cle tH3 C119 - 2.2 g 7.5 g Monoethanolamine Linoleic acid diethanolamide sold under the name of Comperlan F by the Henkel Company 8.0 g - 20% Ammonia solution - 35% Aqueous solution of sodium metabisulphite 1.3 - Hydroquinone 0.15 I-Phenyl-3-methyl-5-pyrazolone 0.2 - Demineralized water qs 100.0 The composition is mixed weight for weight with 20 volume hydrogen peroxide, the pH of which is equal to 3, at the time of use.

The mixture thus obtained is applied for 30 minutes on grey hair containing 90% white hair, then the hair is rinsed, washed, rinsed again and dried. The colour obtained is a coppery beige blonde. APPLICATION EXAMPLE 5 The following tinctorial mixture is prepared: 6-Hydroxy-2ethoxycarbonylindole Para-phenylenediamine Octyldodecanol sold under the name of Eutanol G by the Henkel Company - Oleic acid - Monoethanolamine laurylethersulphate sold under the name of Sipon IM 35 by the Henkel Company - Ethyl alcohol - Benzyl alcohol Cetylstearyl alcohol ethoxylated with 33 moles of ethylene oxide, sold under 10.2 9 9 9 9 9 0.41 g 0.22 g 8.0 g 20.0 g 3.0 g 10. 0 g 10. 0 g the name of Simulsol GS by the Seppic Company Ethylenediaminetetraacetic acid Cationic polymer consisting of recurrent units:

H3 + C83 + (CH2) 3 (CH 6'- CIO H3 CIG) Monoethanolamine Linoleic acid diethanolamide sold under the name of Comperlan F by the Henkel Company 20% Ammonia solution 35% Aqueous solution of sodium metabisulphite 2.4 g 0.2 g 2.2 g 7.5 g 8.0 g 10.2 g 1. 3 g 0. 15 g 0.2 g - Hydroquinone 1-Phenyl-3-methyl-5-pyrazolone - Demineralized water qs 100.0 g The composition is mixed weight for weight with 20 volume hydrogen peroxide, the pH of which is equal to 3, at the time of use.

The mixture thus obtained is applied for 30 minutes on grey hair containing 90% white hair, then the hair is rinsed, washed, rinsed again and dried.

The colour obtained is an ash beige-blonde.

is APPLICATION EXAMPLE 6 The following tinctorial mixture is prepared:

6-Hydroxy-2-carboxyindole Para-phenylenediamine - Octyldodecanol sold under the name of Eutanol G by the Henkel Company Oleic acid Monoethanolamine laurylethersulphate sold under the name of Sipon LM 35 by the Henkel Company Ethyl alcohol Benzyl alcohol Cetylstearyl alcohol ethoxylated with 33 moles of ethylene oxide sold under the name of Simulsol GS by the Seppic Company - Ethylenediaminetetraacetic acid Cationic polymer consisting of recurrent units:

C1i3 __+ 1 C, H 3 (C:H2).3 + 2) 6-- CH3 C10 CH3 C10 Monoethanolamine 0.35 g 0.22 g 8.0 g 20.0 g 3.0 g 10. 0 g 10. 0 g 2.4 g 0.2 g 2.2 g 7.5 g -18Linoleic acid diethanolamide sold under the name of Comperlan F by the Henkel Company - 20% Ammonia solution 5 - 35% Aqueous solution of sodium metabisulphite is 8. 0 g 10. 2 g 1. 3 g - Hydroquinone 0.15 g Demineralized water qs 100.0 g The composition is mixed weight for weight with 20 volume hydrogen peroxide, the pH of which is equal to 3, at the time of use.

The mixture thus obtained is applied for 30 minutes on grey hair containing 90% white hair, then the hair is rinsed, washed, r-Insed again and dried.

The colour is dark coppery beige blonde. APPLICTION EXAMPLE 7 Example 6 is repeated using 0.34 g 6-hydroxy 2,3dimethyl indole instead of the 0.35 g 6-hydroxy 2-carboxy- indole. The dyeing conditins are the same as in Example 6. The colour of the hair is rinsed light blond mahogany. APPLICATION EXAMPLE 8 Example 6 is repeated using 0.34 g 6-hydroxy 2,3dimethyl indole instead of the 0.35 g 6-hydroxy 2- carboxyindole. The dyeing conditions are the same as in Example 6. The hair is dyed and rinsed light blond.

APPLICATION EXAMPLE 9 The following tinctorial mixture is prepared: 7-Hydroxyindole p- Phenylenediamine - Octyldodecanol sold under the name of Eutanol G by the Henkel Company Oleic acid Monoethanolamine laurylethersulphate sold under the name of Sipon IM 35 by the Henkel Company Ethyl alcohol Benzyl alcohol Cetylstearyl alcohol ethoxylated with 33 noles of ethylene oxide sold under 15 the name of Simulsol GS by the Seppic Company Ethylenediaminetetraacetic acid Cationic polymer consisting of recurrent units:

CH3 CH3 4.

1 - (CE12)3 - +N' - ('H2)6 1 1 L-Cl3 C10 X- rjj c, -0 Monoethanolanine Linoleic acid diethanolamide sold under the name of Coraperlan F by the Henkel Company 0.27 g 0.22 g 8. 0 g 20.0 g 3.0 g 10. 0 g 10. 0 g 2.4 g 0.2 g 9 9 8. 0 g 20% Ammonia solution 35% Aqueous solution of sodium metabisulphite 1.3 g - Hydroquinone 0.15 g 1-Phenyl-3-methyl-5-pyrazolone 0.2 g - Demineralized water qs 100.0 g The composition is mixed weight for weight with 20 volume hydrogen peroxide, the pH of which is equal to 3, at the time of use.

The colour is a dark ash pearly blonde. APPLICATION EXAMPLE 10 The Zollowing tinctorial mixture is prepared: 7-Hydroxyindole p- Aminophenol Octyldodecanol sold under the name of Eutanol G by the Henkel Company 20 Oleic acid - Monoethanolamine laurylethersulphate sold under the name of Sipon LM 35 by the Henkel Company - Ethyl alcohol 25 - Benzyl alcohol Cetylstearyl alcohol ethoxylated with 33 moles of ethylene oxide sold under 10.2 g 0.53 g 0.44 g 8. 0 g 20.0 g 3.0 g 10. 0 g 10. 0 g the name of Simulsol GS by the Sepp Company Ethylenediaminetetraacetic acid Cationic polymer consisting of recurrent units:

1 2.4 g 0.2 g Cl3 CH3 __+1 - +1 NI - (C.12)3 2) 6- 1 CI(D M3.1. c H 3 c -:G) Monoethanolamine Linoleic acid diethanolamide sold under the name of Comperlan F by the Henkel Company 20% Ammonia solution 35% Aqueous solution of sodium netabisulphite 1.3 g Hydroquinone 0.15 g 1-Phenyl-3-methyl-5-pyrazolone 0.2 g Demineralized water qs 100.0 g The composition is mixed weight for weight with 20 volume hydrogen peroxide, the pH of which is equal to 3, at the time of use.

The colour is a coppery pearly blonde.

2.2 g 7.5 g 8.0 g 10.2 g -22APPLICATION EXAMPLE 11 Locks of hair containing 90% white hair are dyed with a composition (A9) having the following composition:

- Ethanol 10.0 - Sodium laurylethersulphate 1.0 - Water qs 100.0 g The exposure time is 10 minutes. After rinsing and drying a grey lock of hair with golden highlights is thus obtained. By applying thereafter for 10 minutes a mixture of equal amounts of a 0.5% sglution of N,N-bis-p-hydroxyethyl paraphenylenediamine in water and a 6% hydrogen peroxide solution in water (pH 7) a lock coloured dark blond with purple shades is obtained after rinsing and drying.

is APPLICATION EXAMPLE 12 A 2.5% aqueous-alcoholic solution of 6-hydroxyindole is prepared at pH 9 (NaOH) and applied to hair at a rate of 2.5 g per g of grey hair. After 10 minutes exposure time, rinsing and drying, slightly ash blonde grey hair is obtained.

If a mixture of equal parts of a 0.5% solution of Nmethoxyethyl-paraphenylenediamine at pH 10 and of 6% hydrogen peroxide is then applied for 3 minutes, hair of a light purple-chestnut colour is obtained after rinsing and drying.

9 9 1 PREPARATION EXAMPLE 1 PreiDaration of 6-hvdroxy-1-methylindole 1st staae:

PreDaration of 6-benzvloxv-1-methvlindole 300 ml of toluene, 50 ml of rethylsulphate and 7.36 g of tetrabutylammonium hydrogen sulphate are added to 125 g of sodium hydroxide pellets in 125 ml of water, then, with stirring, 0.33 mole (73.6 g) of 6-benzyloxyindole. Stirring is maintained for 15 minutes after the end of the evolution of heat. The reaction medium is diluted with 2 volumes of water. After separation of the organic phase, the aqueous phase is extracted with toluene. After washing the organic phases with water and drying then, the desired product is obtained by evaporation. It melts at 79'C.

Analysis of the product obtained after recrystal- lization from methanol gives the following results:

Analysis for Calculated for Found C16H15NO 81.01 c H N 0 6.33 5.91 6.75 80.92 6.36 5.80 6.99 2nd stacFe:

Preparation of 6-hydroxv-1-nethylindole The mixture consisting of 0.24 mole (57 g) of 6-benzyloxy-l-methylindole, 5.7 g of 10% palladiun-on charcoal, 114 ml of cyclohexene and 170 ml of 96% ethanol is -24heated for 30 minutes under reflux. The mixture is filtered hot to remove the catalyst. After evaporation of the filtrate under vacuum, an oil is obtained which, dissolved in isopropyl ether, gives the desired product after evaporation to dryness. It melts at 740C.

Analysis of the product obtained gives the following results:

Analysis for Calculated for Found C9H9NO c 73.47 73.57 H 6.12 6.12 N 9.52 9.39 0 10.88 11.07 PREPARATION EXAMPLE 2 greDaration of 7-hvdroxv-3-methvlindole 1st staae: PreDaration of 1-r(31benzvloxv-51-chloro-21-nitro)Dhenyll-2 cyanopropane The reaction mixture consiting of 0.5 mole (151.2 g) of 3-benzyloxy-5-chloro-2-nitrophenylacetonitrile, 152.6 g of methyl iodide and 207 g of potassium carbonate in 500 ml of acetone is taken to reflux for 8 hours. The reaction mediun is diluted with 4 kg of iced water to which has been added 500 ml of acetic acid. The desired product precipitates.

After recrystallization from acetic acid it melts at 180'C.

Analysis of the product obtained gives the following results:

1 Analysis from Calculated for Found C16H13K203C1 c 60.67 60.72 H 4.14 4.12 N 8.84 8.64 0 15.15 15.01 cl 11.19 11.34 2nd staqe:

Preparation of 7-hvdroxv-3-methvlindole The reaction mixture consisting of 20 g of 1-[(31- benzyloxy-51-chloro-21-nitro)phenyl]-2-cyanopropane and 10 g of 10% palladium-on-charcoal in 100 ml of ethanol to which has been added 40 ml of cyclohexene is heated under reflux for 4 hours. At the end of the reaction the catalyst is separated from the reaction medium by filtration. After addition of carbon black to the filtrate, filtration and then evaporation, the desired product, which crystallizes from an isopropylether-chloroform mixture, is obtained. It melts at 1900C. Analysis of the product obtained gives the following results:

Analysis for Calculated for Found C9H9NO c 73.45 73.53 H 6.16 6.23 N 9.52 9.45 0 10.87 10.76

Claims

1. A tinctorial composition suitable for dyeing keratin fibres, which comprises, in a medium suitable for dyeing the fibres, at least one para-type precursor of an oxidation colourant and at least one heterocyclic coupler which is a compound of formula (I):

R3 1 ' ', -, 11 N R 2 CH in which OH occupies position 6 or 7 of the aromatic nucleus; R, represents a hydrogen atom or a Cl-C4 alkyl radical; and R2 and R3, which may be identical or different, each represents a hydrogen atom, a Cl-C4 alkyl radical, a carboxyl radical or a Cl-C4 alkoxycarbonyl radical; or a salt thereof.

2. A composition according to Claim 1, in which the compound of formula (I) is 6-hydroxyindole, 6-hydroxy-3- methoxycarbonylindole, 6-hydroxy-1-methyl-3- nethoxycarbonylindole, 6-hydroxy-1-methyl-2,3dimethoxycarbonylindole, 6-hydroxy-1,2-dimethylindole, 6hydroxy-2-methylindole, 6-hydroxy-2-carboxyindole, 6-hydroxy2,3-dimethylindole, 6-hydroxy-3-carboxyindole, 6-hydroxy-3ethoxycarbonylindole, 6-hydroxy-2-ethoxycarbonylindole, 6-hydroxy-3-methylindole, 6-hydroxy-l-methylindole, 7-hydroxyindole or 7-hydroxy-3-nethylindole.

3. A composition according to Claim 1 or 2, in which the para-type precursor of an oxidation colorant is a z 1 1 para-phenylenediamine, para-aminophenol or para-heterocyclic precursor.

4. A composition according to Claim 3, in which para-phenylenediamine is a compound of formula (II):

, F' 7 F 4 l6 R - 1 W 2 in which R4, R5 and R6, which may be identical or different, each represents a hydrogen or halogen atom, an alkyl radical having 1 to 4 carbon atoms or an alkoxy radical having 1 to 4 carbon atoms; R7 and R8, which may be identical or different, each represents a hydrogen atom or an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbethoxyaminoalkyl, piperidinoalkyl or morpholinoalkyl radical, said alkyl or alkoxy moieties having from 1 to 4 carbon atoms, or R7 and R8 form, together with the nitrogen atom to which they are bonded, a piperidino or morpholino heterocycle, with the proviso that R4 or R6 represents a hydrogen atom when R7 and R8 do not represent a hydrogen atom, or a salt thereof.

5. A composition according to Claim 4, wherein the para-phenylenediamine is p-phenylenediamine, p-toluylenediamine, methoxy- para-phenylenediamine, chloropara-phenylenediamine, 2,6-dimethyl-p- phenylenediamine, 2,5-28dimethyl-para-phenylenediamine, 2-methyl-5-methoxyparaphenylenediamine, 2,6-dimethyl-5-methoxy-paraphenylenediamine, N,Ndimethyl-para-phenylenediamine, 3methyl-4-amino-N,N-diethylaniline, N,Ndi(fl-hydroxy5 ethyl)para-phenylenediamine, 3-methyl-4-amino-N,N-di(Phydroxyethyl)aniline, 3-chloro-4-amino-N,N-di-(p-hydroxyethyl)aniline, 4-amino-N,N-(ethylcarbamylmethyl)aniline, 3nethyl-4-amino-N,N(ethylcarbaTnylnethyl)aniline, 4-amino-N,N(ethyl-ppiperidinoethyl)aniline, 3-methyl-4-amino-N,N(ethyl-p-piperidinoethyl)aniline, 4-amino-N,N-(ethylpnorpholinoethyl)aniline, 3-methyl-4-amino-N,N-(ethylpmorpholinoethyl)aniline, 4-amino-N,N-(ethyl-pacetylaminoethyl)aniline, 4amino-N-(p-methoxyethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-pacetylaminoethyl)aniline, 4- amino-N,N-(ethyl-p-mesylaminoethyl)aniline, 3-Methyl-4-aminoN,N-(ethyl-p- mesylaminoethyl)aniline, 4-amino-N,N-(ethyl-psulphoethyl)aniline, 3methyl-4-amino-N,N-(ethyl-p-sulphoethyl)aniline, N-[(41amino)phenyl]morpholine and N-[(41amino)phenyl]piperidine or a salt thereof.

6. A composition according to any one of Claims 1 to 3, wherein the p-aminophenol is p-aminophenol, 2-methyl-4 aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5 dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5- dimethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-(Phydroxyethyl)- 4-aininophenol, 2-nethoxy-4-aminophenol or 3methoxy-4-aminophenol.

7. A composition according to any one of the preceding Claims, which additionally comprises an ortho-type precursor of an oxidation colorant which is an ortho aninophenol, ortho-phenylenediamine or ortho-diphenol.

8. A composition according to any one of the preceding Claims, which additionally comprises a further coupler which is a meta-diphenol, meta-aminophenol, meta phenylenediamine, meta-acylaminophenol, meta-ureidophenol, meta-carbalkoxyaminophenol, a-naphthol, a 0-ketone compound or a pyrazalone.

9. A composition according to Claim 8, in which the further coupler is 2,4-dihydroxyphenoxyethanol, 2,4 dihydroxyanisol, meta-aminophenol, resorcinol monomethylether, 2-methyl-5-aminophenol, 2-methyl-N-(phydroxyethyl)-5-aminophenol, 2-methyl-N-(p-mesylaminoethyl)5-aminophenol, 2,6-dimethyl-3-aminophenol, 6hydroxybenzomorpholine, 2,4-diaminoanisole, 2,4diaminophenoxyethanol, 6-aminobenzomorpholine, [N-(phydroxyethyl)-2amino-4-amino]phenoxyethanol, 2-amino-N-(p- hydroxyethyl)-4-aminoanisole, (2,4-diamino)phenyl-P,Y dihydroxypropylether or 2,4-diaminophenoxyethylamine or a salt thereof.

10. A composition according to any one of the preceding Claims, which also comprises a direct colorant.

11. A composition according to any one of the preceding claims, in which the para-type precursor of an oxidation colorant and the couplers are present in proportions of from 0.3 to 7% by weight with respect to the total weight of the composition.

12. A composition according to any one of the preceding Claims, in which the compound of formula (I) or salt thereof is present in a proportion of from 0.05 to 3.5% by weight with respect to the total weight of the composition.

13. A composition according to any one of the preceding Claims, in which the medium suitable for dyeing the fibres is aqueous and has a pH of from 8 to 11.

14. A composition according to any one of the preceding Claims, which also comprises an anionic, cationic, nonionic or amphoteric surfactant or mixture thereof.

15. A composition according to any one of the preceding claims, which comprises an organic solvent in a proportion of from 1 to 40% by weight with respect to the total weight of the composition.

16. A composition according to any one of the preceding Claims, which also comprises a thickening agent, antioxidant, penetration agent, sequestering agent, buffer and/or fragrance.

17. A composition according to any one of the preceding Claims, which is in the form of a liquid, cream or gel.

18. A composition according to Claim 17 which is packed in an aerosol in the presence of a propellant.

19. A composition according to Claim 1 substantially as described in any one of the Application Examples.

20. A process for the preparation of a tinctorial composition suitable to be applied immediately to human hair, wherein a composition as defined in any one of the preceding Claims is mixed at the time of use with an oxidizing solution in sufficient quantity to form a colorant.

21. A process for dyeing keratin fibres wherein a composition as defined in any one of Claims 1 to 19 is applied to the fibres in the presence of an oxidizing agent, the composition is left in contact with the fibres for from to 40 minutes, and the application is followed by rinsing the fibres, washing, rinsing and drying.

22. A process for dyeing keratin fibres wherein firstly a para-precursor of an oxidation colorant is applied, and secondly at least one heterocyclic coupler as defined in Claim 1 or 2 is applied, an oxidizing agent being introduced just before use, either in the composition applied in the second stage, or else added onto the fibres in a third stage.

23. A process according to Claim 21 or 22 wherein the keratin fibres are human hair.

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