AU672400B2 - Method for dyeing keratin fibres in an alkaline medium by means of 2-substituted para-aminophenols combined with 6- or 7-hydroxyindole, and compositions therefor - Google Patents

Abstract

A method for dyeing keratin fibres by applying at least one para-aminophenol of formula (I), wherein Y is oxygen or sulphur, and R is alkyl, monohydroxyalkyl or polyhydroxyalkyl, and acid addition salts thereof, as well as 6-hydroxyindole and/or 7-hydroxyindole, the colour being revealed at alkaline pH by means of an oxidizing agent.

Description

7

I

OPI DATE 18/11/93 AOJP DATE 27/01/94 APPLN. ID 39563/931111III1111111111111111111lili PCT NUMBER PCT/FR93/003491111111111 111 liil hEo li AU9339565 DEMANDE INTERNATIONALE PUBLIEE EN VERTU DU TRAITE DE COOPERATION EN MATIERE DE BREVETS (PCT) (51) Classification internationale des brevets 5 Num~ro de publication internationale: WO 93/20794 A61K 7/13 Al (43) Date de publication internationale: 28 octobre 1993 (28.10.93) (21) Num~ro de la deniande internationale: PCT/FR93/00349 (74) Mandataire: BUREAU D.A. CASALONGA 30SF; 8, avenue Percier, F-75008 Paris (FR).

(22) Date de dip6t international: 7 avril 1993 (07.04.93) (81) Etats disignis: AU, CA, JP, US, brevet europ~en (AT, BE, Donnees relatives ii la priorite: CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, 92/04346 9 avril 1992 (09.04.92) FR PT, SE).

(71) D~posant (pour tous les Etats d&ign&s sauf US): L'OREAL Puhli~e [FR/FR]; 14, rue Royale, F-75008 Paris Avec rapport de recherche internationale.

(72) Inventeurs; et 1 r lnventeurs/D~posants (US seulernent) COTTERET, Jeana [FR/FR]; 15, ale des Meuniers, F-78480 Verneuil-sur- 0L Seine AUDOUSSET, Marie, Pascale [FR/FR];40 106, rue Baudin, F-92300 Leval lois- Perret (FR).

(54) Title: METHOD FOR DYEING KERATIN FIBRES IN AN ALKALINE MEDIUM BY MEANS OF 2-SUBSTITUTED PARA-AMINOPHENOLS COMBINED WITH 6- OR 7-HYDROXYINDOLE, AND COMPOSITIONS THERE-

FOR

(54) Titre: PROCEDE DE TEINTURE DES FIBRES KERATINIQUES EN MILIEU ALCALIN METTANT EN (EUVRE DES PARAAMINOPHENOLS SUBSTITUES EN POSITION 2 EN ASSOCIATION AVEC LE 6- OU 7-HYDROXYINDOLE ET COMPOSITIONS MISES EN CEUVRE DANS LE PROCEDE

K--'I

CH2 YR (57) Abstract A method for dyeing keratin fibres by applying at least one para-aminophenol of formula wherein Y is oxygen or sulphur, and R is alkyl, monohydroxyalkyl or polyhydroxyalkyl, and acid addition salts thereof, as well as 6-hydroxyindole and/or 7-hydroxyindole, the colour being revealed at alkaline pH by means of an oxidizing agent.

(57) Abrege L'invention est relative A un procWd6 de teinture des fibres k~ratiniques, caract~ris6 par le fait que V'on applique sur ces fibres au momns un paraaminoph~nol de formule dans laquelle Y est oxyg~ne ou soufre, R est alkyle, monohydroxyalkyle, polyhydroxyalkyle, ainsi que leurs sels d'addition d'acides, et le~ 6-hydroxyindole et/ou le 7-hydroxyindole, la couleur 6tant r&v6l6e i pH alcalin i l'aide d'un agent oxydant.

I Process for dyeing keratinous fibres in alkaline medium using paraaminophenols substituted in position 2 in combination with 6- or 7-hydroxyindole and compositions used in the process.

The present invention relates to a new process for dyeing keratinous fibres and in particular human keratinous fibres, using para-aminophenol substituted in position 2 in combination with 6- or 7-hydroxyindole and an oxidising agent in alkaline medium, and to the compositions used during this process.

It is known to dye keratinous fibres and in particular human hair with dyeing compositions containing oxidation dye precursors, in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols, generally called "oxidation bases", and couplers, also called colouring modifiers, more particularly aromatic meta-phenylenediamines, meta-aminophenols and metadiphenols, which make it possible to modify and enrich with highlights the "base" colourings obtained with the condensation products of the oxidation bases.

Research, in the field of oxidation hair dyeing, is for oxidation dye precursors and couplers which make it possible to confer on hair a colouring having a satisfactory resistance to light, washings, bad weather, perspiration and to the various treatments which hair may be subjected to, and to obtain a wide range of colouring shades.

The para-aminophenols substituted in position 2, and their use in dyeing compositions for keratinous fibres in combination with standard couplers of benzene type are known and described in the patent FR 2,637,282.

A dyeing process for dyeing keratinous fibrls in acid medium is described in the patent FR 2,659,228 of the Applicant as using a composition containing, as coupler, 6-hydroxyindole, 7-hydroxyindole or their derivatives with oxidation dye precursors such as paraaminophenols. However, such a process did not provide, after application to the fibres, a sufficiently resistant colouring.

-RA4 Lo o TNf i f i, i~-j l iI 2 In the patent FR 2,636,236, the Applicant describes dyeing compositions for dyeing keratinous fibres in alkaline medium, containing 6-hydroxyindole or 7-hydroxyindole as coupler combined with an oxidation base including para-aminophenol and some of its derivatives. The colourings obtained with these compositions did not exhibit a satisfactory resistance, especially to light.

The Applicant has discovered, which forms the subject of the invention, that the use of certain para-aminophenols substituted in position 2 as oxidation dye precursors in combination with 6-hydroxyindole or 7-hydroxyindole and of an oxidising agent makes it possible to obtain, in alkaline medium, after application to keratinous fibres and in particular human hair, a wide range of colourings with warm shades exhibiting a resistance to light, to washings and to bad weather, to perspiration and to the various treatments which hair may be subjected to, which is particularly outstanding and greater than those of the prior art.

The subject of the present invention is thus a process for dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising the application to these fibres of at least, as oxidation dye precursor, one para-aminophenol substituted in position 2 of formula below, as coupler, 6-hydroxyindole or 7-hydroxyindole and one oxidising agent, at alkaline pH.

Another subject of the invention is a dyeing agent containing two components, one of the components of which comprises the oxidation dye precursor of formula defined below and 6- or 7-hydroxyindole, and the other the oxidising agent.

Another subject of the invention applies to the ready-to-use composition containing the various agents used for dyeing keratinous fibres in alkaline medium.

Another subject of the invention is dyeing requisites or "kits", containing several components, which make possible the use of the process indicated j II:

V

7- 0

A,

Ii i

S.

ir^

I

1 i i 3 above.

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

The process for dyeing keratinous fibres and in particular human keratinous fibres such as hair in accordance with the invention is essentially characterised in that there is applied to these fibres at least one para-aminophenol substituted in position 2 of formula

(I)

-ir 1 1

I;

a

B

t

I

i 1

I

I:

ii!- I j

I

CH

2

YR

NH

2 in which: Y represents an oxygen atom or sulphur atom, R represents a C 1

-C

4 alkyl, C 1

-C

4 monohydroxyalkyl or C 2

-C

4 polyhydroxyalkyl radical, and their addition salts with an acid; 6-hydroxyindole and/or 7-hydroxyindole; the colour being displayed at a pH greater than 7 using an oxidising agent.

According to the process in accordance with the invention, there is applied to keratinous fibres and in particular human keratinous fibres at least one composition containing, in a medium suitable for dyeing, at least one para-aminophenol substituted in position 2 of formula defined above as oxidation dye precursor, in combination with 6-hydroxyindole and/or 7-hydroxyindole as coupler, the colour being displayed at alkaline pH using an oxidising agent present in the composition (A) or applied separately simultaneously or sequentially by means of a composition containing it in a medium -,le ii i i "It i i i. i Sii i i Ij P l

-J

-4suitable for dyeing.

Among the preferred meanings of the radical R in the para-aminophenol compounds of general formula the C,-C 4 alkyl radical denotes the methyl, ethyl, propyl, isopropyl, butyl or isobutyl radicals and the mono- or polyhydroxyalkyl radical denotes -CH 2

-CH

2

OH,

-CH

2

-CHOH-CH

2 -OH or -CH 2

-CHOH-CH

3 The acid salts corresponding to the para-aminophenol compounds of general formula are preferably chosen from the hydrochlorides, the sulphates, the hydrobromides or the tartrates.

Among the para-aminophenols of general formula there may be mentioned the following compounds: 2-methoxymethyl-4-aminophenol, 2-ethoxymethyl-4-aminophenol, 2-propoxymethyl-4-aminophenol, 2-isopropoxymethyl-4-aminophenol, 2- (p-hyclroxyethoxymethyl) -4-aminophenol, 2-methylthiomethyl-4-aminophenol, 2- (fi-hydroxyethylthiomethyl) -4-aminophenol,, 2- (pe,,-dihydroxypropylthiomethyl) -4-aminophenol, and their salts.

Among the preferred compounds of formula there may be mentioned: 2-methoxymethyl-4-aminophenol 2-ethoxymethyl-4-aiinophenol 2- (p-hydroxyethctxyrnethyl )-4-aminophenol 2-methylthiomethyl-4-aminopheno1 and their salts.

According to the process of the invention, 6-hydroxyindole is preferably used, in combination with the para-aminophenol of general formula defined abvas coupler.

The oxidising agent is preferably chosen from hydrogen peroxide, urea hydrogen peroxide, alkali metal bromates, or persalts such as the perborates and the persulphates. Hydrogen peroxide is particularly prfrrd 7,$ I: IT~r i The composition which contains, as oxidation dye precursor, at least one para-aminophenol of formula and 6-hydroxyindole and/or 7-hydroxyindole as coupler can have a pH of between 3 and 10.5 and can be adjusted to the chosen value by means of basifying agents generally used in dyeing keratinous fibres, such as aqueous ammonia, alkali metal carbonates, alkanolamines such as the mono-, di- and triethanolamines and their derivatives, or sodium or potassium hydroxide, or standard acidifying agents, such as inorganic or organic acids, such as hydrochloric, tartaric, citric and phosphoric acids.

The pH of the composition containing the oxidising agent as defined above is such that, after mixing with the composition A, the pH of the mixture is greater than 7 and preferably of between 8 and 11.

The compounds of formula are present in the composition applied to keratinous fibres in proportions preferably of between 0.05 and 3.5 by weight with respect to the total weight of the composition; 6-hydroxyindole and/or 7-hydroxyindole are present therein in proportions of between 0.01 and 4 by weight with respect to the total weight of the composition.

The dyeing compositions defined above and used in the dyeing process of tb: invention can also contain, in addition to the para-aminophenol of formula defined above, other para and/or ortho oxidation dye precursors known in themselves.

These oxidation dye precursors of ortho or para type can be chosen from para-phenylenediamines, paraaminophenols other than those of formula "paraheterocyclic precursors derived from pyridine or from i pyrimidine, such as 2,5-diaminopyridine, 2-hydroxy- 2 4 ,5,6-tetraaminopyrimidine, 4,5-diamino-l-methylpyrazole or 2-dimethylamino- 4,5,6-triaminopyrimidine, ortho-aminophenols and the socalled "double" bases.

1 i i 4'

-V

I l 1 1 l -6- As para-phenylenediamines, there may more particularly be mentioned the compounds corresponding to the formula

(II):

Ks i

N

RI

R3 O n) R2 NH2 in which:

R

1

R

2 and R 3 which are identical or different, represent a hydrogen or halogen atom, a C 1 -C4 alkyl radical, a C 1

-C

4 alkoxy radical, a C 1

-C

4 hydroxyalkyl radical, a carboxyl radical or a sulpho radical;

R

4 and R 5 which are identical or different, represent a hydrogen atom, or an alkyl, hydroxyalkyl, alkoxyalkyl, carbamoylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, sulphoalkyl, piperidinoalkyl, morpholinoalkyl or phenyl radical, the phenyl optionally being substituted in the para position by an amino group, or else R 4 and R, form, jointly with the nitrogen atom to which they are bonded, a piperidino or morpholino heterocycle, with the proviso that Ri or R 3 represents a hydrogen atom when R. and R 5 do not represent a hydrogen atom, and the salts of its compounds. These alkyl or alkoxy groups have from 1 to 4 carbon atoms and denote especially methyl, ethyl, propyl, methoxy and ethoxy.

Among compounds of formula there may be mentioned para-phenylenediamine, p-toluylenediamine, methoxy-para-phenylenediamine, chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethylpara-phenylenediamine, 2,6-diethyl-para-phenylenediamine, para-phenylenediamine, 2,6-dimethyl-5-methoxy-parary i r O ~rN -7 phenylenediamine,, N,N-dimethyl-para-phenylenediamine, N, N-diethyl -para-phenylenedi amine, N, N-dipropyl -paraphenylenediamine, 3-methyl-4--amino-N ,N-diethylaniline, N,N-di(p-hydroxyethyl) -para-phenylenediamnine, 3-methyl- 4-amino-N,N-di (f-hydroxyethyl) aniline, 3-chloro-4,.amino- N,N-di (p-hydroxyethyl )anlie 4-amino-N-athyl-N-(carbamoylmethyl )aniline, 3-methyl-4-aznino-N-ethyl-N- (carbamoylmethyl) aniline, 4-amino-N-ethyl-N- (p-piperidinoethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (p-piperidinoethyl) aniline, 4 -amino -N-ethyl (p -morphol inoethyl ani line, 3-methyl -4-amino-N-ethyl-N- (,6-morphol inoethyl) aniline, 4-amino-N-ethyl-N-(,p-acetylaminoethyl)aniline, 4-amino-N- (f-methoxyethyl )aniline, 3-methyl-4-amino- N-ethyl-N- (5-acetylaminoethyl )aniline, 4-amino-N-ethyl- N- (p-mesylaminoethyl )aniline, 3-methyl-4-amino-N-ethyl- N- (p-mesylaminoethyl )aniline, 4-amino-N-ethyl-N- (p-sulphoethyl )aniline, 3-methyl-4-amino-N-ethyl-N- (B-sulphoethyl) aniline, N- (4 1 -aminophenyl)morpholine, N- (4 -aminophenyl )piperidine, 2-hydroxyethyl-para-phenylenediamine, fluoro-para-phenylenediamine, carboxy-para-phenylenediamine, sulpho-para-phenylenediamine, 2-isopropyl-paraphenylenediamine, 2- (n-propyl) -para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl- 3 -methyl-para-phenylenediamin6, N-ethyl (5 -hydroxyethyl) -para-phenylenediamine, N-dihydroxypropyl-paraphenylenediamine, N- -aminophenyl) -para-phenylenediamine or N-phenyl-para-phenylenediamine.

These para-phenylenediamines can be introduced into the dyeing composition either in the form of the free base or in the form of salts, such as hydrochloride, hydrobromide or sulphate.

Among the para-aminophenols other than those of formula there may be mentioned p-am~inophenol, 2-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro- 4-aminophenol, 2, 6-dimethyl-4-aminophenol, 4-aminophenol, 2, 3-dimethyl-4-aminophenol, 2, 4-aminophenol, 2-(p-hydroxyethyl) -4-aminophenol, 2-methoxy-4-aminophenol, 3-methoxy-4-aminophenol, 1(1

I

A

1:.

8 1 3-(p-hydroxyethoxy)-4-aminophenol, 2-aminomethyl-4-aminophenol or 2-(A-hydroxyethylaminomethyl)-4-aminophenol.

I The so-called "double" bases are bisphenylalkylenediamines. corresponding to the formula: ZI

Z

2 R6 *N -CH2- -H2- NR9 in which: Zi and Z 2 which are identical or different, represent hydroxyl groups or groups NHR 10 where R 10 denotes a hydrogen atom or a lower alkyl radical;

R

7 and R 8 which are identical or different, represent either hydrogen atoms, or halogen atoms, or also alkyl radicals;

R

6 and R, which-care .J.entical or different, represent a hydrogen atom or an alkyl, hydroxyalkyl or aminoalkyl radical, it being possible for the amino residue to be substituted; Y' represents a radical taken from the group consisting of the following radicals:

-(CH

2 )q-CHOH-(CH 2 q- (2CH)p-;

CH

3 in which n is an integer between 0 and 8 and m, q and p are integers between 0 and 4, it also being possible for this base to be provided in the forn of its addition salts with acids.

The alkyl or alkoxy radicals shown above preferably denote a group having 1 t, 4 car on atoms and especially methyl, ethyl, propyl, mithoxyand ethoxy.

thoxy V. 1 e-th -9- Among 'the compounds of formula (III), there may be mentioned N,N'-bis (p-hydroxyethyl)-N,N'-bis(4 '-aminophenyl) -1 ,3-diamino-2-propanol, N,N' -bis (fl-hydroxyethyl) N, N'-bis (4 '-aminophenyl )ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'I -bis (#p-hydroxyethyl) N I -b i's (4 -aminophenyl) tetramethylenediamine, N,N'-bis (4-methylamnophenyl )tetramethylenediamine, N,N'-bis (ethyl)-N,N'-bis(4 '-amino- 3' -methyiphenyl )ethylenediamine.

The oxidation dye precursors of ortho type are chosen from ortho-aminophenols, such as 1-amino- 2-hydroxybenzene, 6-;rethyl-l-hydroxy-2-aninobenzene or 4-methyl-1-amino-2-hydroxybenzene, and ortho-phenylenediamines.

The compositions defina-1 above, applied in the dyeing of keratinous fibres, can also contain, in addition to 6-hydroxyindole and/or 7-hydroxyindole used as couplers, othur coup,-ers known in themselves, such as meta-diphenols, meta-aminophanols, meta-phenylenediamines, meta-acylaminophenols, meta-ureidophenols, metacarbalkoxyaminophenols, a-naphthol, or couplers having an active methylene group, such as p-ketone compounds or pyrazolones.

Among these couplers, there may be more particularly mentioned 2,4-dihydroxyphenoxyethanol 2,4-dihydroxyanisole, meta-aminophenol, resorcinol monomethyl ether, resorcinol, 2-methylresorcinol, 2-methyl-5-amino phenol, N-(p-hydroxyethyl) N- -mesylaminoethyl) -2-methyl-5-aminophenol, 2, 6-dimethyl-3-aminophenol, 6-hydroxybenzomorpholiie, 2, 4-diaminoanisole, 2, 4-diaminophenoxyethanol, 6-aminobenzomorpholine, (p-hydroxyethyl )amino-4-amino ]phenoxyethanol, 2-amino-4-[ (p-hydroxyethyl)amino]anisole, 2, 4-diaminophenyl p y-dihydroxypropyl ether, 2, 4-diaminophenoxyethylamine, 1, 3-dimethoxy-2, 4-diaminobenzene, 1,3, 5-trimethoxy-2, 4-diaminobenzene, -,.-amino-3, 4-methylenedioxybenzene, 1 -hydroxy- 3,4 -methylenedioxybenzene, 2-chloro-6-rnethyl-3-aminophenol, 2-methyl-3-aminophenol,

J

A

Ai 2-chlororesorcinol, 6-methoxy-3-hydroxyethylaminoaniline, 1-ethoxy-2-bis (-hydroxyethyl)amino-4-am inobenzene, 3-diethylaminophe.nol, 1,3-dihydroxy-2-methylbenzene, 1-hydroxy-2,4-dichloro-3-aminobenzene, 4,6-hydroxyethoxy- 1,3-diaminobenzene, 4-methyl-6-ethoxy-1,3-diaminobenzene, 4 -chloro-6-methyl-3-aminophenol, 6-chloro-3-trifluoroethylaminophenol and their salts.

There may be added to these compositions, as is well known in the state of the art, especially for the purpose of shading or enriching in highlights the colourings introduced by the para-aminophenol combined with 6-hydroxyindole and/or 7-hydroxyindole, direct dyes such as azo dyes, anthraquinone dyes or nitrated derivatives of the benzene series.

The combined oxidation dye precursors of para and/or ortho type, as well as the couplers used in the dyeing compositions used in the process according to the invention, preferably represent from 0.3 to 7 by weight with respect to the weight of the said composition.

The dyeing compositions used in the process according to the invention also contain, in their preferred embodiment, anionic, cationic, nonionic or amphoteric surface-active agents or their mixtures. Among these surface-active agents, there may be mentioned alkylbenzenesulphonates, alkylnaphthalenesulphoxA:tes, suldhates, ether sulphates and fatty alcohol sulphonates, quaternary ammonium salts such as trimethylcetylammonium bromide, or cetylpyridinium bromide, optionally oxyethylenated fatty acid ethanolamides, polyoxyethylenated acids, alcohols or amines, polyglycerolated fatty alcohols, polyoxyethylenated or polyglycerolated alkylphenols, and polyoxyethylenated alkyl sulphates.

These surface-active agents are present in the compositions in proportions of between 0.5 and 55 by weight, preferably between 2 and 50 by weight with respect to the total weight of the composition.

i~hi 7A,cv 11 These. compositions can also contain organic solvents for solubilising the components which would not be sufficiently soluble in water. Among these solvents, i there may be mentioned, by way of example, CiC 4 lower alcohols, such as ethanol or isopropanol; glycerol; glycols or glycol ethers such as 2-butoxyethanol, ethylene glycol, propylene glycol and the monoethyl ether and the monomethyl ether of diethylene glycol, and the aromatic alcohols such as benzyl alcohol or phenoxyethanol, the analogous products and their mixtures.

The solvents are preferably present in proportions 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.

The thickening agents which it is possible to add to the compositions used in the process according to the invention can be chosen from sodium alginate, gum arabic, optionally crosslinked acrylic acid polymers, cellulose derivatives or heterobiopolysaccharides such as xanthan gum. It is also possible to use inorganic thickening agents such as bentonite.

These thickening agents are preferably present in proportions of between 0.1 and 5 and in particular between 0.2 and 3 by weight with respect to the total weight of the composition.

The antioxidising agents which can be present in the compositions are chosen in particular from sodium sulphite, thioglycolic acid, sodium bisulphite, dehydroascorbic acid, hydroquinone and homogentisic acid.

These antioxidising agents are present in the composition in proportions of between 0.05 and 1.5 by weight with respect to the total weight of the composition.

These compositions can also contain other cosmetically acceptable adjuvants, such as, for example, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, treatment agents, conditioning agents, film-forming agents, preserving agents, INTERNATIONAL SEARCH REPORT International application No.

PCT/FR 93/00349 1 3 12 opacifying agents and the like.

The composition applied to the hair can be provided in various forms, such as in the liquid, cream or gel form or any other form suitable for carrying out dyeing of keratinous fibres and especially of human hair.

These compositions can be packaged under pressure in aerosol containers in the presence of a propellant and to form foams.

Another subject of the invention is the ready-touse composition used in the process defined above.

According to a particularly preferred embodiment, the process comprises a preliminary stage consisting in storing in a separate form, on the one hand, the composition containing, in a medium suitable for dyeing, at least, as oxidation dye precursor, one para-aminophenol corresponding to the formula defined above and, as coupler, 6-hydroxyindole and/or 7-hydroxyindole in the form of a component and, on the other hand, a composition containing the oxidising agent as defined above in the form of a component and in mixing them extemporaneously before applying this mixture to keratinous fibres, as shown above, the resulting composition having a pH value greater than 7 and preferably between 8 and 11.

In accordance with the invention, the dyeing process consists in applying the mixture obtained to hair, in leaving the mixture exposed for 10 to minutes, preferably 15 to 30 minutes, and then rinsing the hair, washing it with the shampoo, rinsing it again and drying it.

It is also possible, in accordance with the invention, to apply separately a composition containing the para-aminophenol of formula 6-hydroxyindole and/or 7-hydroxyindole and the oxidising agent which can be introduced, just before application, into the composition applied in the second stage or else be added to the keratinous fibres in a third stage, so that the mixture S which forms in situ in the fibres has a pH greater than :i i i ii

I

i ?in \L7* o/ i II i~Zs_ I -13-i 31 7, the exposure, washing and drying conditions being the same as above.[ Another subject of the invention is an ,agent for dyeing keratinous fibres, in particular huinan hair, essentially characterised in that it comprises at least two components, one of the components consisting of the composition defined above and the other consisting of the composition also defined above, the pH of the compositions and being such that, after mixing in proportions of 90 to 10 for the composition and of to 90 for the composition the resulting composition has a pH greater than 7, and preferably of between 8 and 11.

The composition applied to keratinous fibres results in particular from a mixture of 10 to 90 %of the component with 90 to 10 of the component (B) containing an oxidising agent and has a pH greater than 7 and preferably of between 8 and 11.

This two-component dyeing agent can be packaged4 in a multi-compartment device or dyeing kit which constitutes another subject of the invention, or any other multi-compartment packaging syetem in which one of the compartments contains the component and the second compartment contains the component these devices can be equipped with a means making it possible to deliver the desired mixture to the hair, such as the devices described more particularly in patent US-A-4,823,985 of the Applicant.

The examples which follow are intended to illustrate the invention without having in any way a limiting character.I 7 ~EXAMPLES i to The dyeing of hair is carried out by applying, to permanent wave or non-permanent wave grey hair containing 90 white hairs, an extemporaneous mixture of the dyeing composition and of the oxidising composition This mixture is left to act for 30 minutes, the hair is then rinsed and shampooing is carried out. Af terJ Rq/ 1e, 7

QJ

'r 0 I

,"I

i i cn

I

r

F

i 1

I

14 drying, the hair is dyed in the shade specified at the bottom of the table below.

in g 1 2 3 4 A) Dyeing composition 6-Hydroxyindole 0.532 0.798 0.266 7-Hydroxyindole 0.532 2-Methoxymethyl-4-aminophenol 0.436 0.918 0.918 0.612 3-Amino-6-methylphenol 0.246 6- (f-hydroxyethoxy)- 1,3-diaminobenzene 0.482 Substrate 1 x x Substrate 2 X X Water qs 100 100 100 100 B) Oxidising composition Hydrogen peroxide solution, 20 volumes 100 100 100 100 Phosphoric acid qs pH 3 3 3 3 1/3 A 2/3 B w/w mixture X A B w/w mixture X X X pH of the mixture 9.8 9.8 9.6 9.8 Shades obtained on cop- cop- cop- strong permanent wave hair pery pery pery iridescontaining 90 white golden dark red cent hairs blonde blonde chest- blonde nut dark blonde

I

4i

I

K\'V7- O' Nt 4 I-MCAM;ilb 15 in g 5 6 7 8 A) Dyeing coiposition 6-Hydroxyindole 0.532 0.532 0.532 0.266 2-Methoxymethyl-4aminophenol 0.612 2-Ethoxymethyl-4aminophenol hydrochloride 0.815 2-(p-hydroxyethoxymethyl)- 4-aminophenol monohydrate monotartrate 1.405 2-Methylthiomethyl-4aminophenol 0.338 Substrate 3 X Substrate 2 X X X Water qs 100 100 100 100 B) Oxidising composition Hydrogen peroxide solution, 20 volumes 100 100 100 100 Phosphoric acid qs pH 3 3 3 3 A+B w/w mixture X X X X pH of the mixture 10.0 9.5 9.5 9.8 Shades obtained on non- golden permanent wave grey coppe natural hair containing white hairs On permanent wave grey strong strong slightnatural hair containing golden cop- ly 90 white hairs cop- pery golden pery coppery £4 4 b7 .W |i Br- I j i

I

uUjecr or the invention is dyeing requisites or "kits", containing several components, which make possible the use of the process indicated I Y4rr---4t:rr..--

I

t'' \i l 1 i-; r 16 COLOURING SUBSTRATE No.1 Octyldodecanol sold under the name Eutanol G by the company Henkel Triethanolamine lauryl sulphate containing 40 of AM Ethyl alcohol Benzyl alcohol Oleocetyl alcohol oxyethylenated with 30 mol of ethylene oxide Cationic polymer in solution containing 60 of AM, consisting of recurrent units: CH3

H

3 N- (CH2)3 -(CH2) C3 crl CH 3 cr Monoethanolamine Linoleic acid diethanolamide sold under the name of Comperlan F by the company Henkel 20 Aqueous ammonia Aqueous sodium metabisulphite solution containing 35 of AM Hydroquinone 1-Phenyl-3-methyl-5-pyrazolone Sequestering agent qs 8 g 1.2 gAM 10.5 g 10 g 2.7 g 2.22 gAM ii

'I

41 7.2 g 8 g 10.2 g 0.46 gAM 0.15 g 0.2 g 4' 9:i i 1:I; i:: i 18 i i

O

ii i iY o~ 4- L~ j- 1 one I W~ 17

I

I

i COLOURING SUBSTRATE No.2 Octyldodecanol sold under the name Eutanol G by the company Henkel Oleic acid Monoethanolainine lauryl ether sulphate sold under the name Sipon LM 35 by the company Henkel Ethyl alcohol Benzyl alcohol Cetearyl alcohol oxyethylenated with 33 mol of ethylene oxide, sold under the name Simulsol GS by the company Seppic Ethylenediaminetetraacetic acid Cationic polymer consisting of recurrent units, containing 60 of AM 8 g 20 g 3 g 10 g 10 g 2.4 g 0.2 g 2.2 g AM -2) I C1, C3 CH3 Monoethanolainine Linoleic acid diethanolamide sold under the name Comperlan F by the company Henkel 20 Aqueous ammonia Aqueous sodium metabisuiphite solution containing 35 of AM Hydroquinone 1-Phenyl-3.methyl-5-pyrazolone 7.5 g 8 g 10.2 g 0. 46 g AM 0. 15 g 0.2 g kL

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18 COLOURING SUBSTRATE No. 3 Oleic alcohol polyglycerolated with 2 mol of glycerol Oleic alcohol polyglycerolated with 4 mol of glycerol, containing 78 of AM Oleic acid Oleic amine oxyethylenated with 2 mol of ethylene oxide, sold under the name Ethomeen o 12 by the company Akzo Diethylaminopropyl laurylaminosuccinamate, sodium salt, containing 55 of AM Oleic alcohol Coconut oil acid diethanolamide Propylene glycol Dipropylene glycol Ethyl alcohol Propylene glycol monomethyl ether Aqueous sodium metabisulphite solution containing 35 of AM Ammoniumi acetate Monoethanolamine qs pH =9.8 Antioxidising agent, sequestering agent qs 4 g 5.7 g AM 3.0 g 7 g 3 g AM 5 g 12 g 3.5 g 0.5 g 7.0 g 9 g 0.46 g AM 0.8 g

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Claims (12)

1. Process for dyeing keratinous fibres, in par- ticular human keratinous fibres, such as hair, charac- terised in that there is applied to these fibres at least one para-aminophenol substituted in position 2 of for- mula: i CH2YR in which: Y represents an oxygen atom or sulphur atom, R represents a Cl-C 4 alkyl, C 1 -C4 monohydroxyalkyl or C 2 -C 4 polyhydroxyalkyl radical, and their addition salts with an acid; and, 6-hydroxyindole and/or 7-hydroxyindole; the colour being displayed at alkaline pH and using an oxidising agent.

2. Process according to Claim 1, characterised in that there is applied to keratinous fibres, in particular human keratinous fibres, at least one composition (A) containing, in a medium suitable for dyeing, at least, as oxidation dye precursor, one para-aminophenol substituted in position 2 of formula and 6-hydroxyindole and/or

7-hydroxyindole as coupler; the colour being displayed at alkaline pH and using an oxidising agent present in the composition or applied separately simultaneously or sequentially by means of a composition containing it in a medium suitable for dyeing. 3. Process according to Claim 1 or 2, characterised in that the oxidising agent is chosen from hydrogen peroxide, urea hydrogen peroxide, alkali metal bromates and persalts. jl B amine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl- para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, para-phenylenediamine, 2,6-dimethyl-5-methoxy-para- I -9 4. Process according to any one of Claims 1 to 3, characterised in that, in the compounds of formula R denotes a methyl, ethyl, propyl, iso-propyl, butyl or isobutyl radical or a mono- or polyhydroxyalkyl radical chosen from: CH 2 -CH 2 -OF, -CH -CHOH-CH 2 -OH or -CH 2 -CHOH-CH 3 Process according to any one of Claims 1 to 4, characterised in that the compounds of formula are chosen from the following compounds: 2-methoxymethyl-4-aminophenol, 2-ethoxymethyl-4-aminophenol, 2-propoxymethyl-4-aminophenol, 2-isopropoxymethyl-4-aminophenol, 2-(p-hydroxyethoxymethyl)-4-aminophenol, 2-methylthiomethyl-4-aminophenol, 2-(p-hydroxyethylthiomethyl)-4-aminophenol, 2- p, -y-dihydroxypropylthiomethyl) -4-aminophenol, and their salts. 6. Process according to any one of Claims 1 to characterised in that 6-hydroxyindole is applied to keratinous fibres as coupler. 7. Process according to any one of Claims to 6, characterised in that the pH of the composition(s) applied to keratinous fibres is such that the final pH value of the fibres is between 8 and 11.

8. Process according to any one of Claims 2 to 7, characterised in that the composition contains 0.05 to 3.5 by weight of the total weight of the composition of at least one compound of formnula

9. Process according to any one of Claims 2 to 8, characterised in that the composition contains from 0.01 to 4 by weight, with respect to the total weight of the composition, of 6-hydroxyindole and/or 7-hydroxy- indole. I

10. Process according to any one of Claims 2 to 9, characterised in that the composition contains, besides the para-aminophenol of formula defined above, other oxidation dye precursors of ortho or para A L "s~B 1 3 'r -:I o I i i t* r d 21 type chosen .from para-phenylenediamines, para-amino- ph6nols other than those of formula para heterocyclic precursors derived from pyridine or from pyrimidine, ortho-aminophenols, ortho-phenylenediamines and bisphenylalkylenediamines.

11. Process according to any one of Claims 2 to 10, characterised in that the composition contains, besides 6-hydroxyindole and/or 7-hydroxyindole, other couplers such as meta-aminophenols, meta-phenylenedia- mines, meta-acylaminophenols, meta-ureidophenols, meta- carbalkoxyaminophenols, a-naphthol or couplers having an active methylene group.

12. Process according to any one of Claims 2 to 11, characterised in that the composition iontains from 0.3 to 7 by weight, with respect to the total weight of the composition, of oxidation dye precursor of ortho and/or para type and of coupler.

13. Process according to any one of Claims 2 to 12, characterised in that the composition contains cationic, anionic, nonionic or amphoteric surface-active agents or their mixtures, in concentrations of betw en and 55 by weight with respect to the total weight of the composition; organic solvents in concentrations of between 1 and 40 by weight with respect to the total weight of the composition; thickening agents in con- centrations of between 0.1 and 5 by weight with respect to the total weight of the composition; antioxidising agents in proportions of between 0.05 and 1.3 by weight with respect to the total weight of the composition, direct dyes, fragrances, sequestering agents, film- forming agents, treatment agents, dispersing agents, conditioning agents, preserving agents, opacify.ng agents and any other agent generally used in dyeing compositions.

14. Process according to any one of Claims 2 to 13, characterised in that the compositions and are provided in the liquid, cream or gel form or any other Ssuitable form, or can be packaged under pressure in 4z I i k 111 Q I r .:i r 4: i i 1I i i ii j 4 ii~7 L_ II~ I _I i I t 22 aerosol containers in the presence of a propellant and to form foams. Process according to Claim 1, characterised in that there is applied to keratinous fibres and more particularly human hair, in a first stage, a composition containing at least one para-aminophenol of formula in a second stage, a composition containing 6-hy- droxyindole and/or 7-hydroxyindole, and the colouring is developed using an oxidising agent present in this latter composition or else this oxidising agent is applied in a third stage, the pH of the mixture forming at the level of the fibre being greater than 7.

16. Oxidation dyeing process according to any one of Claims 1 to 15, characterised in that, after application to keratinous fibres, and more particularly human hair, the mixture is left exposed for 10 to 40 minutes, preferably 15 to 30 minutes, the hair is rinsed, is washed with the shampoo, is rinsed again and is dried. Agent for dyeing kratinu ir human hair, characterised in that it comprises at at two components, one of the components consi g of the composition defined in any one of aims 2 to 14 and the other consisting of the co sition also defined in any one of Claims 2 t 4, the pH of the compositions and bei uch that, after mixing in proportions of 90 to for the composition and of 10 to 90 f-he composition the resulting composition has a pN-I greater than 7. 11,. Composition intended to be used for colouring keratinous fibres at basic pH, characterised in that it results frolt the mixing of 10 to 90 of the composition defined, in any <ne of Claims 2 to 14 with 90 to 10 of the composition defined in any one of Claims 2 to 14 and in that it has a rH greater than 7.

19. Multi--o-mpartmnt d vic or dyeing kit, -charac- terised in that it comprises, in a first co rntthe composition definad i e of Clai 1 2 to 14 and, in a sec artment, the composition defined in I ;I I1 4i i~i 'Z) -i I L L cIA t FR C 605 GD/VL/CP 92/202 ABSTRACT Process for dyeing keratinous fibres in alkaline medium using para- aminophenols substituted in position 2 in combination with 6- or 7-hydroxyindole and compositions used in the process. The invention relates to a process for dyeing keratinous fibres, characterised in that there is applied to these fibres at least one para-aminophenol of formula: 6 1 i; if I i i CH2 YR NH 2 in which, Y is oxygen or sulphur, R is alkyl, monohydroxyalkyl or polyhydroxyalkyl, and their acid addition salts, and 6-hydroxyindole and/or 7-hydroxyindole, the colour being displayed at alkaline pH using an oxidising agent. f% p 4f; r :O I:i- :3 ~1 .1 A'' AA: A' INTERNATIONAL SEARCH REPORT International application No. PCT/FR 93/00349 A. CLASSIFICATION OF SUBJECT MATTER IPC 5 A61K7/13 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC 5 A61K Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of tha relevant passages Relevant to claim No, Y EP,A,0 395 837 (WELA AKTIENGESELLSCIJAFT) 1-18 7 November 1990 see the whole document Y FR,A,2 636 236 (L'OREAL) 1-18 16 March 1990 cited in the application see the whole document Y FR,A,2 636 235 (L'OREAL) 1-18 16 March 1990 see page 9, line 26 page 10, line 18; claim 1 A EP,A,0 359 618 (L'OREAL) 1-18 21 March 1990 cited in the application see claims I--]Further documents are listed in the continuation of Box C, See patent family annex, Special categories of cited documents: later document published after the international filing dateor priority document defining the general state the art which Is not considered date and not in conflict with the application but cited to understand to be of particular relevance the principle or theory underlying the invention earlier document but published oH or after the lnternational filing date document of particular relevance: the claimed invention cannot be considered noyel or cannot be consIdered to involve an inventive document which may throw doubts on priolity claim(s) or which is step wen th ocument is taken alone voe inve cited to establish the publication date of another citation or other special reason (as speclfii document of particular relevance: the claimed invention cannot be document referring to an oral disclosure, use, exhibition or other considered to involve an inventive step when the document is means combined withoneor more othersuch documents, such combination mean .being obvious to a person skilled in the art documenc published prior to the international filing date but later than ben obou t sil the priority date claimed document member of the same patent family Date ofthe actual completion of the interational search Date of mailing of e international search report 24 June 1993 (24.06.93y 08 July 1993 (08.07.93) Ii If it ~II Nams and mailing address of the ISA/ EUROPEAN PATENT O(l'ICE Fasimile No. Form PCT/ISA/21Q (second sheet) (July 1992) Authorized officer Telephone No. 4.'t P '1 A f INTERNATIONAL SEARCH REPORT International application No. PCr/FR 93/00349 C (Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages }Relevant- to claim No. EP,A,0 446 132 (LOREAL) 11 September 1991 cited in the application see claims 1,3,4,7 1-18 :f J -d Form PC'I/ISA21O (continuation of second ahet) (July IM9) keratinous f ibres in a third stage, so that the milxture which forms in situ in the f ibres has a pH greater than LI: ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. FR SA 9300349 72656 This annex lists the patent family members relating to dhe patent documents cited in the above-mentioned international eare report. The members are as contained in the European Patent Office EDP fie an Te European Patent Office is in no way liable for dhese particulars; which are merely given for die purpose of informoation. 24/06/93 EP-A-0395837 07-11-90 DE-A- 3914253 31-10-90 US-A- 4997451 05-03-9 1 FR-A-2636236 16-03-90 LU-A- 87337 06-04-90 AU-B- 626579 06-08-92 AU-A- 4120789 15-03-90 BE-A- 1002235 30-10-90 CH-A- 679551 13-03-92 DE-A- 3930473 15-03-90 GB-A,B 2224518 09-05-90 JP-A- 2121912 09-05-90 NL-A- 8902281 02-04-90 FR-A-2636235 16-03-90 LU-A- 87336 06-04-90 AU-A- 4120489 15-03-90 BE-A- 1003574 28-04-92 CH-A- 679450 28-02-92 DE-A- 3930474 15-03-90 GB-A,B 2224517 09-05-90 JP-A- 2121913 09-05-90 NL-A- 8902280 02-04-90 US-A- 5034015 23-07-91 EP-A-0359618 21-03-90 FR-A- 2637282 06-04-90 JP-A- 2113071 25-04-90 US-A- 5053052 01-10-91 US-A- 5202487 13-04-93 EP-A-0446132 11-09-91 FR-A- 2659228 13-09-91 AU-A- 7269291 12-09-91 US-A- 5207798 04-05-93 6For mour details cheat this nmes: Official Journal of die E~rePME Paint Office, No. 1212