AU622878B2

AU622878B2 - Process for dyeing fibres with oxidation dyes combined with indole derivatives and dyeing compositions employed

Info

Publication number: AU622878B2
Application number: AU27026/88A
Authority: AU
Inventors: Jean Cotteret; Didier Garoche; Jean-Francois Grollier
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1987-12-18
Filing date: 1988-12-19
Publication date: 1992-04-30
Anticipated expiration: 2008-12-19
Also published as: JP2595076B2; AU2702688A; CH677873A5; GB2211517A; GB2211517B; DE3842508A1; IT1224001B; PT89238B; NL8803075A; IT8868119A0; ZA889447B; JPH01199906A; FR2624730A1; GB8829595D0; GR1000167B; BE1001329A3; FR2624730B1; PT89238A; LU87086A1

Description

I.C

i i

I

N.45300 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-1973 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: CLASS INT. CLASS -'APPLICATION NUMBER:

LODGED:

SCOMPLETE SPECIFICATION LODGED:

ACCEPTED:

PUBLISHED:

PRIORITY:

RELATED ART: SNAME OF APPLICANT: ADDRESS OF APPLICANT:

L'OREAL

14, Rue Royale, 75008 Paris France.

ACTUAL INVENTOR(S): ADDRESS FOR SERVICE: Jean Francois GROLLIER, Jean COTTERET and Didier GAROCHE Edward Waters Son, Queen Street, Melbourne, Victoria 3000,

AUSTRALIA.

COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: "PROCESS FOR DYEING FIBRES WITH OXIDATION DYES COMBINED WITH INDOLE DERIVATIVES AND DYEING COMPOSITIONS

EMPLOYED"

The following statement is a full description of this invention, including the best method of performing it known to us:- 1 la "PROCESS FOR DYEING KERATINOUS FIBRES WITH OXIDATION DYES COMBINED WITH INDOLE DERIVATIVES AND DYEING COMPOSITIONS

EMPLOYED"

The invention relates to a new process for dyeing keratinous fibres, especially human keratinous fibres such as the hair, with indole derivatives combined with certain oxidation dyes chosen from so-called "rapid" oxidation dyes :5 and couplers, to the compositions employed in this process and to devices for dyeing.

**Ot British Patent Applications 8812348.4 and 8812349.2 filed 25th May 1988, based on Luxembourg Patent Application No. 86.899, filed on 25th May 1987, describe a process for 10 dyeing keratinous fibres essentially characterized in that at least one composition containing, in a medium 9 i suitable for dyeing, at least one oxidation dye in o6.o: combination with iodide ions is applied on these fibres, the application of the composition being preceded or followed by the application of a composition which contains, in a medium suitable for dyeing, hydrogen peroxide at a pH of between 2 and 12.

Many processes are, moreover, known for dyeing keratinous fibres, especially the hair, employing 5,6-dihydroxyindole, and more especially a process that consists in e.) 4 4: t 4 t 4 C 2 dyeing hair in two distinct stages, applying on the hair a composition containing 5,6-dihydroxyindole in combination with iodide ions in a medium suitble for dyeing, this application being preceeded or followed by the application of hydrogen peroxide. Such a process is described, in particular, in FR-2,593,061.

It has been found that colorations particularly sought after in hair dyeing could be obtained in a broad palette of varied tints having glints, in particular varied hues of chestnut brown and of blond, by using certain oxidation dyes described in LU 86, 899, in combination with 5,6-dihydroxyindole or its derivatives.

Moreover, the varied hues thereby obtained show improved resistance to external agents including, in 15 partiuclar, greater resistance to light and/or to washing compared with the colorations obtained using the compositions described previously containing either the oxidation dye or the indole derivative. This result is especially noteworthy when the indole derivative is used in compositions containing oxidation dyes which, in themselves, give, on .development, relatively light colorations not possessing much depth, since depth is generally desired in hair dyeing.

Accordingly, the present invention provides a process for dyeing keratinous fibres which comprises applying to the fibres, in any order, a composition comprising, in a tii a 1 c;tr ~cr Et C IL( C I~-ii qpp i I^ 3 o a o O 4 o 4 49 o o a 1 a a o 0040 o 4o *a 44« 4 4 «a a 0 4 4 4 4 4 4 44 0 4 9 4 4 4 medium suitable for dyeing, at least one indole derivative and at least one oxidation dye which is a rapid oxidation dye or a coupler, and either iodide ions, or (b) hydrogen peroxide, at a pH of from 2 to 7, and preferably from 2 to 5, and a composition which comprises, in a medium suitable for dyeing: either hydrogen peroxide at a pH of from 2 to 12 and preferably from 2 to 7 when includes iodide ions; or iodide ions at a pH of from 3 to 11 when composition includes hydrogen peroxide.

The invention also provides a composition suitable for dyeing keratinous fibres which comprises an indole derivative and at least one oxidation dye which is a rapid oxidation dye or a coupler, in combination with iodide ions.

15 The invention further provides a multi-compartment device or kit comprising the different compositions suitable for carrying out the process according to the invention.

The application of the compositions and is optionally separated by a rinse.

20 In one embodiment of the process composition (A) comprises iodide ions and compositions comprises hydrogen peroxide.

In the process according to the invention, the indole derivative preferably has the formula -4in which: R is hydrogen, a lower alkyl group or a group -SiR 2

R

13

R

1 4

R

8 and R 9 which may be identical or different, are each hydrogen or a lower alkyl group, a carboxyl group, a lower alkoxycarbonyl group or a group -COOSiR 1 2

R

1 3

R

1 4 SRi0 and R 1 which may be identical or different, S are each hydrogen, a C -C 2 0 linear or branched alkyl group, 00. 10 a formyl group, a linear or branched C-C 2 0 acyl group, a linear or branched C 3

-C

2 0 alkenoyl group, a group S-SiR 2

R

3

R

1 4 a group -P(O)(OR 1 2 or a group R 1 5 0SO 2 or and Rl together with the oxygen and carbon atoms to which they are attached, form a ring which is unsubstituted o Q 15 or substituted by a carbonyl group, a methylene group, a a°o thiocarbonyl group or a group: o

PO(O))R

1 or 7CR R 1 7 *i a R and R 6 which may be identical or different, are each a hydrogen atom or a lower alkyl group, R 1 is a lower alkoxy group or a mono- or dialkylamino group, R 1 R, and 5

R

14 which may be identical or different, are each a linear or branched lower alkyl group; and the addition salts with inorganic or organic acids and the corresponding salts of alkali metals, alkaline-earth metals or amines.

The lower alkyl or alkoxy radicals are typically C 1

-C

6 radicals.

Examples of compounds of formula include 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 5-methoxy-6-hydroxyindole, (5 or 6)-acetoxy-(6 or 5)-hydroxyindole, 2-carboxy-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole and 2,3-dimethyl-5,6-dihydroxyindole.

SThe iodide ion suitably derives from an alkali metal iodide, alkaline-earth metal iodide or ammonium iodide, o° especially potassium iodide.

15 The so-called "rapid" oxidation dyes are dye precursor compounds having a benzene structure which are capable of generating coloured compounds by simple oxidation in the air during the exposure time on the hair. This generally occurs in less than 1 hour and in the absence of another oxidizing agent. Examples of such compounds include trihydroxylated derivatives of benzene, diaminohydroxyben- Si1 zenes, aminodihydroxybenzenes, triaminobenzenes, aminodihydroxybenzenes and substituted 1,2-dihydroxybenzenes.

Suitable trihydroxylated derivatives of benzene, include 1,2,4-trihydroxybenzene, 1,2,4-trihydroxy-5-alkylbenzenes in which the alkyl group is a C -C 6 lower alkyl group and 1,2,3-trihydroxybenzene and their salts.

Suitable diaminohydroxybenzenes include 2,4-diamino- -6phenol, 2,5-diamino-4--methoxy-l-hydroxybenzene and their salts.

Suitable aminodibvd roxybenzenes include 2-amino--l,4dihydroxybenzene, l,4-dihydroxy--2-diethylaminobenzene, 4aminoresorcinol and their salts.

Among substituted 1,2-dihydroxybenzenes, 1,2-dihydroxybenzenes substituted by a C-C 6 alkyl or C-C 6 alkoxy group are particularly suitable.

Examples of aminohydroxybenzenes include 2-amino-4methoxyphenol, 2-aminophenol, 4,6-dimethoxy-3-amino-l-hydroxybenzene, 2,6-dimethyl-4-fN-(p-hydroxyphenyl)amino]-1hydroxybenzene and their salts.

Suitable triaminobenzenes include l,5-diamino-2-methyl -4-IN.-(p-hydroxyphenyl)amino)-benzene and its salts.

The modifiers or "couplers" are compounds that are 0 t known to react with oxidation bases, also known as oxidation 01 4 4 41 1*1 4 0 0 00 ~1 14 444 t~ 4 4 0 4444 dye precursors, by an oxidative condensation process, giving coloured compounds specific to the base and the coupler in question. This reaction is referred to as "coupling". They are typically chosen from phenols, meta-diphenols, metaaminophenols, ortho-diphenol, meta-phenylenediamines, monoor polyhydroxylated derivatives of naphthalene and of aminonaphthalene, pyrazolones and benzomorpholines.

Suitable couplers or modifiers include compounds having the formula (II) -7- 41 4 in which R 1 is an OH group, or an amino group that is unsubsituted or substituted by one or more CIhydroxyalkyl groups; R 3 and R 5 are each, independently of one another, hydrogen, an OH group, an amino group unsubstituted or substituted by a C.-C 6 alkyl group or a hydroxy Cl-Cs alkyl group; R, R 4 and R 6 are each, 1 6 independently of one another, hydrogen, a Cl-C 6 alkoxy group, a C 1

-C

6 alkyl group or a hydroxy 6 alkyl group, or Rand R 4 together form a methylenedioxy group.

Examples of suitable couplers, include 3-amino-6methyiphenol, 3-aminophenol, l,3-dihydroxybenzene, 1,2-dihydroxybenzene, 2-methoxy-5-aminophenol, 2-methoxy-5-[N-(2hydroxyethyl)aminojphenol, 1, 3 -diamino-2,6-dimethoxybenzene, 2 -methoxy-l-(N-methylamino)-4-(2-hydroxyethyloxy)aminobenzene, 1,3-diamino-6-methoxybenzene, l,3-diamino-4,6-dimethoxybenzene, 4 6 -dimthoxy-1,3-bis[N-(2-hydroxyethyl)amino] -8benzene, 2,6-dimethoxy-3-[N-(2-hydroxyethyl)amino]-l-aminobenzene, 2,4-dimethoxy-3-[N-(2-hydroxyethyl)amino]-1-aminobenzene, 2-methyl-5-[N-(2-hydroxyethyl)aminojphenol, 1,3-his [N(2-hydroxyethyl)amino]-4-methoxybenzene, 3-amino-4-methoxyphenol, 3,4-methylenedioxy-l-aminobenzene, 3,4-methylenedioxy-6-methoxy-l-aminobenzene, 2,6-dimethyl-3-(N-(2-hydroxyethyl)aminolphenol, 2,6-dimethyl-3-aminophenol, 4-ethoxy-1amino-3-[N,N-bis(2-hydroxyethyl)amino]benzene, (2,4-diaminophenoxy)ethanol, [2-amino--4-(N-methylamino)-phenoxy]ethanol, 1-methoxy-2-[N-(2-hydroxyethyl)aminol-4-aminobenzene and their salts.

Other suitable couplers are 6-aminobenzomorpholine, 6hydroxybenzomorpholine, l-naphthol and l-amino-7--naphthol and their salts.

15 These different oxidation dyes are used as mixtures or alone, in combination with iodide ions and indole derivatives.

One preferred embodiment of the invention comprises using, in combination with 5,6-dihydroxyindole and iodide ions, at least one trihydroxylated derivative of benzene, such as 1,2,4-trihydroxybenzene or 1,2,4-trihydroxy-5-methylbenzene, or alternatively a coupler such as 1,3-dihydroxybenzene, 3-aminophenol, 3-amino-6-methylphenol, 3,4-methylenedioxy-6-methoxy-1-aminobenzene, l-naphthol or a mixture thereof.

The result obtained with the combination according to the invention is epsecially surprising in view of the dyeing 4, 0~ e~ p .3 4.34 .3.3 44 4 9 properties of these oxidation dyes in traditional systems, especially couplers which give rise to a coloration only in the presence of a base or oxidation dye precursor, by an oxidative condensation process.

According to the present invention, the composition suitable for dyeing keratinous fibres, especially human hair, typically comprises at least 5,6-dihydroxyindole or one of its derivatives of formula an oxidation dye which is a "rapid" oxidation dyes or a coupler, and iodide -ions, in a medium suitable for dyeing. The oxidation dyes used in the composition of the invention are generally chosen from the preferred dyes defined above.

The composition comprising 5,6-dihydroxyindole or aa Qd S one of its derivatives of formula the oxidation dye and o 15 the iodide ions, generally comprises the oxidation dye in a o9 B proportion of from 0.01 to 10% by weight relative to the total weight of composition for example from 0.25 to by weight. The 5,6-dihydroxyindole or one of its derivatives of formula is generally present in 4 4 20 proportions of from 0.01 to 5% by weight, for example from '4 Si 0.03 to 3% by weight, relative to the total weight of the o composition The proportion of iodide in these same o compositions is typically from 0.007 to 4% by weight, 4 expressed as I-ions, for example from 0.08 to 1.5% by weight, expressed as I-ions, relative to the total weight of the compositions The hydrogen peroxide content used in the compositions Ir 4 44 1 4 4 4 4

I

I I 4 t tI 4 4 III I 1

I

'1 10 is typically from 1 to 40 volumes, preferably from 2 to volumes, for example from 3 to 10 volumes.

The ratio by weight of the indole derivative of formula and oxidation dye to iodide ions is typically from 0.05:1 to 10:1, for example from 0.5:1 to 2:1.

The process according to the invention is carried out by arranging exposure times, for the different compositions applied in each of the different steps of the process, of from 10 seconds to 45 minutes, typically of the orde_ of 2 to 25 minutes, for example 2 to 10 minutes.

It has been found that the process according to the invention enables various colorations to be obtained over a wide range of hues capable of being well endowed with glints, the colorations being both rapid and strong, 15 penetrating well into the fibres, and in particular human keratinous fibres such as the hair, without degrading them.

These colorations also show an improved resistance to erternal agents including, more especially, an improved resistance to light and/or to washing compared with 20 processes exclusively employing 5,6-dihydroxyindole or one of its derivatives of formula in combination with iodide ions, or exclusively the oxidation dye in combination with iodide ions.

It has also been noted that hair dyed several times, following regrowth, by means of the processes and the compositions employed according to the invention is softer, more shiny and has good mechanical properties, compared with

L

11 hair dyed employing the processes and the compositions of the prior art.

By means of the process and the compositions according to the invention, relatively intense colorations are obtained in relatively short times, of the order of 5 to minutes.

The compositions used for carrying out the process according to the invention may be presented in various forms, such as thickened or gelled liquids, creams, emulsions, foams or other forms suitable for carrying out 0 dyeing.

o.o The dyeing compositions designed for use in the .c process according to the invention, and containing 5,6dihydroxyindole or one of its derivatives of formula and 15 the oxidation dye in combination with iodide ions suitably comprise an aqueous medium consisting of water or a water/ ,solvent mixture, the solvent typically being an organic solvent comprising at least one of ethyl alcohol, propyl or 0i isopropyl alcohol, tert-butyl alcohol, ethylene glycol, t 20 ethylene glycol monomethyl, monoethyl ether acetate, propylene glycol, propylene glycol and dipropylene glycol monomethyl ethers and methyl lactate. The especially "i preferred solvents are ethyl alcohol and propylene glycol.

The indole derivatives and the oxidation dyes may also be stored with the iodides in a medium comprising anhydrous solvents, this composition being mixed at the time of use with an aqueous medium.

A

*12 12 When the medium is aqueous, the composition has a pH of from 2 to 7, for example from 3.5 to 7.

According to the invention, a solvent comprising less than 1% of water is referred to as an anhydrous solvent.

When the medium consists of a water/solvent mixture, the solvent is typically present in a concentration of from to 75% by weight relative to the total weight of the composition, for example from 2 to 50%, especially from 2 to The compositions according to the invention suitably include other conventional adjuvants customarily used in the o a dyeing of keratinous fibres.

Examples of such adjuvants, suitable for hair dyeing, include fatty amides in proportions of 0.05 to 10%, anionic, 15 cationic, nonionic or amphoteric surfactants, or mixtures thereof, present in proportions of from 0.1 to 50% by weight, thickeners, perfumes, sequestering agents, film-forming agents, treatment agents, dispersants, conditioners, preservatives, opacifiers and agents for swelling keratinous fibres.

Examples of thickeners include sodium alginate, gum arabic, guar gum, biopolymers such as xanthan gum or scleroglucans, cellulose derivatives such as methylcellulose, hydroxyethylcellulose,hydroxypropylmethylcellulose and carboxymethylcellulose sodium salt, and acrylic acid polymers. It is also possible to use inorganic thickening agents such as bentonite. These thickeners, used 13 alone or as mixtures, are generally present in a proportion of from 0.1 to 5% by weight relative to the total weight of the composition, particularly from 0.5 to 3%.

Suitable acidifying agents for use in the process, when the compositions are at acid pH, include lactic acid, acetic acid, tartaric acid, phosphoric acid, hydrochloric acid and citric acid.

It is also possible to adjust the pH with alkalinizing agents chosen, for example, from amines such as alkanolamines, alkylamines and alkali metal or ammonium hydroxides or carbonates, in partiuclar when the precursors are used in the form of salts of strong acids.

When the composition is used in the form of a foam, it Va is suitably packaged under pressure in an aerosol device in t*0 .O 15 the presence of a propellant and at least one foam generator. The foam generators can be anionic, cationic, nonionic or amphoteric foaming polymers, or surfactants of the type defined above.

For the purpose of carrying out the process according S o 20 to the invention, the different compositions are conveniently packaged in a multi-compartment device, also 0o referred to as a dyeing kit or outfit, 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 suitably comprise a first compartment containing the composition (A) comprising an indole derivative and oxidation dye, both as 14 14 defined above, in the presence of iodide ions in a medium suitable of dyeing, and a second compartment comprising a hydrogen peroxide solution.

When the medium containing the indole derivative, the oxidation dye and the iodide ions is an anhydrous medium, mixing is performed, before use, with an aqueous vehicle suitable for dyeing, present, where appropriate, in a third compartment.

The composition containing the indole derivative, the oxidation dye and the iodide ions in an anhydrous medium can optionally be applied directly on the wet keratinous fibres.

When the composition applied on the fibres oI t 04 contains hydrogen peroxide, the dyeing outfit typically comprises, in a first compartment a composition (A) containing, in a medium suitable for dyeing, an indole derivative and oxidation dye as defined above, in a second compartment a composition containing iodide ions, and a third compartment containing an aqueous hydrogen peroxide composition, the content of the third compartment being 20 designed to be mixed with the content of the first compartment immediately before use.

When the medium suitable for dyeing is aqueous the composition of the first compartment suitably has a pH of from 2 to 7, for example from 3.5 to 7. The pH of the composition containing hydrogen peroxide is from 2 to 12, but it is typically from 2 to 7, for example from 2 to The multi-compartment devices which are usable 15 according to the invention may be equipped with means, known per se, for mixing at the time of use, and be packaged under an inert atmosphere.

The process and the compositions used according to the invention may be employed for dyeing natural or already dyed hair, permanent-waved or otherwise or straightened, or strongly or lightly bleached and optionally permanent-waved hair. It is also possible to use them for dyeing furs or wool.

The following examples further illustrate the invention.

t f t EXAMPLE 1 The following compositions are prepared: COMPOSITION A I I 5,6-Dihydroxyindole 0.30 g 1,2,4-Trihydroxybenzene 1.00 g Potassium iodide 1.00 g 4* 4 Ethyl alcohol 10.00 g Guar gum, sold by the company 16 Itt1

A

0% CELANESE under the name "JAGUAR HP 60" 1.00 g Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" 5.00 g AS Preservative qs Natural pH 5.8 Water qs 100.00 g COMPOSITION B containing 12.5 volumes of hydrogen peroxide: Hydrogen peroxide 3.75 g Ammonium lauryl sulphate 6.70 g Gum arabic 1.00 g Stabilizer 0.03 g Perfume qs 2-Amino-2-methyl-1-propanol qs pH 4 Water qs 100.00 g The dyeing of 90% white natural hair is performed by applying the composition The composition is left in place for minutes. After rinsing with water, the "12.5 volumes" hydrogen peroxide composition is applied and left to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a golden light chestnut brown with red glints.

EXAMPLE 2 The following composition is prepared: It 1% t 0 i 0 0 -7-7 17- COMPOSITION A,: 5,6-Dihydroxyindole 1,3-Dihydroxybenzene 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 concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" Preservative qs Natural pH 0.60 0.05 0.40 1.00 10.00 1.00 g 5.00 g AS *4#4

S*

a: 44 4i Ir I 4 4 t 4 4 44 4I 4 Water qs 100.00 g 15 The dyeing of 90% white permanent-waved hair is performed by applying the composition (Az).

The composition is left in place for 15 minutes.

After rinsing with water, a "12.5 volumes" hydrogen peroxide composition is applied and left to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a dark chestnut brown with a natural glint.

EXAMPLE 3 The following composition is prepared: COMPOSITION A,: 5,6-Dihydroxyindole 0.20 g 3-Aminophenol 0.10 g Potassium iodide 1.00 g 18 Ethyl alcohol 10.00 g Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" 1.00 g Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" 5.00 g AS Preservative qs Natural pH 7 Water qs 100.00 g The dyeing of 90% white natural hair is performed by applying composition

A

3 The composition is left in place for 15 minutes.

4 After rinsing with water, a "12.5 volumes" hydrogen ,peroxide composition is applied and left to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a golden blond with a natural glint.

EXAMPLE 4 The following composition is prepared: COMPOSITION A,: S 20 5,6-Dihydroxyindole 0.70 g 1,2,4-Trihydroxy-5-methylbenzene 3.00 g Potassium iodide 2.00 g Ethyl alcohol 10.00 g Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" 1.00 g Glycoside alkyl ether, sold at a concentration of 60% AS by the company i

I

/19 19 SEPPIC under the name "TRITON CG 110" 5.00 g AS Preservative qs Natural pH 5.4 Water qs 100.00 g The dyeing of 90% white permanent-waved hair is performed by applying the composition The composition is left in place for 15 minutes.

After rinsing with water, a "12.5 volumes" hydrogen peroxide composition is applied and left to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed an auburn dark blond.

EXAMPLE The following composition is prepared: S" COMPOSITION As: 5,6-Dihydroxyindole 0.50 g 1,3-Dihydroxybenzene 0.50 g Potassium iodide 1.00 g Ethyl alcohol 10.00 g Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" 1.00 g Glycoside alkyl ether, sold at a sconcentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" 5.00 g AS Preservative qs Triethanolamine qs pH 6 Water qs 100.00 g S_

A

The dyeing of 90% white permanent-waved hair is performed by applying the composition (A 5 The composition is left in place for 15 minutes.

After rinsing with water, a "12.5 volumes" hydrogen peroxide composition is applied and left to act for minutes. After rinsing with water and shampooing, the hair is dyed an ash-blond chestnut brown.

EXAMPLE 6 The following composition is prepared: COMPOSITION

A

6 0, 5,6-Dihydroxyindole 0.20 g .oF 3-Aminophenol 0.10 g 1,2,4-Trihydroxybenzene 0.40 g Potassium iodide 0.50 g Ethyl alcohol 10.00 g Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" 1.00 g Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" 5.00 g AS Preservative qs Natural pH 6.3 Water qs 100.00 g The dyeing of 90% white natural hair is performed by applying the composition The composition is left in place for 15 minutes.

After rinsing with water, a "12.5 volumes" hydrogen

I

21 o c a-d .4 41 0.444 B z 0.

o 8i 4 4.

o 84 8 peroxide composition is applied and left to act for minutes. After rinsing with water and shampooing, the hair is dyed a slightly ashen golden blond.

EXAMPLE 7 The following composition is prepared: COMPOSITION A 7 5,6-Dihydroxyindole 0.30 g 3-Amino-6-methylphenol 0.30 g 1,2,4-Trihydroxybenzene 0.30 g Potassium iodide 0.80 g Ethyl alcohol 10.00 g Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" 1.00 g Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" 5.00 g AS Preservative qs Natural pH 6.7 Water qs 100.00 g 20 The dyeing of 90% white natural hair is performed by applying the composition (A 7 The composition is left in place for 15 minutes.

After rinsing with water, a "12.5 volumes" hydrogen peroxide composition is applied and left to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a russet brown.

Ill~l~-L1 22 EXAMPLE 8 The following composition is prepared: COMPOSITION A 9 5,6-Dihydroxyindole l-Naphthol Potassium iodide Ethyl alcohol Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" Preservative qs Triethanolamine qs pH 0.40 g 0.40 g 0.80 g 10.00 g 1.00 g 5.00 g AS Itc a ar

'I

a.

a a Water qs 100.00 g The dyeing of 90% white natural hair is performed by applying the composition (Ag).

The composition is left in place for 15 minutes.

After rinsing with water, a "12.5 volumes" hydrogen peroxide composition is applied and left to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed a light chestnut brown with an ashen glint.

EXAMPLE 9 The following composition is prepared: COMPOSITION Ag 5,6-Dihydroxyindole 0.30 g 4 r_ i 4' 4 23 3,4-Methylenedioxy-6-methoxy- 1-aminobenzene Potassium iodide Ethyl alcohol Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" Preservative qs Triethanolamine qs pH 6 0.30 g 0.50 g 10.00 g 1.00 g 5.00 g AS 1 a tr 4 I 4.

4 4 4 t 4 4t 4 Water qs 100.00 g The dyeing of 90% white natural hair is performed by applying the composition (A The composition is left in place for 15 minutes.

After rinsing with water, a "12.5 volumes" hydrogen peroxide composition is applied and left to act for minutes. After rinsing with wrter and shampooing, the hair is dyed a light chestnut brown.

EXAMPLE The following composition is prepared: COMPOSITION

A

1 0: Sodium iodide 0.40 g Ethyl alcohol 5.00 g Propylene glycol 5.00 g Xanthan gum, sold by the company RHONE POULENC under the name 1 4 24 "RHODOPOL SC" 2.00 g Preservative 0.10 g Triethanolamine qs pH Demineralized water qs 100.00 g COMPOSITION B,: 5,6-Dihydroxyindole 1.00 g 2,4-Diaminophenoxyethanol dihydrochloride 1.20 g 3-Amino-6-methylphenol 0.50 g Glycoside alkyl ether sold at a concentration of 60% AS by the company SSEPPIC under the name "TRITON CG 110" 7.50 g AS Xanthan gum, sold by the company RHONE POULENC under the name "RHODOPOL SC" 3.00 g Ethyl alcohol 12.00 g Triethanolamine qs pH Demineralized water qs 100.00 g The composition A 10 is applied for 15 minutes on natural grey hair containing 90% of white hairs. A rinsing is performed. A weight-for-weight mixture of the composition B, with a hydrogen peroxide at pH 3 assaying at 20 volumes, this mixture being prepared at the time of use, is then applied for 15 minutes. The hair is then rinsed and dried. It is coloured a slightly ashen natural blond.

EXAMPLE 11 The following composition is prepared: COMPOSITION An: 5,6-Dihydroxyindole 0.45 g 6-Hydroxybenzomorpholine 0.45 g Ethylene glycol monobutyl ether 8.50 g Potassium iodide 0.30 g Hydroxyethylcellulose, sold by the company AQUALON under the name "NATROSOL 250 HHR" 1.00 g Tartaric acid qs pH *4 Demineralized water qs 100.00 g 4 Natural grey hair containing 90% of white hair is 4 pretreated for 10 minutes with a hydrogen peroxide composition B 2 at pH 3, assaying at 30 volumes. After rinsing, the composition is applied for 20 minutes.

t After rinsing and drying, the hair is dyed in a very ashen light blond hue. If the intermediate rinse is eliminated, the hue obtained is a pearly ashen dark blond.

EXAMPLE 12 The following composition is prepared: COMPOSITION A 2 2-Methyl-5,6-dihydroxyindole hydrobromide 0.70 g Resorcinol 0.40 g 3-Aminophenol 0.10 g 26 3-Amino-6-methylphenol 0.25 g Potassium iodide 0.60 g Ethyl alcohol 10.00 g Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" 1.00 g Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" 5.00 g AS Triethanolamine qs pH 6 Preservatives 0.60 g Demineralized water qs 100.00 g This composition is applied for 20 minutes on natural grey hair containing 90% of white hairs. After rinsing, a hydrogen peroxide composition B 3 at pH 3, assaying at 12.5 volumes, is applied for 10 minutes.

After rinsing and drying, the hue obtained is an ashen golden light blond.

EXAMPLE 13 Example 12 is repeated, but the pH of the hydro- I 20 gen peroxide used is brought to 8.5 before use with 2amino-2-methyl-1-propanol. A very light blond with a J golden ashen glint is obtained as the final hue.

EXAMPLE 14 The following composition is prepared: COMPOSITION A 13 5-Acetoxy-6-hydroxyindole 0.60 g 6-Aminobenzomorpholine dihydrochloride 0.80 g I Ij .4 4 f

*II

1 4.44 -2^ 27 1,2,4-Trihydroxybenzene 0.40 g Potassium iodide 1.00 g Ethyl alcohol 15.00 g Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" 5.00 g AS Xanthan gum, sold by the company RHONE POULENC under the name "RHODOPOL SC" 1.50 g Preservatives 0.15 g Triethanolamine qs pH 7 Demineralized water qs 100.00 g This composition is applied for 12 minutes on natural grey hair containing 90% of white hairs, and is then rinsed off. The hair is then treated with a hydrogen peroxide composition B 3 at pH 3, assaying at 12.5 volumes, for 8 minutes. After rinsing and drying, the hair is coloured in a natural light blond hue with a slightly golden ashen glint.

EXAMPLE Example 14 is repeated, but the pH of the hydrogen peroxide used is brought to 8 before use with triethanolamine. The same final dyeing result is obtained as in Example 14, that is to say a natural light blond hue with a slightly golden ashen glint.

EXAMPLE 16 The following composition is prepared: ;2

L

.7 'p 28 4 1: 41i 41r 4- 4 4 1 4, 1C 4( 4 4 4: 4r S 444 1( COMPOSITION A 14 5,6-Dihydroxyindole 1,2,4-Trihydroxybenzene 3-Aminophenol Sodium iodide Ethylene glycol monoethyl ether Sodium lauryl ether sulphate containing 2 moles of ethylene oxide, sold by the company LEVER in a strength solution in water under the name "SACTIPON 8533" Hydrochloric acid qs pH Preservatives Demineralized water qs 10 COMPOSITION B, containing 12.5 volumes of H,0,: Hydrogen peroxide Ammonium lauryl sulphate Thickener Stabilizer Perfume qs Monoethanolamine qs pH Water as 10 0.50 g 0.50 g 0.15 g 0.40 g 7.50 g 3.00 g AS 0.15 0.00 3.75 6.70 1.00 0.03 I0.0 a The composition A, 1 is applied for 15 minutes on natural grey hair containing 90% of white hairs. It is rinsed off and the hydrogen peroxide composition B 4 is applied for 10 minutes. After rinsing and drying, a natural light blond coloration with a slightly ashen -I

%J

29 glint is obtained.

EXAMPLE 17 The following composition is prepared: COMPOSITION A 15 5,6-Dihydroxyindole 4-Methyl-1,2-dihydroxybenzene Potassium iodide Ethyl alcohol Guar gum, sold by the company CELANESE under the name "JAGUAR HP 60" Glycoside alkyl ether, sold at a concentration of 60% AS by the company SEPPIC under the name "TRITON CG 110" Triethanolamine qs pH 7 Preservative qs Water qs 1 0.10 g 1.00 g 1.00 g 10.00 g 1.00 g 5.00 g AS 1 (r

I

00.00 g The dyeing of 90% white natural grey hair is performed by applying the composition A 1 s, which is left in place for 10 minutes. After rinsing with water, a 20 volumes" hydrogen peroxide composition pH 3.8, is applied and left to act for 5 minutes. After rinsing with water and shampooing, the hair is dyed ash blond.

Claims

2. A process according to Claim 1 wherein the composition comprises iodide ions and composition (B) comprises hydrogen peroxide.
3. A process according to Claim 1 or 2 in which the indole derivative has the formula -R9 I (I) in which: R7 is hydrogen, a lower alkyl group or a group -SiR 1 2 R 13 R 1 4 -*2 31 R and which may be identical or differnnt, are each hydrogen or a lower alkyl group, a carboxyl group, a lower alkoxycarbonyl group or a group -COOSiR 1 2 R 1 3 R 1 4 R and R which may be identical or different, are each hydrogen, a Ci-C 2 0 linear or branched alkyl group, a formyl group, a linear or branched C 2 -C 2 0 acyl group, a linear or branched C 3 -C 2 0 alkenoyl group, a group -SiR 2 R 3 R 4 a group -P(O)(OR15) 2 or a group R 1 5 S0 2 or Rio and R together with the oxygen and carbon atoms to which they are attached, form a ring which is unsubstituted or substituted by a carbonyl group, a methylene group, a thiocarbonyl group or a group: i t 7IPO(O) )R 15 or CR6 R 7 R, and R 16 which may be identical or different, are each a hydrogen atom or a lower alkyl group, R 17 is a lower alkoxy group or a mono- or dialkylamino group, R R 13 and R 4' which may be identical or different, are each a linear or branched lover alkyl group; and the addition salts with inorganic or organic acids and the corresponding salts of alkali metals, alkaline-earth metals or amines.
4. A process according to any one of Claims 1 to 3, in whcih the indole derivative is 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 5-methoxy-6-hydroxyindole, or 6)-acetoxy-(6 or 5)-hydroxyindole or 2-carboxy-5,6-dihy- droxyindole.
32- I 11< i rt, t t i I A process according to any one of the preceding claims which comprises applying to the fibres, in any order, a composition comprising, in a medium suitable for dyeing, 5,6-dihydroxyindole and at least one oxidation dye which is a rapid oxidation dye or a coupler in combination with iodide ions and a composition which comprises, in a medium suitable for dyeing, hydrogen peroxide at a pH of from 2 to 12. 6. A process according to any one of the preceding claims in which the iodide ions derive from alkali metal, alkaline-earth metal or ammonium iodides. 7. A process according to any one of the preceding claims in which composition comprises an alkali metal iodide, alkaline-earth metal iodide or ammonium iodide and 15 the composition comprises, in a medium suitable for dyeing, hydrogen peroxide. 8. A process according to any one of the preceding claims in which the hydrogen peroxide is an aqueous composition of "1 to 40 volumes". 9. A process according to Claim 8 in which the hydrogen peroxide is an aqueous composition of "2 to volumes" A process according to any one of the preceding claims in which the compositions and are each applied to the fibres for 10 seconds to 45 minutes. 11. A process according to Claim 10 in which compositions and are each applied to the fibres for r i 33 2 to 25 minutes. 12. A process according to claim 1 and substantially as hereinbefore described in any one of Examples 1 to 17. 13. A composition suitable for dyeing keratinous fibres to be used in the process as claimed in any one of claims 3 to 12 which comprises an indole derivative as defined in claim 3 or 4 and at least one oxidation dye which is a rapid oxidation or a coupler, in combination with iodide ions. 14. A composition according to claim 13 in which the oxidation dye consists of a coupler. A composition according to claim 14 in which the coupler is a phenol, meta- .diphenol, meta-aminophenol, ortho-diphenol, meta-phenylenediamine, mono- or poly- S hydroxylated derivative of naphthalene or of aminonaphthalene, pyrazolone or l benzomorpholine. f 16. A composition according to claim 14 or 15, in which the coupler is a i compound of formula (II): R 6 R in which R 1 is an OH group, or an amino group that is unsubstituted or substituted by one or more C1-C 6 hydroxyalkyl groups; R 3 and Rs are each, independently of one another, hydrogen, an OH group, an amino group unsubstituted or substituted by a C1-Cs alkyl group or a -34 hydroxy C 1 -C 6 alkyl group; R 2 R, and R 6 are each, independently of one another, hydrogen, a C 1 -C 6 alkoxy group; a C -C 6 alkyl group or a hydroxy (C -C 6 )alkyl group; or R 3 and R 4 together form a methylenedioxy group. 17. A composition according to Claim 16 in which the coupler of formula (II) is 3-aminophenol, 1,3-dihydroxy- benzene, 1,2-dihydroxybenzene, 3-amino-6-methylphenol, l,3-diamino-4,6-dimethoxybenzene, 2-methoxy-5-[N-(2-hydroxyethyl)aminojphenol, 1,3-diamino-2, 6-dimethoxybenzene, 2-methoxy--1-(N-methylamino)-4-(2-hydro- xyethyloxy)aminobenzene, 1,3-diamino-6-methoxybenzene, 4,6- diehx-,-i[-2hdoyty4mnlezn,26dm dethoxy-13i[N-(2-hydroxyethyl)aminomnbenzene, 2-6-dim- ethoxy-3-[N-(2-hydroxyethyl)amino]-l-aminobenzene, 2,-my- 5-[N-(2--hydroxyethyl)aminolphenol, 4-methoxy--1,3-bis[N-(2- hydroxyethyl)amino]benzene, 3-amino-4-methoxyphenol, 3,4- methylenedioxy-1-aminobenzene, 3,4-methylenedioxy-6-methoxy- 1-aminobenzene, 2,6-dimethyl-3-[N-(2-hydroxyethyl)amino] phenol, 2,6-dimethyl-3-aminophenol, 4-ethoxy-1-amino-3-[N,N- bis(2-hydroxyethyl)aminolbenzene, (2,4-diaminophenoxy) ethanol, [2-amino-4-(N-methylamino)phenoxy]ethanol, 1-meth- oxy-2-(N-(2-hydroxyethyl)amino]-4-aminobenzene or a salt thereof. 18. A composition according to Claim 14 or 15, in which the coupler is 6-aminobenzomorpholine, 6-hydroxy- benzomorpholine, 1-napthol, 1-amino-7-naphthol or a salt thereof. a' o Ii a 4410 I lIt I', 41 a I I' 4 35 19. A composition according to Claim 13 in which the oxidation dye comprises a rapid oxidation dye which is a trihydroxylated derivative of benzene, a diaminohydroxy- benzene, aminodihydroxybenzene, aminohydroxybenzene, triam- inobenzene or substituted l,2-dihydroxybenzene. A composition according to Claim 19 in which the rapid oxidation dye is l,2,4-trihydroxybenzene, 1,2,4-tni- 1 -C 6 alkyl)-benzene, l,2,3-trihydroxybenzene, 4-aminoresorcinol, 2-amino-l,4-dihydroxybenzene, 2-amino-4- methoxyphenol, 2,4-diaminophenol, 2-aminophenol, 4-methyl-i, 2-dihydroxybenzene, 3-methoxycatechol, l,4-dihvdroxy-2- diethylaminobenzene, 2,5-diamino-4-methoxy-l-hydroxybenzene, 4,6-dimethoxy, 3-amino-l-hydroxybenzene, 2,6-dimethyl-4-[N- (p-hydroxyphenyl)amino1-1-.hydroxybenzene, or 1,5-diamino-2- 15 methyl-4-[N-(p-hydroxyphenyl)amino]benzene, or a salt thereof. 21. A composition according to Claim 13 which comprises iydroxyindole or an indole derivative as defined in Claim 3, an oxidation dye which is 1,2,4-tri- hydroxybenzene, l,2,4.-trihydroxy-5-methylbenzene, 1,3-di- hydroxybenzene, 3-aminophenol, 3-amino-6-methylphenol, 3,4- methylenedioxy-6-methoxy-1-aminobenzene or 1-naphthol, and iodide ions. 22. A composition according to any one of Claims 13 to 21 in which the oxidation dye is present in a proportion of from 0.01 to 10% by weight and the indole derivative is present in a proportion of from 0.01 to 5% by weight, a 1 4 1 a I It IL #401 a 4 to t~lt*~ i i 36 relative to the total weight of the composition. 23. A composition according to Claim 22 in which the oxidation dye is present in a proportion of from 0.25 to by weight and the indole derivative is present in a proportion of from 0.03 to 3% by weight, relative to the total weight of the composition. 24. A composition according to any one of Claims 13 to 23 in which iodide is present in a proportion of from 0.007 to 4% by weight, expressed as I-ions, relative to the total weight of the composition. A composition according to Claim 24 in which the iodide is present in a proportion of from 0.08% to 1.5% by weight, expressed as I-ions, relative to the total weight of the composition. 26. A composition according to any one of Claims 13 to 25 in which the ratio by weight of the indole derivative and the oxidation dye to iodide is from 0.05:1 to 10:1. 27. A composition according to Claim 26 in which the ratio is from 0.5:1 to 2:1. 28. A composition according to any one of Claims 13 to 27 in which the medium suitable for dyeing is an aqueous medium comprising water or a mixture of water and a solvent having a pH of from 2 to 7. 29. A composition according to Claim 28 in which the pH is from 3.5 to 7. A composition according to any one of Claims 13 to 29 which comprises at least one anhydrous solvent. 37 31. A composition according to claim 30 in which the solvent is ethyl alcohol, propyl or isopropyl alcohol, tertbutyl alcohol, ethylene glycol, ethylene glycol monomethyl, monoethyl or monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol, propylene glycol or dipropylene glycol monomethyl ether or methyl lactate. 32. A composition according to any one of claims 13 to 31 which comprises at least one adjuvant which is a fatty amide in a proportion of 0.05 to 10% by weight, an anionic, cationic, nonionic or amphoteric surfactant or a mixture thereof, present in a proportion of from 0.1 to 5% by weight, a perfume, sequestering agent, film-forming agent, treatment agent, dispersant, conditioner, preservative, opacifiers or an agent for swelling keratinous fibres.
33. A composition according to claim 13 and substantially as hereinbefore described in any one of Examples 1 to 17. S34. A process for dyeing keratinous fibres according to any one of claims 1 to 11 in which the composition is as defined in any one of claims 13 to 33. 0 A process according to claim 34 in which the keratinous fibres are human hair.
36. A multi-compartment device or kit for dyeing which comprises, in a first compartment, in a medium suitable for dyeing, a composition as defined in any one of claims 13 to 33, and in a second compartment, in a medium suitable for dyeing, an aqueous hydrogen peroxide composition'. when used in the process defined in any one of claims 1 to 12.
37. A device or kit according to claim 36 in which the aqueous hydrogen peroxide composition has a pH of from 2 to 12.
38. A device or kit according to claim 37 in which the pH is from 2 to 7.
39. A multi-compartment device or kit for dyeing keratinous fibres which y do^ comprises a first compartment containing a composition containing, in an anhydrous solvent medium, iodide ions, an indole derivative as defined in claim 3 or 4 and at least S one oxidation dye or a coupler; a second compartment containing an aqueous medium 38 suitable for dyeing; and a third compartment containing an aqueous composition of 1 to volumes hydrogen peroxide at a pH of from 2 to 12, the composition contained in the second compartment being designed to be mixed with the content of the first compartment at the time of use, when used in the process as claimed in any one of claims 3 to 12. A multi-compartment device or kit according to claim 39 in which the pH in the third compartment is from 2 to 7.
41. A mlti-compartment kit or kit device when used for dyeing according to the process as claimed in any one of claims 3 to 12 which comprises a first compartment containing a composition comprisirng, in a medium suitable for dyeing, an indole derivative as defined in claim 3 or 4 and at least one oxidation dye which is a rapid oxidation dye or a coupler; a second compartment containing a composition comprising, in a medium suitable for dyeing, iodide ions; and a third compartment containing hydrogen peroxide in an aqueous medium, the content of the third compartment being designed to be mixed with the content of the first compartment immediately before use. DATED this 17th day of January, 1992. L'OREAL WATERMARK PATENT TRADEMARK ATTORNEYS Ji THE ATRIUM 4 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA