GB2207443A

GB2207443A - Dyeing keratinous fibres, especially human hair, with an indole dye and iodide ions

Info

Publication number: GB2207443A
Application number: GB08817070A
Authority: GB
Inventors: Jean-Francois Grollier
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1987-07-17
Filing date: 1988-07-18
Publication date: 1989-02-01
Anticipated expiration: 2008-07-18
Also published as: GB8817070D0; FR2618070A1; ES2007267A6; LU86947A1; JPH0193516A; IT8867673A0; GB2207443B; IT1223701B; PT87991B; PT87991A; DE3824122A1; CH676926A5; BE1002155A5; NL8801811A; FR2618070B1

Description

2 U 7 4. r J Process for dyeing keratinous-fibres, especially human

keratinous fibreso with at Least one indote dye.

1 25 The invention relates to a new process for dyeing keratinous fibres, especially human keratinous fibres such as the hair and hairs (beard, moustache, eyelashes, eyebrows), for the purpose of imparting a natural colouring to them, employing an indote dye.

The dyeing of human hair with 5,6-dihydroxyindole or its derivatives is well known. It is also known that the colour of the hair originates mainly from the melanin pigments secreted by the melanocytes, and that these pigments of natural origin comprise eumetanins whose natural biosynthesis takes place in several stages by the poly- merization of the oxidation product of an amino acid, namely tyrosine, one of the oxidation products of tyrosine being 5,6-dihydroxyindole.

In his French Patent Applications Nos. 2,593,061 and 2,606,636. the Applicant has described a process for dyeing keratinous fibres with 5,6-dihydroxyindole andlor its derivatives comprising the application on these fibres of at Least one composition (A) containing, in a medium suitable for dyeing, 5,6-dihydroxyindole andlor its derivatives in combination with iodide ions, the application of the composition (A) being preceded or followed by the application of a composition (8) which contains hydrogen peroxide in a medium suitable for dyeing.

The Applicant has just found that it was possible to improve, surprisingly, the strength of colouring obtained by means of this process, by following the application of composition Mly a stage of drying or evaporation of the liquid medium.

Among the dyeing or bleaching techniques commonly used in the hair-care field, one of these consists in partially treating the hair in order to obtain a so-called "highlight" effect.

This effect is generally obtained by applying the dyeing or bleaching product on isolated locks, the locks either having been drawn through a plastic bonnet placed on the scalp or having been isolated by another process such as with cotton, with aluminium foil, or the like, or alternatively by the so-called "sweeping" technique wi-th a comb.

In t he light of the value of 5,6-dihydroxyindole and of its derivatives, the prospect was envisaged of also applying this dyeing process employing iodide ions and hydrogen peroxide for the purpose of obtaining the socalled "highlight" effect.

The Applicant found, however, that, by carrying out this process in several stages in order to dye the hair partially for the purpose of obtaining the so-called "highlight" effect, an imperfect and unattractive dyeing was obtained.

In effect, the Applicant found that this process i 1 3 - often led to a staining of the hair in proximity to the Locks on which the composition was applied, as a result of the considerable diffusion of the dye onto adjacent fibres during the development with hydrogen peroxide.

This drawback manifests itself above all when it is desired to perform dyeing of white or grey short hair, and more especially of men's hair at the temples. In effect, in this case, it is virtually impossible to perform a dyeing using a bonnet, since the hair is too short.

moreover, the fact of not using a bonnet also enables time to be gained.

The Applicant has found that, surprisingly, it was possible to remedy the problems of staining or of unattractiveness of appearance caused by this two-stage dyeing process described above, and that it was also possible, as stated above, to obtain colourings possessing improved strength.

This process employs the application of at least one indole dye with iodide ions, followed by the applica- tion of hydrogen peroxide, and is characterized by an interfflediate stage of drying or evaporation of the dyeing medium.

The subject of the invention hence consists of a new process for dyeing keratinous fibres, and especially human keratinous fibres.

other subjects of the invention will become apparent on reading the description and the examples which

4 - follow.

The process for dyeing keratinous fibres, and especiatly human keratinous fibres, is essentially characterized in that, in a first stage, a liquid composition -M suitable for dyeing is applied on these fibres, this composition (A) containing at least one indole dye of f o r m u 1 a:

R4 R3 R 5 R2 in which:

R1 denotes a hydrogen atom, a lower alkyl group or a group -SiR9R1OR11; R2 and R3, which may be identical or different, denote a hydrogen atom or alternatively a lower alkyL group, a carboxyl group, a lower alkoxycarbonyl group or a group -COOSiR9R1OR11; and R4 and R5, which may be identical or different, denote a hydrogen atom, a CI-C20 linear or branched alkyl group, a formyl group, a linear or branched C2-C20 acyl group, a linear or branched C3-C20 atkenoyL group, a group -SiRgRIOR11, a group -P(O)(OR6)2 or a group R60S02, or alternatively R4 and RS, together with the oxygen atoms to which they are attached, form a ring optionally containing a carbonyl group, an optionally substituted methylene group, a thiocarbonyl group or a group:

( I) ' P(COR6. or alternatively -----CR7R8; R6 and R7 denoting a hydrogen atom or a tower alkyL group, R8 denoting a Lbwer atkoxy group or a monoor dialkyLamino group, R9, R10 and R11, which may be identicat or different, denoting linear or branched tower alkyl groups, and the addition salts with inorganic or organic acids as well as the corresponding salts of alkali metals, alkaline earth metals or amines, or mixtures thereof, in combination with iodide ions, in a second stage, the fibres are brought to the dry state by drying or evaporation of the liquid medium, and in a third stage, a composition (8) containing hydrogen peroxide in a liquid medium suitable for dyeing is applied.

Preferred compounds of the formula (I) correspond to the formula:

g 5 ------- F 8 4 3 ( I I) R'2 in which R12 and V3, which may be identical or different, denote a hydrogen atom, a Cl-C6 lower alkyl group, a carboxyL group or a lower alkoxycarbonyl group in which the alkoxy group is a Cl-C6 group, and V4 and V5, which may be identical or different, denote a hydrogen atom, a Cl- C6 lower atkyl group, a C2-C20 linear acyl group or a trimethylsilyl group, or alternatively V4 and C5, is together with the oxygen atoms to which they are attached. form an optionally substituted methylenedioxy or a carbonyldioxy ring.

Among these compounds, special mention may be made of 5,6-dihydroxyindole, 5-methoxy-6-hydroxyindote. 3-methyl56-dihydroxyindole, 2-methyl-5,6dihydroxyindote, 5-acetoxy6-hydroxyindole, 2-ethoxycarbonyt-5,6dihydroxyindole, 2,3dimethyl-5,6-dihydroxyindote and their salts.

An especially preferred embodiment of the invention consists in using 5(hydroxy or methoxy)-6-hydroxyindole.

The iodide ion used in the process according to the invention is preferably an alkali metal or alkaline earth metal or ammonium iodide, and more especially potassium iodide.

During the process according to the invention, it is possible, after drying, to remove by brushing the product dried at the surface of the fibres, in order to leave only the dye which has penetrated.

This process is preferably used for partially dyeing hair which has become white or grey through loss of the natural pigmentation, to obtain a so-called "highLighC effect.

This process is especially advantageous for dyeing men's hair at the temples, or the hairs of the beard, the moustache, the eyelashes or the eyebrows.

In the compositions used in the process according to the invention, the indole dye(s) islare generally present in proportions of between 0.01 and 5% by weight, and preferably between 0.03 and 3% by weight, relative to the weight of the composition (A). The proportion of iodide in the composition (A), applied during the process according to the invention, is between 0.007 and 4%, expressed as I ions, and preferably between 0.08 and 2.5% relative to the total weight of the composition (A).

The indole dye/C ratio is preferably between 0.05 and 10, and more especially between 0.5 and 2.

The pH of the composition (A) is preferably between 2 and 7.

Hydrogen peroxide is present in the composition (8) in proportions generally of between 1 and 40 volumes, and preferably between 2 and 20 volumes, and more espe- cially between 3 and 15 volumes. This composition has a pH of between 2 and 11.

The process according to the invention is carried out by arranging exposure times for the composition (A), containing the indole dye(s) of formula I in combination with the iodide ions, of between 10 seconds and 45 minutes, and preferably of the order of 2 to 25 minutes, and more especially in the region of 2 to 15 minutes, and for the composition (B), containing hydrogen peroxide, exposure times of between 10 seconds and 45 minutes, and preferably between 1 minute and 30 minutes.

The drying or evaporation time is preferably between 2 minutes and 50 minutes, and is performed at a temperature of between 200C and SOOC.

The Applicant has found that the process employed enabled 'highLighC effects having strong colourings, penetrating well into the fibres, especially human keratinous fibres such as the hair or hairs, to be obtained in relatively short times. of the order of 2 to 15 minutes.

The process according to the invention also enabLes Light hues to be obtained, either by using Low con- centrations of indoLe dye(s) and iodide within the limit of the indoLe dye/I ratio stated above, and very short exposure times for the application of the hydrogen peroxide composition (B), or by Lightening of the deep colours aLready obtained, by Leaving the hydrogen peroxide composi- tion (B) in place for a prolonged period.

The compositions used for carrying out the process according to the invention may be presented in various forms, such as more or Less thickened or geLLed Liquids, creams, emulsions, foams or other forms suitable for carrying out a dyeing.

The dyeing compositions intended for use in the process according to the invention, and containing either the indote dye(s) of formula (I) in combination with iodide ions, or hydrogen peroxide, generally contain an aqueous medium consisting of water or a waterlsoLvent(s) mixture, the soLvent(s) preferably being chosen from organic solvents such as ethyl alcohol, propyL or isopropyL alcohol, tert-butyl aLcohoL, ethyLene gLycoL, ethyLene gLycoL monomethyL, monoethyL or monobutyL ether. ethyLene gLycoL monoethyll ether acetate, propyLene gLycoL, propytene gLycoL and dipropyLene gLycoL monomethyt ethers. and methyt Lactate.

The preferred soLvents are ethyt aLcohoL and propyLene gLycoL.

It is aLso possibLe to store the indoLe dye(s) of formuLa (I) andlor the iodide in a medium consisting of essentiaLLy anhydrous soLvents. and to mix this/these soLvent(s) with an aqueous medium at the time of use.

The soLvents are chosen from those mentioned above.

The designation anhydrous soLvent refers to a soL- vent comprising Less than 1% of water.

When the medium consists of a waterlsoLvent(s) mixture. the soLvents are-present in concentrations of between 0.5 and 75%, and especiaLLy between 2 and 50%. by weight reLative to the totaL weight of the composition, and more especiaLLy between 2 and 20%.

The composition (A) can contain other dyes, either oxidation dyes or direct dyes, which enabLe a coLouring or hue to be obtained in the presence of iodide ions and hydrogen peroxide.

Oxidation dyes are understood to mean compounds which are generaLLy not dyes in themseLves. but intermediate compounds which are initiaLLy onLy sLightLy coLoured or coLourLesso referred to. in particuLar, as "oxidation bases or precursors" and which deveLop their dyeing power in an oxidizing medium,.generally consisting of hydrogen peroxide, to give rise in a basic medium to a dye according to a process of oxidative condensation, either of the oxidation dye "precursor" with itself, or of the oxidation dye-"base or precursor" with a compound referred to as a "modifier" or "coupler". Oxidation dyes also comprise the couplers and the so-called "rapid" oxidation dyes.

The oxidation dyes are chosen, in particular, from 10 paraphenylenediamines preferably corresponding to the formula:

NR 17 R 16 R1 R 15 R1 R12 1H2 ( I I I) in which:

R17 and R16, which may be identical or different, can denote hydrogen, a Cl-C6 lower alkyl group, a Cl-C6 alkyl radical substituted with one or more hydroxy group(s) or with a methoxy, methytsutphonylamino or aminocarbonyl group, a furfuryl group or a phenyl radical optionally substituted with an amino group; R15 and R14, can denote, independently of one another, hydrogen, a Cl-C6 lower alkoxy group, a halogen atom such as chlorine, a Cl-C6 tower alkyl group, or a Cl-C6 lower alkyl group substituted with one or more hydroxy group(s); and R12 and R13 can denote, independently of one ano- ther, hydrogen. a Cl-C6 lower atkoxy group. a Cl-C6 Lower alkyl group or a halogen atom such as chlorine, it not being possible for R16 and R.17-to denote hydrogen simul taneousty when R12, R13, R14 and R15 all denote hydrogen, as welt as their salts with inorganic or organic acids; N,NI-diphenylalkylenediamines in which the phenyl groups are para-substituted with an OH or amino group optionally substituted with a Cl-C6 aLkyl group, it being possible for the amino groups joined by the alkylene group to be substituted with Cl-C6 alkyl, Cl-C6 hydroxyalkyl or Cl-C6 aminoalkyl; para-aminophenots, ortho-aminophenols; ortho-phenylenediamines; and heterocyclic oxid ation bases.

Among the compounds of formula (III) which are more especially preferred, there may be mentioned 2-methyL para- phenytenediamine, 2-methoxy-para-phenylenediamine, N-methyl-2-chloro-para- phenylenediamine, N-furfuryl-paraphenylenediamine. 3-methoxy-N 1-methytpara-phenylenediamine, 2-chloro-para-phenylenediamine, N-methyt-paraphenylene- diamine, 2,3-dimethyl-para-phenytenediamine, 5-chloro-N 1 methyt-p- phenylenediamineo 5-methyl-N 1..N 1_ dimethyl-pphenyLenediamine. 5-methyl- N 1-ethyt-N 1-(aminocarbonylmethyL)-p-phenylenediaminee 5-methyl-Nl-ethyl- N1-(methytsutphonylaminoethyl)-p-phenylenediamine, N-(2-methoxy- ethyl)-p-phenylenediamineo 2,6-dimethyl-p-phenylenediamine and N,N-bis(2- hydroxyethyl)-p-phenylenediamine, as well as their salts with acids such as the monohydrochlorides, ---1 dihydrochlorides or sulphates. Among N,V-diphenylalkylenediamines, there may be mentioned N,NI-U-hydroxyethyON,NI-(p-aminophenyt)ethytenediamine.

Among p-aminophenoLs which are more especially usable according to the invention, there may be mentioned para- aminophenol, 2-methyl-p-aminophenol, 2,3-dimethyl-paminophenol, 2,6dimethyl-p-aminophenot, 3-methoxy-p-aminophenol, 2-chloro-p-aminophenol, N-methyl-p-aminophenol and 3-(methylthio)-p-aminophenol, of which 2methyl-p10 aminophenol is preferred.

Among ortho bases, ortho-aminophenol, 5-chloroortho-aminophenol and orthophenylenediamine are chosen more especially, according to the invention.

Among heterocyclic bases, it is preferable accord is ing to the invention to us.e 2,3-diamino-6-methoxypyridine, 2-(2-hydroxyethyl)amino-5-aminopyridine, and still more es pecialty 3,6-diaminopyridine, 2,6-di-methoxy-3-aminopyri dine and 2-methytamino-3-amino-6-methoxypyridine, and their salts.

These various oxidation bases may be used mixed or alone.

The couplers are chosen from phenols, meta-diphenols, meta-aminophenots, meta-phenylenediamines, mono- or polyhydroxylated derivatives of naphthalene and of aminonaphthalene, pyrazolones and benzomorpholines.

Among couplers or modifiers, there may be mentioned, in particular, compounds corresponding to the formula (IC - 13 R;II IR20 R 22 H R19 1 -R 23 LS (IV) in which:

R21 denotes hydroxy or an amino group which can be substituted with one or more Cl-C6 hydroxyalkyl groups; R23 and R19, independently of one another, can denote hydrogen, a hydroxy group, an amino group option ally substituted with a Cl-C6 lower hydroxyalkyl group, or a Cl-C6 tower alkyl group; and R22, R18 and R20 can denote a hydrogen atom or a Cl-C6 alkoxy group.. a hydroxyalkoxy group or a Cl-C6 lower alkyl group; it also being possible for R23 and R18 together to form a methylenedioxy group.

Among especially preferred couplers, there may be mentioned 2-methoxy-S-aminophenol, 2-methoxy-S-IN-(2-hyd- roxyethyl)aminolphenot, 1,3-diamino-2,6-dimethoxybenzene, 2-methoxy-l-(N-inethylamino)-4-(2-hydroxyethyloxy)-3-amino- benzene, 1,3-diamino-6-methoxybenzene, 1,3-diamino-4,6 dimethoxybenzene, 4,6-dimethoxy-1,3-bis[N-(2-hydroxyethyt)- aminolbenzene, 2,6-dimethoxy-3-[N-(2-hydroxyethyl)aminol- 1-aminobenzene, 2,4-dimethoxy-3-EN-(2-hydroxyethyl)aminol- - 14 1-aminobenzene, 2-methyl-S-EN-(2-hydroxyethyl)aminolphenol, 103-bis[N-(2hydroxyethyl)aminol-4-methoxybenzene, 3-amino4-methoxyphenot, 3,4methytenedioxy-l-aminobenzene, 2,6dimethyt-3-EN-(2hydroxyethyt)aminolphenot, 2,6-dimethyl- 3-aminophenot, 4-ethoxy-l-amino-3-EN,N-bis(2-hydroxyethyl)aminolbenzene, (2,4-diaininophenoxy)ethanoto 12-amino-4-(Nmethytainino)phenoxylethanol, 1-methoxy-2-EN-(2-hydroxyethyt)aminol-4-aminobenzene, 3,4-methylenedioxy6-methoxyphenol, 3-amino-6-methylphenol, 3,4-methytenedioxy-6methoxyaminobenzene, 3-aminophenol and 1,3-dihydroxybenzene.

Other preferred couplers are 6-aminobenzomorpholine, line, 1-amino-7naphthol, 6-hydroxybenzomorpholine, l-naphthol, 1,3-dihydroxynaphthalene and 1,2-dihydroxybenzene.

The so-called "rapid" oxidation dyes are dye pre- cursors capable of generating coloured compounds by simple oxidation in the air during the exposure time on the hair, that is to say generally less than 1 hour, this occurring in the absence of another oxidizing agent. They are chosen, in particular, from trihydroxylated derivatives of benzene, diaminohydroxybenzenes, aminodihydroxybenzenes, triaminobenzenes, aminohydroxybenzenes, and 1,2-dihydroxybenzenes substituted on the benzene ring.

Among trihydroxylated derivatives of benzene, there may be mentioned 1,2,4-trihydroxybenzene, the 1,2,4trihydroxy-5- atkylbenzenes in which the alkyl group is a Cl-C6 lower alkyl group, and 1,2,3-trihydroxybenzene, 1 1 1 - is - and their salts.

Among diaminohydroxybenzenes, there may be mentioned 2,4-diaminophenoLO 2, 5-diamino-4-metboxy-lhydroxybenzene and their salts.

Among aminodihydroxybenzenes. there may be mentioned 2-amino-1,4dihydroxybenzene, 1,4-dihydroxy-2-di e. thylaminobenzene, 4aminoresorcinol and their salts.

Among substituted 1.2-dihydroxybenzenes. 4-methyl1,2-dihydroxybenzene and 3-methoxy-1,2-dihydroxybenzene are especially preferred.

The aminohydroxybenzenes are chosen, in particular. from 2-amino-4methoxyphenol. 2-aminophenol, 4,6-di-. inethoxy-3-amino-l-hydroxybenzene. 2,6-dimethyl-4-EN-(phydroxyphenyl)aminol-1-hydroxybenzene and their salts.

By way of triaminobenzenes. there may be mentioned 1,5-diamino-2-methyl-4-[N-(p-hydroxyphenyl)aminolbenzene and its salts.

Other so-called "rapid" oxidation dyes that are usable are chosen, in particular, from braziLin. haema- toxyLin and alkanet extract.

These various oxidation dyes may be used mixed or alone. in combination with iodide ions and the indoLe dye(s) of formula I.

The direct dyes are chosen. in particular, from nitrated benzene derivativeso anthraquinones and benzoquinones.

The compositions used according to the invention can contain fatty amides, such as mono- or diethanotamides, of acids derived from copra, of lauric acid or of oleic acid, at concentrations of between 0.05 and 10% by weight.

They can also contain anionic, cationic, nonionic or amphoteric surfactants, or mixtures thereof.

These surfactants are preferably used in proportions of between 0.1 and 50% by weight, relative to the total weight of the composition, and advantageously between 1 and 20% by weight.

The compositions defined above and used in the process according to the invention can be thickened with thickening agents such as sodium alginate, gum arabic, guar gum, biopolymers such as xanthan gum or scleroglucans, cellulose derivatives such as methylcetlulose, hydroxy- ethylcellulose, hydroxypropylmethylcellulose and the sodium salt of carboxymethylcellulose, and crosslinked or non-crosslinked polymers of acrylic acid. It is also possible to use inorganic thickening agents such as bentonite. These thickeners are used alone or mixed, and are preferably present in proportions of between 0.1 and 5% by weight relative to the total weight of the composition, and advantageously between 0.5 and 3%.

The alkalinizing agents that are usable in these compositions can be, in particular, amines such as alkan- olamines, alkylamines and alkali metal or ammonium hydroxides or carbonates. The acidifying agents that are usable can be chosen from lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid and citric acid, but it is naturally possible to use other alkaLinizing or acidifying agents suitable for dyeing.

it is possible, as an option, to add an agent for swelling the keratinous fibre, such as, for example, urea, to each of these compositions.

When the composition containing the indole dye(s) is/are used in the form of a foam, it may be packaged under pressure in an aerosol device in the presence of a pro- pellant agent and a foam generator. The foam generators can be anionic, cationic, nonionic or amphoteric foaming polymers, or surfactants as mentioned above.

The compositions employed in the process according to the invention can contain, in addition, various adju- vants such as perfumes, sequestering agents, film-forming agents, fibre treatment agents, dispersants, conditioners, preservatives and opacifiers.

For the purpose of carrying out the process according to the invention, the compositions may be packaged in multi-compartment devices, also referred to as "dyeing kits" or outfits containing all the components designed to be applied for a single dyeing on keratinous fibres, in successive applications with or without premixing.

Such devices are known per se, and can comprise a first compartment containing the indole dye(s) in the presence of iodide ions in a liquid medium suitable for dyeing, in a second compartment a hydrogen peroxide solution, ---1 i - 18 and optionally a third compartment containing an alkatinizing agent in a inedium suitable for dyeing. It is also possible to provide a fourth compartment containing one or more oxidation or direct dyes, in a medium suitable for dyeing, the contents of the third and the second coopartments being mixed immediately before use and that of the fourth compartment being designed to be mixed with the content of the first compartment.

If the medium containing the indole dye consists of an anhydrous solvent, mixing with an aqueous medium suitable for dyeing, optionally present in a fifth compartment, is performed before use.

The indole dye(s) in an anhydrous medium can also be applied directly on the wet keratinous fibres.

is According to another embodiment, the dyeing kit or outfit comprises a first compartment containing a composition containing iodide ions in a medium suitable for dyeing, a second compartment containing a composition containing the indole dye(s) in a Liquid medium suitable for dyeing, a third compartment containing a hydrogen peroxide solution. and optionally a fourth compartment containing an alkalinizing agent. The composition contained in the second compartment is designed to be mixed. at the time of use, with the content of the first compartmento and that contained in the fourth is designed to be mixed at the time of use with that of the third.

These devices can be equipped with mixing means z 19 - that are known per se, and can be packaged under an inert atmosphere.

The processes according to the invention and the corresponding compositions may be used for dyeing natural or already dyed hair, permanent-waved or otherwise, or straightened, or strongly or lightly bleached and optionally permanent-waved hair. As stated above, they are preferably applied to partial dyeing for obtaining a socalled "highlighC effect, in particular on short hair that has partly lost its natural pigmentation, but also on hairs such as those of the beard, moustache, eyelashes and eyebrows, where the use of a bonnet is not possible.

The process of the.invention may be preceded or followed by other cosmetic treatments that are known per se.

It is also possible to carry it out for dyeing furs or wool.

The examples which follow are intended to illustrate the invention, no limitation of the latter being 20 implied.

EXAMPLE 1

On a head of hair comprising 80% of white hairs, the composition (A) is applied with a small brush on a portion of the head of hair, from the root to the tip, so that only half of the white hairs are covered with the composition (A).

Drying is performed under a dryer for 10 minutes.

- 20 The composition (S) is applied for 10 minutes.

The hair is rinsed and dried. Drying is performed under a dryer (200C to 5000. After drying, a portion of the hair is black, while the,remaining hairs have remained white, restoring the head of hair collectively to approximatety 40% of white hairs. Composition A: 5,6-Dihydroxyindole Potassium iodide Ethyl alcohol Guar gum sold by the company CELANESE under the name "JAGUAR HP 6V Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" Natural pH 6.5 Water Composition 8: Hydrogen peroxide Ammonium lauryl sulphate CARSOPOL 940 (crosslinked acrylic polymer) sold by the company GOODRICH Stabilizer Perfume 2-Amino-2-methyt-l-propanol cis PH 4 Water 2.5 9 2.0 9 10.0 9 1.0 g 5.0 9 AS 100.0 9 3.75 9 6.7 9 1.0 9 0.03 9 q s q s 100.0 9 EXAMPLE 2

Example 1 is repeated, using the following composition by way of composition M:

5,6-Dihydroxyindole 2.0 9 Potassium iodide 1.0 g E-thyl alcohol 10.0 g Guar gum sold by the company CELANESE under the name "JAGUAR HP 6V GLycoside alkyl ether sold at a concentra tion of 60% AS by the company SEPPIC under the name "TRITON CG 110" Triethanolamine qs pH 6 Water qs 100.0 g The composition B is identical to that of Example 1 A brown'colouring is obtained on the dyed portion of the hair.

EXAMPLE

1.0 g 5.0 9 AS 3 Example 1 is repeated, using the following com- position by way of composition M:

5-Methoxy-6-hydroxyindole 2.0 9 Potassium iodide 2.0 9 Ethyl alcohol 10.0 9 Guar gum sold by the company CELANESE under the name "JAGUAR HP W' Glycoside alkyl ether sold at a concentra tion of 60% AS by the company SEPPIC under the name "TRITON CG 110" 1.0 g 5.0 9 AS 22 - Natural pH 6.2 Water qs 100.0 9 The composition (B) has the following composition:

Hydrogen peroxide 3.75 9 Ammonium Lauryl sulphate 6.7 9 CARSOPOL 1345 (crosslinked acrylic polymer) sold by the company GOODRICH 0.7 9 -Stabilizer 0.03 9 Perfume qs 2-Amino-2-methyl-l-propanol qs pH 3.8 Water qs 100.0 9 A black colouring is obtained on the dyed portion of the hair.

EXAMPLE 4

Example 1 is repeated, using the following compo- sition by way of composition M:

5,6-DihydroxyindoLe 3.0 g Sodium iodide 3.0 g 2-Butoxyethanol Xanthan gum sold by the company RHONE POULENC under the name RHODOPOL SC Glycoside alkyl ether sold at a concentration of 60% AS by the company SEPPIC under the name TRITON CG 110 25 Water Natural pH 4.61 The composition (B) 10.0 g 2.0 9 2.1 g AS qs 100.0 g a "20 volumes" aqueous hydrogen peroxide solution having a pH adjusted to 10 with monoethanolamine.

A coppery Light chestnut colouring is obtained on the dyed portion of the hair.

EXAMPLE 5

Example 1 is repeated, using the following com- position by way of composition M:

N,N-Sis(2-hydroxyethyl)-p-phenylene- diamine sulphate 1.0 g 5,6-Dihydroxyindole 0.2 g Potassium iodide Ethyl alcohol Xanthan gum sold by the company RHONE POULENC under the name RHODOPOL 23 SC Glycoside alkyl ether sold by the company SEPPIC under the name TRITON CG 110 2.1 g AS Triethanolamine qs pH 6 Water qs 100.0 g The composition (E) is a "20volumes" aqueous hyd- rogen peroxide solution at pH 3.

A slightly pearly medium grey colouring is obtained on the dyed portion of the hair.

EXAMPLE 6

Example 1 is repeated, using the following com- position by way of composition M: Composition A: 5,6-Dihydroxyindole 1.0 g 0.0 g 2.0 g 0.6 9 1 1,3-Diflydroxybenzene 3-Aminophenol Potassium iodide Ethyl alcohol Guar gum sold by the- company CELANESE under the name JAGUAR HP 60 Glycoside alkyl ether sold at a concentra tion of 60% AS by the company SEPPIC under the name TRITON CG 110 Preservative Natural pH 6.5 Water qs 100.0 9 Composition (B) containing "12.5 volumes" hydrogen per- oxide Hydrogen peroxide Ammonium lauryl sulphate Gum arabic Stabilizer Perfume 2-Amino-2-methyL-1-propanol Water 100.09 A natural deep chestnut colouring is obtained on the dyed portion of the hair.

EXAMPLE 7

0.05 9 0.4 9 1.0 9 10.0 9 1.0 9 5.0 9 AS qs 3.75 9 6.70 9 1.0 9 0.03 9 qs qs pH 4 Example 1 is repeated, using the following-com- position by way of composition M:

i Composition A:

5,6-Dihydroxyindote 1,2,4-Trihydroxy-5-methylbenzene Potassium iodide Ethyl alcohol Guar gum sold by the company CELANESE under the name JAGUAR HP 60 glycoside aLkyl ether sold at a concentra tion of 60% AS by the company SEPPIC under the name TRITON CG 110 Preservative Natural pH 5.4 Water qs 100.0 9 The composition (8) is the same as that of Example 6.

An auburn deep blonde colouring is obtained on the dyed portion of the hair.

EXAMPLE 8

Example 1 is repeated, using the following composi- tion by way of composition (A):

Composition A:

5,6-Dihydroxyindole 3-Amino-6-methylphenol 1,2,4-Trihydroxybenzene Potassium iodide Ethyl alcohol Guar gum sold by the company CELANESE under the name JAGUAR HP 60 0.7 9 3.0 g 2.0 g 10.0 g 1.0 9 5.0 9 AS qs 0.3 9 0.3 9 0.3 g 0.8 g 10.0 g 1.0 9 Glycoside alkyl ether sold at a concentra tion of 60% AS by the company SEPPIC under the name TRITON CG 110 Preservative Natural pH 6.7 Water 5.0 9 AS qs qs 100.0 9 The composition (8) is the same as that of Exam- ple 6.

A reddish maroon colouring is obtained on the dyed 10 portion of the hair.

EXAMPLE 9

3Methyl-5,6-dihydroxyindole 1.0 g Sodium iodide 1.0 9 Ethyl alcohol 10.0 9 Water qs 100.0 g Natural pH 4.9 The composition (B) is a "20 volumes" aqueous 20 hydrogen peroxide solution at pH 3.

A bluish black colouring is obtained on the dyed portion of the hair.

EXAMPLE 10

Example 1 is repeated, using the following com position by way of composition M:

2-Methyt-5,6-dihydroxyindole 1.0 g 5,6-Dihydroxyindote 0.3 g Potassium iodide Ethyl alcohol Guar gum sold by the company CELANESE under the name JAGUAR RP 60 glycoside alkyl ether sold at a concentra tion of 60% AS by the company SEPPIC under the name TRITON CG 110 Triethanolamine Water qs 100.0 9 and, by way of composition (B), a composition identical to that of Example 6.

0.5 9 10.0 g 1.0 9 5.0 9 AS qs pH 6.5 is A golden chestnut colouring is obtained on the dyed portion of the hair.

EXAMPLE 11 Example 1 is repeated, using the following com- position by way of composition M:

2-Ethoxycarbonyl-5,6-dihydroxyindole 1.3 g 5,6-Dihydroxyindole 0.3 g Potassium iodide 1.0 g Ethyl alcohol 10.0 g Guar gum sold by the company CELANESE under the name JAGUAR RP 60 1.0 g Glycoside alkyl ether sold at a concentra tion of 60% AS by the company SEPPIC under the name TRITON CG 110 5.0 g AS Triethanolamine qs pH 6.5 Water qs 100.0 g and, by way of composition (8), that described in Example 6.

A deep ash blond colouring is obtained on the dyed portion of the hair.

EXAMPLE 12

2,3-Dimethyl-5,6-dihydroxyindole 0.8 9 5,6-Dihydroxyindole 0.3 9 Potassium iodide Ethyl alcohol Guar gum sold by the company CELANESE under the name JAGUAR HP 60 Glycoside alkyL ether sold at a concentra tion of 60% AS by the company SEPPIC under the name TRITON CG 110 Triethanolamine qs pH 6.5 Water qs 100.0 g and, by way of composition (9), that described in Example 6.

An ash blond colouring is obtained on the dyed 20 portion of the hair.

EXAMPLE 13 Example 1 is repeated, using the following com- position by way of composition M:

5-Acetoxy-6-hydroxyindole 0.8 g 506-Dihydroxyindole Potassium iodide Ethyl alcohol 0.9 g 10.0 g 1.0 9 5.0 9 AS 0.4 g 0.5 g 10.0 g t - 29 Guar gum sold by the company CELANESE under the name JAGUAR HP 60 Glycoside alkyL ether sold at a concentra tion of 60% AS by the company SEPPIC under the name TRITON CG 110 Triethanolamine qs pH 6.5 Water qs 100.0 9 and, by way of composition (B), that described in Exam- ple 6.

A deep chestnut colouring is obtained on the dyed portion of the hair. EXAMPLE 14 Example 1 is repeated, using the following com- position by way of composition M:

2-Methyl-5,6-dihydroxyindole hydrobromide 1.0 g Ammonium iodide 1.0 g Ethyl alcohol Guar gum sold by the company CELANESE under the name JAGUAR HP 60 Glycoside alkyl ether sold at a concentra tion of 60% AS by the company SEPPIC under the name TRITON CG 110 Triethanotamine qs pH 6.6 Water qs 100.0 g and, by way of composition (B), that described in Example 6.

1.0 9 5.0 9 AS 10.0 9 1.0 g 5.0 9 AS A golden light chestnut colouring is obtained on the dyed portion of the hair.

Claims

CLAIMS 1. Process for dyeing keratinous fibres which comprises, in a first stage, applying thereto at least one composition (A) containing at least one indole dye of the formula: R4 -R 3 R5: R2 in which:

1 denotes a hydrogen atom, a lower alkyl group or a -SiR 9 R 10 R 11 group; 2 and R 3' which may be identical or different, denote a hydrogen atom or a lower alkyl group, a carboxyl group, a lower alkoxycarbonyl group or a -COOSiR 9 R 10 R 11 group; and R 4 and R 5' which may be identical or different, denote a hydrogen atom, a C l-C 20 linear or branched alkyl group, a formyl group, a linear or branched C 2-C 20 acyl group, a linear or branched C 3-C 20 alkenoyl group, a -SiR 9 R 10 R,, group, a -P(O)(OR 6)2 group or a R 60S02 group, or alternatively R 4 and R 5' together with the oxygen atoms to which they are attached and the carbon atoms to which said oxygen atoms are attached, form a ring (I) optionally containing a carbonyl group, an optionally substituted methylene group, a thiocarbonyl group or a group:

P(O)OR 6. or alternatively CR 7 R8; R 6 and R 7' which may be identical or different, denoting a hydrogen atom or a lower alkyl group, R 8 denoting a lower alkoxy group or a mono- or dialkylamino group, R.P R 10 and R,,, which may be identical or different, denoting a linear or branched lower alkyl group, or an inorganic or organic acid addition salt thereof or a 10 salt thereof with an alkali metal, alkaline earth metal or amine, and a source of iodide ions, in a second stage, drying or evaporating the liquid medium of said composition on the fibres, and, in a third stage, applying a composition (B) which contains hydrogen peroxide in a 15 liquid medium suitable for dyeing.

2. Process according to claim 1 in which the indole dye has the formula:

Rs 4 R 3 c)-7 r, 1 - 11 - - (I I) R' 50 N -----R'2 H in which R' 2 and R' 3' which may be identical or different, Ir 33 denote a hydrogen atom, a C l-C 6 alkyl group, a carboxyl group or alkoxycarbonyl group in which the alkoxy group is a C l-C 6 group, and R'4 and R',, which may be identical or different, denote a hydrogen atom, a C l- C 6 alkyl group, a C 2-C 20 linear acyl group or a trimethylsilyl group, or alternatively R' 4 and R' 51 together with the oxygen atoms to which they are attached, form an optionally substituted methylenedioxy or a carbonyldioxy group.

3. Process according to claim 1 or 2, in which the indole dye is 5,6-dihydroxyindole, 5-methoxy-6-hydroxyindole, 3methyl-5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 5-acetoxy-6hydroxyindole, 2-ethoxycarbonyl5,6-dihydroxyindole or 2,3-dimethyl-5,6dihydroxyindole or a salt thereof.

4. Process for dyeing keratinous fibres, which comprises, in a first stage, applying thereto a composition (A) containing at least one indole derivative and a source of iodide ions in a liquid medium suitable for dyeing, in a second stage, drying or evaporating the liquid medium of said composition on the fibres, and, in a third stage, applying a composition (B) which contains hydrogen peroxide in a liquid medium suitable for dyeing.

5. Process according to any one of claims 1 to 4, in which the drying or evaporation of the liquid medium is carried out for 2 minutes to 50 minutes at a temperature of 20 to 50 0 C.

1

6. Process according to any one of claims 1 to 5, in which the source of iodide ion is an alkali metal, alkaline earth metal or ammonium iodide.

7. Process according to any one of claims 1 to 6. in which the indole dye(s) is/are present in.the composition (A) in an amount from 0.01 to 5% by weight, relative to the total weight of the composition (A).

8. Process according to claim 7 in which the indole dye(s) is/are present in composition (A) in an 10 amount from 0.03 to 3% by weight.

9. Process according to any one of claims 1 to 8 in which the iodide ions are present in composition (A) in an amount from 0.007 to 4% by weight, expressed as I ions, relative to the total weight of the composition (A).

10. Process according to claim 9 in which the iodide ions are present in composition (A) in an amount from 0.08 to 2.5% by weight.

11. Process according to any one of claims 1 to 10 in which the ratio of the indole dye(s) to iodide ions 20 is from 0.05:1 to 10.

12. Process according to claim 11 in which the said ratio is from 0.5:1 to 2:1.

13. Process according to any one of claims 1 to 12 in which the content of hydrogen peroxide in composition 25 (B) is from 1 to 40 volumes.

14. Process according to claim 13 in which the 1 - 35 content of hydrogen peroxide in composition (B) is from 2 to 20 volumes.

15. Process according to claim 13 in which the content of hydrogen peroxide in composition (B) is from 3 5 to 15 volumes.

16. Process according to any one of claims 1 to 15 in which composition (A) contains an oxidation dye or a direct dye which enables a colouring or a hue to be obtained in the presence of iodide ions and hydrogen peroxide.

17. Process according to claim 16 in which the oxidation dye is-a paraphenylenediamine, N,W-diphenylalkylenediamine, para-aminophenol, orthoaminophenol, ortho-phenylenediamine or heterocyclic oxidation base.

is

18. Process according to claim 16 in which the oxidation dye is a coupler which is a phenol, meta-diphenol, meta-aminophenol, meta-phenylenediamine, mono- or polyhydroxylated naphthalene or aminonaphthalene, a pyrazolone or a benzomorpholine.

19. Process according to claim 16 in which the oxidation dye is a rapid oxidation dye which is a trihydroxylated benzene, diaminohydroxybenzene, aminodihydroxybenzene, triaminobenzene, aminohydroxy benzene or a 1,2-hydroxy-substituted benzene.

20. Process according to any one of claims 1 to 19 in which composition (A) is applied in the first stage, X - 36 followed by composition (B) containing hydrogen peroxide at a pH of 2 to 11.

21. Process according to any one of claims 1 to 20 in which composition (A) is applied for 10 seconds to 45 minutes and composition (B) is applied for 10 seconds to 45 minutes.

22. Process according to claim 21 in which composition (A) is applied for 2 to 25 minutes and composition (B) is applied for 1 to 30 minutes.

23. Process according to claim 21 or 22 in which composition (A) is applied for 2 to 15 minutes.

24. Process according to any one of claims 1 to 23 in which at least one of the compositions is in the form of thickened or gelled liquid, cream, emulsion or foam.

25. Process according to any one of claims 1 to 24 in which composition (A) comprises an aqueous medium consisting of water or a water/solvent(s) mixture, having a pH of 2 to 7.

26. Process according to any one of claims 1 to 24 in which composition (A) is applied as an anhydrous solution.

27. Process according to any one of claims 4 to 26 in which the liquid medium comprises ethyl, propyl, isopropyl or tert-butyl alcohol, ethylene glycol, ethylene glycol monomethyl, monoethyl or monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol, propylene 1 - 37 glycol or dipropylene glycol monomethyl ether or methyl lactate.

28. Process according to any one of claims 1 to 27 in which at least one of the compositions contain one or more fatty amides in an amount of 0.05 to 10% by weight, anionic, cationic, nonionic and amphoteric surfactants in an amount of 0.1 to 50% by weight, thickening agents in an amount of 0. 1 to 5% by weight, or perfumes, sequestering agents. film-forming agents, treatment agentsf dispersants.

conditioners, preservatives, opacifiers and agents for swelling keratinous fibres.

29. Process according to any one of claims 1 to 28 in which the keratinous fibres are human hair.

30. Process according to any one of claims 1 to 29 in which the partial dyeing of human keratinous fibres is performed by applying composition (A) on locks of hair that have totally or partially lost their natural pigmentation, or hairs of the beard, moustache, eyelashes or eyebrows.

31. Process according to claim 1 substantially as described in any one of the Examples.

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