AU626579B2 - Tinctorial compositions for keratin fibres containing precursors of oxidation colorants and indole couplers, and dyeing processes using these compositions - Google Patents

Description

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1 Ri~a~ i-i I0 vLp4~ QL9~~P~ Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class Application Number: Lodged: Int. Class Complete Specification Lodged: 9 Priority: Related Art Related Art: 4 Accepted: Published: Name of Applicant: Address of Applicant: 0 i Actual Inventor: Address for Service:

L'OREAL

14, rue Royale, 75008 Paris, France ALEX JUNINO, GERARD LANG and JEAN-JACQUES VANDENBOSSCIHE S4.3F Aiij~gW Watermark Patent Trademark Attorneys 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: TINCTORIAL COMPOSITIONS FOR KERATIN FIBRES CONTAINING PRECURSORS OF OXIDATION COLORANTS AND INDOLE COUPLERS, AND DYEING PROCESSES USING THESE COMPOSITIONS The following statement is a full description of this invention, including the best method of performing it known to Us __I ~I

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r I r 11D Tinctorial compositions for keratin fibres containing precursors of oxidation colorants and indole couplers, and dyeing processes using these compositions.

The present invention relates to new tinctorial compositions for keratin fibres and in particular for human hair, containing precursors of oxidation colorants and indole couplers, and a dyeing process using such compositions.

It is known to dye keratin fibres, and in 10 particular human hair, with tinctorial compositions containing precursors of oxidation colorants and in particular p-phenylenediamines or ortho- or paraaminophenols 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 4 44 0 06 Scolour modifiers, and more particularly aromatic meta- So diamines, meta-aminophenols and meta-diphenols.

In the field of hair dyeing, precursors of oxida- 20 tion 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.

The applicant has just discovered, which is the subject of the invention, that the use of certain indole i ~~i 2 t t 2 derivatives as couplers, with precursors of oxidation colorants of the para-type, allowed dyes having particularly remarkable resistance to light, to washing, to bad weather and to perspiration to be obtained after application on keratin fibres and in particular hair.

One subject of the invention therefore comprises oxidation tinctorial compositions, intended to be used for dyeing keratin fibres, containing at least one precursor of an oxidation colorant of the para-type with o ,10 certain indole, derivatives defined below.

0*00 °.o0 Another subject of the invention comprises the 00 0 o process of coloration of keratin fibres, in particular of S° human hair, using such a composition.

Other subjects of the invention will appear on reading the description and the examples which follow.

The oxidation tinctorial composition according to o 0 o 0 0 0 0 0o0 the invention, which is intended to be used for dyeing keratin fibres and in particular hair, is essentially 0 0 characterized in that it contains, in an acceptable solvent medium, at least one para- precursor of an oxidation colorant and at least one heterocyclic coupler corresponding to formula A-

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-3in which OH occupies positions 6 or 7 of the aromatic nucleus and R, designates a hydrogen atom or a Cl-C,,alkyl radical; and R 3 1 which may be identical. or different, designate a hydrogen atom, a Cl-C, lower alkyl radical, a carboxyl radical or a C 1 -C 4 alkoxycarbonyl radical as well as their salts.

Among the compounds of formula the particularly preferred compounds are the compounds in which the alkyl radical designates methyl or ethyl and the alkoxycarbonyl radical designates methoxy- or ethoxycarbonyl.

Among these compoundk5, there may be mentioned 0 0e0 0 6-hydroxyindole, 6-hydr"xy-3-methoxycarbonylindole, 6-hydroxy-l-methyl-3-methoxycarbonylindole, 6-hydroxy-- 4,1O5 methyl-2, 3-dimethoxycarbonylindole, 6-hydroxy-1,2dimethylindole, 6-hydroxy-2-methylindole, 6-hydroxy-2carboxyindole, 6-hydroxy-2, 3-dimethylindole, 6-hydroxy- 3-carboxyindole, 6-hydroxy-3--ethoxycarbonylindole, oo6-hydroxy-2-ethoxycarbonylindole, 6-hydroxy-3-methyl- 0.6.20indole, 6-hycdroxy-l--methylindole, 7-hydroxyindole and 7hydroxy-3-methylindole.

Among these compounds 6-hydroxy 1-methylinclole and 7-hyciroxy 3-methylirn1ole are novel, their synthesis is described thereafter.

£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.

4 4 These compounds contain functional groups, in particular amino or hydroxyl groups, in the para-position with respect to each other.

These para-type colorant precursors are chosen in particular from the para-phenylenediamines, the paraaminophenols and the para-heterocyclic precursors such as 2-hydroxy-5-aminopyridine and tetraaminopyrimidine.

As regards para-phenylenediamines, there may be 10 more particularly mentioned the compounds which coro*il$, respond to formula (II) below: -7 ea

R

Sin which R 4

R

5 and R 6 which may be identical or different, represent a hydrogen or halogen atom, an alkyl radical having 1 to 4 carbon atoms or an alkoxy radical having 1 to 4 carbon atoms, R, and which may be identical or different, represent a hydrogen atom or an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbethoxyaminoalkyl, piperidinoalkyl or morpholinoalkyl radical.

These alkyl or alkoxy groups having from 1 to 4 carbon atoms, or again R, and R 8 form, together with the nitrogen atom to which they are bonded, a piperidino or morpholino heterocycle, with the reservation that R 4 or R 6 represent a hydrogen atom when R 7 and R. do not represent a hydrogen atom, as well as the salts of these compounds.

Among the compounds of formula (II) there may more particularly be mentioned p-phenylenediamine, p-toluylenediamine, methoxy-para-phenylenediamine, chloro-para-phenylenediamine, 2, 6-dimethyl-p-phenylenediainine, 2, 5-dimethyl-para-phenylenediamine, 00 o 0 10 methoxy-para-phenylenediamine, 2, para-phenylenedianine, N,N-dimethyl-para--phenylenediainine, 3-methyl-4-amino-N,N-diethylaniline, N,N-di(B- 0 0 0hydroxyethyl )para-phenylenediamine, 3-methyl-4-antino-N,Ndi- (B-hydroxye-thyl) aniline, 3-chloro-4-ainino-N,N-di-(Bhydroxyethyl aniline, 4-amino-N,N-(ethylcarbanylinethyl) aniline, 3-methyl-4-amino-N,N- (ethylcarbamylmethyl) 0000aniline, 4-amino-N,N-(ethyl-p-piperidinoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-p-piperidinoethyl)aniline, a 0 4-amino-N,N- (ethyl-pa-morpholinoethyl) aniline, 3-methyl- :020 4-amino-N,N-(ethyl-p-morpholinoethyl)aniline, 4-amino- 0' N,N-(ethyl.-p-acetylaininoethyl)aniline, 4-amino-N-( 1 8methoxyethyl)aniline, 3-methyl-4-amino-N,N-(ethylacetylaminoethyl) aniline, 4-amino-N,N-(ethyl-~A-mesylaminoethyl) aniline, 3 -methyl 4-amino-N, N.-(ethyl -mesyl aminoethyl)aniline, 4-amino-Ni,N-(ethyl-p-sulphoethyl)aniline, 3-ehl4aioNN(ehl,-upoty) aniline, (4'-axino)phenyl]morpholine and

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-6 00 0 000 49,0 0 0044 99 I 0 4 1 0 94 9090 9 4 1,4,4 0 4~ 04 amino) phenyl]piperidine. These para-type precursors of oxidation colorants can be introduced into the tinctorial compositi-on either in the form of the free base, or in the form of salts, such as in the form of 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-dimethyl-4-aminophenol, 3 ,5-dimethyl-4-aminophenol, 10 2 ,3-dimethyl-4-aminophenol, 2 ,5-dimethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-(,B-hydroxyethyl) -4aminophenol, 2-methoxy-4-aminophenol and 3-methoxv-4aminophenol.

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

The tinctorial compositions can also contain, in addition to the heterocyclic coupler corresponding to formula above, other couplers which are known per se, such as meta-diphenols, meta-aminophenols, metaphenylenediamines, meta-acylaminophenols, metaureidophenols, meta-carbalkoxyaminophenols, a-naphthol or couplers having an active methylene group such as p ketone compounds and pyrazolones.

9,94 9 94 90 4 4 00 0 09 0.044 0 9 9 4~4 4 0 0~~a".0 9 0 0 9 7 In particular there may be mentioned as examples 2,4-dihydroxyphenoxyethanol, 2,4-dihydroxyanisole, meta-aminophenot, resorcinol monomethylether, 2-methyl- 2-methyl-N-(A-mesylaminoethyl)-5-aminophenol, 2,6dimethyl-3-aminophenol, 6-hydroxybenzomorpholine, 2,4diaminoanisole, 2,4-diaminophenoxyethanol, 6-aminobenzomorpholine, -hydroxyethyl)-2-amino-4-amino]phenoxyethanol, 2-amino-N- (-hydroxyethyl)-4-aminoanisole, (2,4- 10 diamino)phenyl-p ,7-dihydroxypropylether and 2,4-diaminophenoxyethylamine and their salts.

0 4 9 There may be added to these compositions, as is 0co. 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 4" view to shading or enriching with glints the colours afforded by the precursors of oxidation colorants.

All of the para-type precursors of oxidation colorants as well as the couplers used in the tinctorial compositions according to the invention preferably a represent from 0.3 to 7% by weight with respect to the 2 weight of the said composition. The concentration of compounds can vary between 0.05 and 3.5% by weight of the total weight of the composition.

The acceptable solvent medium is generally aqueous, and its pH can vary between 8 and 11, and it is preferably between 9 and 11.

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2 8 It is adjusted to the desired value with the aid of an alkalinizing agent such as ammonia, the alkali carbonates or the-alkanolamines 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 their mixtures. 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 present in the compositions according to the invention in proportions of between and 55% by weight, and preferably between 2 and 50% by weight with respect to the total weight of the composition.

o 00 0 0 Oo'00 00. 0 0404 00 0 0 0 0 a

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These compositions can also contain organic solvents to solubilize the compounds which would not be sufficiently soluble in water. Among these solvents, there may be mentioned as examples, the C 1

-C

4 lower alkanols such as ethanol and isopropanol; glycerol; the r

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I-l-~-il i--l-ii~ ii 9

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o co 44 4 0 4 4 0 *4 *ob 001 4, O 0 p 44044* 0 glycols or glycol ethers such as 2-butoxyethanol, 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 their mixtures.

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

.0 The thickening agents which can be added to the compositions according to th invention can be chosen in particular from sodium alginate, gum arabic, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose and carboxymethylcellulose, 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 between 0.1 to and in particular between 0.2 and 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 present in the composition in proportions of between 0.05 and by weight with respect to the total weight of the composition.

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"14 i 10 These compositions can also contain other cosmetically acceptable additives, such as, for example, penetration agents, sequestering agents, buffers, fragrances and the like.

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.

°o The tinctorial compositions according to the invention which contain a para-type precursor of an 0o oxidation colorant and a coupler of formula are used 0 15 in processes for dyeing keratin fibres, and in particular human hair, according to a process using development by means of an oxidizing agent.

0 According to this process, the tinctorial composition described above is mixed at the time of use with 20 an oxidizing solution in sufficient quantity to develop a coloration, then the mixture obtained is applied on LL( keratin fibres and in particular human hair.

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.

1 ll~~~-rr~a~r R n-r 11 The mixture obtained is applied on the hair and left in place for 10 to 40 minutes, preferably 15 to minutes, after which the hair is rinsed, washed with shampoo, rinsed again and dried.

The heterocyclic coupler of formula defined above can also be used in a process of several stages, consisting in one of its stages in applying the paraprecursor of an oxidation colorant by means of a composition defined above, and in another stage in applying the o00 Sooo 10 coupler of formula 0000 ooo 0 The oxidizing agent can be introduced into the 00 0 o 00 composition applied in the second stage immediately 00o000 0 0 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.

o The following examples are intended to illustrate the invention without, however, having a limiting i e character.

0 0 0 0 12 APPLICATION EXAMPLE 1 The following tinctorial mixture is prepared: 6-Hydroxyindole 0.33 g p-Phenylenediamine 0.27 g Oleyl alcohol polyglycerolated with 2 moles of glycerol 4.5 g Oleyl alcohol polyglycerolated with 4 moles of glycerol 4.5 g Ethomeen O 12 Armoon Hess Chemical "<oo 10 Company Ltd (oleylamine ethoxylated 4.5 g 0 0 with 12 moles of ethylene oxide) 0 0 0 Comperlan KD Henkel Company 9.0 g 0 0 0o (copra diethanolamide) Propylene glycol 4.0 g 2-Butoxyethanol 8.0 g 96% Ethanol 6.0 g o 0 Masquol DTPA Protex Company 2.0 g (pentasodium diethylenetriaminepentacetate) Hydroquinone 0.15 g 35°Be sodium bisulphite solution 1.3 g 0 22°Be ammonia solution 10.0 g Water qs 100.0 g pH 10.5 100 g of 20 volume hydrogen peroxide is added at the time of use. The mixture, applied for 20 minutes at 34°C on hair containing 90% naturally white hair, gives 4

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404 04 0 04 13 it, after shampooing and rinsing, a medium golden brown colour.

APPLICATION EXAM4PLE 2 The following tinctorial mixture is prepared: 6-Hydroxyindole 0.33 g p-Aminophenol 0.27 g Oleyl alcohol polyglycerolated with 2 moles of glycerol 4.5 g Oleyl alcohol polyglycerolated with 4 moles of glycerol 4.5 g Ethomeen 0 12 Armoon Hess Chemical Company Ltd. 4.5 g (oleylamine ethoxylated with 12 moles of ethylene oxide) Comperlan KD Henkel Company 9.0 g (copra diethanalamine) Propylene glycol 4.0 g 2-Butoxyethanol 8.0 g 96% Ethanol 6.0 g Masquol DTPA Protex Company 2.0 g (pentasodium diethylenetriaminepentacetate) Hydroquinone 0.15 g 35OBe sodium bisulphite solution 1.3 g 22*Be ammonia solution 10.0 g Water qs; 100.0 g pH 10.5 14 2 o 0 o eQ o *o a 0 0 0 0 9 0 0o 0400~ 0J 0400o 100 g of 20 volume hydrogen peroxide is added at the time of use. The mixture, applied for 20 minutes at 34°C on bleached hair, gives it, after shampooing and rinsing, a golden beige colour.

APPLICATION EXAMPLE 3 The following tinctorial mixture is prepared: 6-Hydroxy-l-methylindole 0.73 g Bis-(,-hydroxyethyl)-4-aminoaniline dihydrochloride 1.34 g 10 Cellosize WP 03 Union Carbide Company 2.0 g (hydroxyethylcellulose) Ammonium laurylsulphate 5.0 g 2-Butoxyethanol 15.0 g 96% Alcohol 5.0 g Masquol DTPA Protex Company 2.0 g (pentasodium diethylenetriaminepentacetate) Water qs 100.0 g pH 10.5 20 100 g of 20 volume hydrogen peroxide is added at the time of use. The mixture, applied for 20 minutes at 34"C on hair containing 90% naturally white hair, gives it, after shampooing and rinsing, a dark purple-grey colour.

0*00 0 0 *0 i 0 00 0o 0 0 *0 0000 *0 4 0 j I i!

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L, g 15 APPLICATION EXMPLE 4 The following tinctorial mixture is prepared: 6-Hydroxy-l-methylindole 0.29 g Para-phenylenediamine 0.22 g Octyldodecanol sold under the name of Eutanol G by the Henkel Company 8.0 g Oleic acid 20.0 g Monoethanolamine laurylethersulphate sold under the name of Sipon LM 35 by the Henkel Company 3.0 g Ethyl alcohol 10.0 g Benzyl alcohol 10.0 g Cetylstearyl alcohol ethoxylated with 33 moles of ethylene oxide, sold under the name of Simulsol GS by the Seppic Company 2.4 g Ethylenediaxninetetraacetic acid 0.2 g Cationic polymer consisting of recurrent units: 10 0 0 o $4.94 .9 .9.94.9 ~9.9 0 o .9.9 .9 .9, .9 o .9 .9 0440 o .9 .9 .94 .9 o .9.9 .9 .9 .9 .9 .9.

.9,9.9.9 o .9 .9 .9.9 .9 .9.9,9.9.94 .9 0 .9 .9.9.9.9.9, .9 .9

-(CH

2 )3 C96- -I 3 i CH 3 Cie Monoethanolamine Linoleic acid diethanolamide sold under the name of Comperlan F by the Henkel Company 2.2 g 7.5 g 8.0 g 16 20% Ammonia solution 10.2 g 35% Aqueous solution of sodium metabisulphite 1.3 g Hydroquinone 0.15 g l-Phenyl-3-methyl-5-pyrazolone 0.2 g Demineralized water qs 100.0 g The composition is mixed weight for weight with volume hydrogen peroxide, the pH of which is equal to 3, at the time of use.

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

~The colour obtained is a coppery beige blonde.

.o APPLICATION EXAMPLE The following tinctorial mixture is prepared: 6-Hydroxy-2-ethoxycarbonylindole 0.41 g 4 Para-phenylenediamine 0.22 g Octyldodecanol sold inder the name of 8 Eutanol G by the Henkel Company 8.0 g Oleic acid 20.0 g Monoethanolamine laurylethersulphate sold under the name of Sipon LM 35 by the Henkel Company 3.0 g Ethyl alcohol 10.0 g Benzyl alcohol 10.0 g Cetylstearyl alcohol ethoxylated with 1 33 moles of ethylene oxide, sold under i 17 the name of Simulsol GS by the Seppic Company 2.4 g Ethylenediaminetetraacetic acid 0.2 g Cationic polymer consisting.of recurrent units: C3 3

(CH

2 3

(CH

2 6

CH

3 Cl

!H

3 ClG 2.2 g o. Monoethanolamine 7.5 g

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Linoleic acid diethanolamide sold under the name of Comperlan F by the Henkel Company 8.0 g 20% Ammonia solution 10.2 g 35% Aqueous solution of sodium metabisulphite 1.3 g Hydroquinone 0.15 g l-Phenyl-3-methyl-5-pyrazolone 0.2 g Demineralized water qs 100.0 g The composition is mixed weight for weight with volume hydrogen peroxide, the pH of which is equal to 3, at the time of use.

The mixture thus obtained is applied for 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.

I 1 ie i. r 18 .4 a 4 a $4~ *#24 10 442: 24 4442~ tUt *442 4444 4 2 44 2 t~ 4 4 4 4 41L4 4 2 44 4 APPLICATION EXAMPLE 6 The following tinctorial mixture is prepared: 6-Hydroxy-2-carboxyindole 0.35 Para-phenylenediamine 0.22 Octyldodecanol sold under the name of Eutanol G by the Henkel Company Oleic acid 20.0 Monoethanolamine laurylethersulphate sold under the name of Sipon LM 35 by the Henkel Company Ethyl alcohol ±0.0 Benzyl alcohol 10.0 Cetylstearyl alcohol ethoxylated with 33 moles of ethylene oxide sold under the name of Simulsol GS by the Seppic Company 2.4 Ethylenediaminetetraacetic acid 0.2 Cationic polymer consisting of recurrent units: a 4,4.1*t'4 4 4 4$ 44 4 44 0 I- CH 2 3 1 kC

ICH

3 C1 0

CH

3 C le Monoethanolamine 2.2 g 7.5 g 19 -19 Linoleic acid diethanolamide sold under the name of Comperlan F by the Henkel Company 8.0 g 20% Ammonia solution 10.2 g 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 .0 ~equal to 3, at the time of use.

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

The colour is dark coppery beige blonde.

a 4 APPLICATION EXIAPLE 7 040 Example 6 is reproduced by using 0.29 g of 7-hydroxy 3-methyl indole instead of the 0.35 g of 6-hydroxy 2-carboxy-indole.

'The dyeing conditions are the snme as in Example 6.

.o The colour of the hair is irised light blond mahogany.

40 -APPLICATION EXAMPLE 8 Example 6 i s reproduced by using 0.34 g of 6-hydroxy 2,3-dimethyl indole instead of the 0.35 g of 6-hydroxy 2-carboxyindole.

The dyeing conditions are the same as in Example 6.

The hair is dyed in an irised light blond.

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APPLICATION EXAMPbE c The following tinctorial mixture is prepared: 7-Hydroxyindole 0.27 g p-Phenylenediamine 0.22 g Octyldodecanol sold under the name of Eutanol G by the Henkel Company 8.0 g Oleic acid 20.0 g Monoethanolamine laurylethersulphate 012,5t sold under the name of Sipon LM 35 by the Henkel Comlpany 3.0 g Ethyl alcohol 10.0 g Benzyl alcoh~ol 10.0 c Cetyistearyl alcohol ethoxylated with 33 moles of ethylene oxide sold under the name of Simulsol GS by the Seppic Company 2.4 g Ethylenediaminetetraacetic acid 0.2 g Cationic polymer consisting of recurrent units: o 11 CCH3 -otaolmn -ioecai itaoaiesl ne 04 00 0 the name of Comperlan F by the Henkel *Company 8.0 g Ammonia solution 10.2 g -35% Aqueous solution of sodium metabisulphite 1.3 g Hydroquinone 0.15g l-Phenyl-3- inethyl-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.

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

The colour is a dark ash pearly blonde.

APPLICATION EXAMPLE The following tinctorial mixture is prepared: 7-Hydroxyindole 0.53 g p-Aminophenol 0.44 g oo Octyldodecanol sold under the name of goo S..o 10 Eutanol G by the Henkel Company 8.0 g eo O Oleic acid 20.0 g $00000 Monoethanolamine laurylethersulphate sold under the name of Sipon LM 35 by the Henkel Company 3.0 g Ethyl alcohol 10.0 g S- Benzyl alcohol 10.0 g Cetylstearyl alcohol ethoxylated with o 0w o 33 moles of ethylene oxide sold under the name of Simulsol GS by the Seppic Company 2.4 g Ethylenediaminetetraacetic acid 0.2 g Cationic polymer consisting of recurrent units: JCh3 R3 (CH2) 3

(H

2 6 Ch3 Cl Ch3 C O 2.2 g ~7

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22 Monoethanolamine Linoleic acid diethanolamide sold under the name of Comperlan F by the Henkel 7.5 g Company 8.0 g 20% Ammonia solution 10.2 g 35% Aqueous solution of sodium metabisulphite 1.3 g Hydroquinone 0.15 g 1-Phenyl-3-methyl-5-pyrazolone 0.2 g 1o0 Demineralized water qs 100.0 g The composition is mixed weight for weight 6 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 .15 minutes on grey hair containing 90% white hair, then the hair is rinsed, washed, rinsed again and dried.

a 0 0 The colour is a coppery pearly blonde.

APPLICATION EXAMPLE 11 SLocks of hair containing 90% white hair are dyed 20 with a composition (Ag) having the following composition: S" '6-4lycroxyindole 2.0 g Ethanol 10.0 g Sodium laurylethersulphate 1.0 g 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.

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-22a- By applying thereafter during 3 minutes a mixture in equal amounts of a 0.5% solution of N,N-bis4 -hydroxyethyl paraphenylenediamine in water and a hydrogen peroxide solution in water at (pH 7) a lock coloured in a dark blond with purple shades is obtained after rinsing and drying.

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23 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 N-methoxyethyl-para-phenylenediamine at pH 10 and of 6% hydrogen peroxide is then applied for 3 minutes, hair of 'o 10 a light purple-chestnut colour is obtained after rinsing and drying.

o PREPARATION EXAMPLE 1 Preparation of 6-hydroxy-l-methylindole i1st stage: Preparation of 6-benzyloxy-l-methylindole S3 300 ml of toluene, 50 ml of methylsulphate and o 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 o 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 them, the desired product is obtained by evaporation. It melts at 79°C.

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C C oe a C 5I a CL O "a O C) Analysis of the product obtained after recrystallization from methanol gives the following results: Analysis for Calculated for Found

C

15

H

15

NO

C 81.01 80.92 H 6.33 6.36 N 5.91 5.80 0 5.75 6.99 2nd stace: 10 Preparation of 6-hvdroxv-1-methylindole The mixture consisting of 0.24 mole (57 g) of 6-benzyloxy-l-methylindole, 5.7 g of 10% palladium-oncharcoal, 114 ml of cyclohexene and 170 ml of 96% ethanol is heated 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 74 0

C.

Analysis of the product obtained gives the following results: Analysis for Calculated for Found CHgNO 73.47 6.12 9.52 10.88 73.57 6.12 9.39 11.07 PREPARATION EXAMPLE 2 Preparation of 7-hydroxy-3-methylindole 1st stace: Preparation of 1-F (3'-benzvloxy-5'-chloro-2'-nitro)- PhenylA-2-cyanooropane 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 Carbonatein 500 ml of acetone is taken to reflux for 8 hours. The reaction medium is diluted with 4 kg of iced 0:.::water to which has been added 500 ml of acetic acid. The desired product precipitates. After recrystallization from acetic acid it melts at 180 0

C.

Analysis of the product obtained gives the *0-o following results: CAnalysis from Calculated for Found O00

C

15

H,~N

2

O

00-20C C 60.67 60.72 H 4.14 4.12 0 0 N 8.84 8.64 0 15.15 15.01 Cl 11.19 11.34 2nd stage: Preparation of 7-hydroxy-3--methylindole The reaction mixture consisting of 20 g of 1-1 (3'-benzyloxy-5'-chloro-2'-.nitro)phenyl]-2-cyanopro.

pane and 10 g of 10% palladium-on-charcoal in 100 ml of 26 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 190 C.

Analysis of the product obtained gives the following results: 0949 Analysis for Calculated for Found o a CgHNO C 73.45 73.53 H 6.16 6.23 N 9.52 9.45 05 O 10.87 10.76 0 0O o 0

Claims (13)

1. Tinctorial composition for keratin fibres, characterized in that it contains, in a medium which is appropriate for dyeing these f ibres, at least one para- type precursor of an oxidation colorant in association with at least one heterocyclic coupler corresponding to formula: R 1 R 00(I 0coo( R Pop in which OH occupies positions 6 or 7 of the aromatic nucleus and R, represents a hydrogen atom or a CI-C 4 alkyl 0 Irl radical; R 2 or R 3 which may be identical or different, CC 0 designate a hydrogen atom, a Cl-C 4 lower alkyl radical, a carboxyl radical or a- C 1 -CZ, alkoxycarbonyl radical; 4s well as "o 00 their salts.

2. Composition according to Claim 1, characterized 00 oog in that the compounds of formula are chosen from Q6-hydroxyindole, 6-hydroxy-3-methoxycarbonylindole,

6-hydzoxy-l-methyl-3-methoxycarbonylindole, 6-hydroxy-1- methyl-2,3-dimethoxycarbonylindole, 6-hydroxy-,2- dimethylindole, 6-hydroxy-2-methylindole, 6-hydzoxy-2- carboxcyindole, 6-hydroxy-2, 3-dimethylindole, 6-hydroxy- 3-carboxyindole, 6-hydroxy-3-ethoxycarbonylindole, 6-hydroxy-2-ethoxycarbonylindole, 6-hydroxy-3- 7_ 1T; :nii; 28 methylindole, 6-hydroxy-l-methylindole, 7-hydroxyindole and 7-hydroxy-3-methylindole. 3. Composition according to either one of Claims 1 or 2, characterized in that the para-type precursors of oxidation colorants are chosen from the para-phenylene- diamines, the para-aminophenols and the para-heterocyclic precursors. 4. Composition according to any one of Claims 1 to 3, characterized in that the para-phenylenediamines are Schosen from the compounds of formula (II): oo o 7 000 (II) 0 8 0000 n 0000 RS ar in which R4, R, and which may be identical or dif- 0 0, ferent, represent a hydrogen or halogen atom, an alkyl radical having 1 to 4 carbon atoms or an alkoxy radical 0 0 having 1 to 4 carbon atoms, R 7 and which may be identical or different, represent a hydrogen atom or an o alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesyl- aminoalkyl, acetylaminoalkyl, ureidoalkyl, carbethoxy- aminoalkyl, piperidinoalkyl or morpholinoalkyl radical, these alkyl or alkoxy groups having from 1 to 4 carbon atoms, or again R 7 and form, together with the nitro- gen atom to which they are bonded, a piperidino or ge |ji V 29 00 0 0 000 0000 0 0000 00 0 0 0 .~00 0-. 0 0 0000 0 0 0 00 4 0 00 00 0 O 0~4 uJOO 0 0 0 ~4 0 A 00 OOOb 0 0 morpholino heterocycle, with the reservation that R, or R., represent a hydrogen atom when R 7 and R. do not represent a hydrogen atom, as well as the salts of these compounds. Composition according to Claim 4, characterized in that the compounds of formula (II) are chosen from p- phenylenediamine, p-to luylenediamine, methoxy-para- phenylenediamine, chloro-para-phenylenedianine, 2, 6- dimethyl-p-phenylenediamine, 2, diamine, 2-methyl-5-methoxy--para-phenylenediamine, 2,6- dimethyl-5-methoxy-para-phenylenediamine, N, N-dimethyl- para-phenylenediamine, 3-methyl-4-amino-N,N-diethyl- aniline, N,N-di(B-hydroxyethyl )para-phenylenediamine, 3-methyl-4-amino-N,N-di-(,B-hydroxyethyl)aniline, 3 -c hloro- 4-amnino N-di- (B-hydroxyethyl) an i line, 4-amino- N,N- (ethylcarbamylmethyl) aniline, 3-methyl-4-amino-N,N- (ethy'lcarbamylmethyl)aniline, 4-amino-N,N-(ethyl-g- piperidinoethyl) aniline, 3-methyl-4-amino-N,N-(ethyl-pa- piperidinoethyl) aniline, 4-amino-N (ethyl-,e-morpholino- ethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-p-morpholino- ethyl) aniline, 4-amino-N,N-(ethyl-,p-acetylaminoethyl) aniline, 4-amino-N- (B-methoxyethyl) aniline, 3-methyl-4- amino N- (ethyl- 1 8ac etyl aminoethyl) aniline, 4-amino-N,N- (ethyl 1

8-mesylaminoethyl) aniline, 3-methyl-4-amino-N,N- (ethyl -,a-mesylaminoethyl) aniline, 4-amino-N,N- (ethyl- sulphoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-fl- sulphoethyl) aniline, N- (4 '--amino) phenyl ]morpholine and (4 '-amino)phenyl]piperidine and their salts. V 30 9 1 0 0 0 00 o ao 09 0 S0 00 0 9~ D,4 4a 9 0 6. Composition according to any one of Claims 1 to 4, characterized in that the p-aminophenols are chosen from p-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4- aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-amino- phenol, 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-(B-hydroxy- ethyl)-4-aminophenol, 2-methoxy-4-aminophenol and 3- methoxy-4-aminophenol. 7. Composition according to any one of Claims 1 to 6, characterized in that the composition contains, in addition, ortho-type precursors of oxidation colorants, chosen from the ortho-aminophenols, the ortho-phenylene- diamines and the ortho-diphenols. 8. Composition according to any one of Claims 1 to 7, characterized in that the composition also contains, in addition to the heterocyclic couplers of formula meta-diphenols, meta-aminophenols, meta-phenylenedi- amines, meta-acylaminophenols, meta-ureidophenols, meta- carbalkoxyaminophenols, a-naphthol, 6-ketone compounds and pyrazalones.

9. Composition according to Claim 8, characterized in that the couplers which are different from the hetero- cyclic couplers of formula are chosen from 2,4- dihydroxyphenoxyethanol, 2,4-dihydroxyanisol, meta-aminophenol, resorcinol monomethylether, 2-methyl- 2-methyl-N- 31 2,6-dimethyl-3-aminophenol, 6-hydroxybenzomorpholine, 2,4-diaminoanisole, 2,4-diaminophenoxyethanol, 6-amino- benzomorpholine, [N-(B-hydroxyethyl)-2-amino-4-amino]- phenoxyethanol, 2-amino-N-(p-hydroxyethyl)-4-aminoani- sole, (2,4-diamino)phenyl-p,--dihydroxypropylether and 2,4-diaminophenoxyethylamine and their salts. 9 0 Composition according to any one of Claims 1 to 0 0 o, 0 9, characterized in that the composition also contains 0 0a .o direct colorants. 0o

11. Composition according to any one of Claims 1 to characterized in that the para-type oxidation color- ants and the couplers are present in proportions of ,o between 0.3 and 7% by weight with respect to the total 0 a weight of the composition.

12. Composition according to any one of Claims 1 to 11, characterized in that the compound of formula is present in proportions of between 0.05 and 3.5% by weight with respect to the total weight of the composition.

13. Composition according to any one of Claims 1 to 12, characterized in that the medium which is appropriate for dyeing these fibres is aqueous and has a pH of between 8 and 11. 1A----Compos-i-sion-a-ee-d-i-ng-e-a-ny-one-of-eraims--t 13, characterized in that the compo i-i-on also contains i anionic, cationic i-Oonic or amphoteric surfactants or t-r mixtures. 1 -i 31a

14. Composition according to any one of Claims 1 to 13, characterized in that the composition also contains anionic, cationic, nonionic, or amphoteric surfactants or their mixtures present in proportions of between 0.5 and 55% by weight with respect of the total weight of the composition. I i I tIll 4 *4 4 f:-A 4 cc- (4r 21.\ 32 Composition according to any one of Claims 1 to 14, characterized in that the composition also contains organic .solvents in proportions of between 1 and 40% by weight with respect to the total weight of the compo- sition.

16. Composition according to any one of Claims 1 to characterized in that the composition also contains 00 C05 '"ef denes) (Co \xe>-jr crie o thickening agentsf, antioxidants), penetration agents, 0" sequestering agents, buffers and/or fragrances.

17. The composition according to any one of Claims 1 to 16, characterized in that it is presented in the form of liquids, creams or gels and that it is optionally packed in aerosols in the presence of a propellant.

18. Process for the preparation of a tinctorial oo composition intended to be applied immediately on human 0 0Q hair, characterized in that the tinctorial composition defined in any one of Claims 1 to 17 is mixed at the time of use with an oxidizing solution in sufficient quantity to form a colorant.

19. Process for dyeing keratin fibres, in particular human hair, characterized in that a composition as defined in any one of Claims 1 to 17 is applied on the said fibres in the presence of an oxidizing agent, that the composition is left in contact with the fibres for to 40 minutes, and that the application is followed by rinsing the hair, washing, rinsing and drying. Li^ -33- Process for dyeing keratin fibres, in particular human hair, characterized in that firstly the para- precursor of the oxidation colorant is applied, and secondly at least one heterocyclic coupler of formula (I) is applied, the 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 S oo stage. 0 0 o 0 0 DATED this 8th day of September 1989. O L'OREAL o t 4 l WATERMARK PATENT TRADEMARK ATTORNEYS QUEEN STREET MELBOURNE. VIC. 3000. I It