JP2595076B2 - Keratin fiber dyeing method and dyeing composition - Google Patents

Description

The present invention relates to the dyeing of keratin fibres, in particular human keratin fibres, such as hair, by indole derivatives selected from so-called "fast" oxidation dyes and couplers. It relates to a new method of using in combination with certain oxidation dyes and to the compositions used in that method.

BACKGROUND OF THE INVENTION Applicants have applied to Luxembourg Patent Application No. 86,899, filed May 25, 1987, applying at least one composition (A) on keratin fibers, wherein the composition (A) is used for dyeing. At least one oxidation dye in combination with an iodine ion in a suitable medium, the application of the composition (A) being performed prior to or subsequent to the application of the composition (B); Described a method for dyeing keratin fibers essentially comprising hydrogen peroxide at pH 2 to 12 in a medium suitable for dyeing.

On the other hand, a number of methods are known for dyeing using keratin fibres, in particular hair, 5,6-dihydroxyindole, and still more particularly methods comprising dyeing the hair in two different stages, This method applies, on the hair, a composition comprising 5,6-dihydroxyindole in combination with iodide ions in a medium suitable for dyeing, and the application can be preceded or followed by the application of hydrogen peroxide. Done. One such method is described, for example, in French Patent Application No. 2,593,061.

SUMMARY OF THE INVENTION Applicants have found that a particularly wide range of colors and glosses, particularly those that are required for dyeing hair, for example, in various shades of maroon and blond, are of the prior applicant. It has been discovered that certain oxidation dyes described in Luxembourg Patent Application No. 86,899 can be obtained by using them in combination with 5,6-dihydroxyindole or derivatives thereof.

On the other hand, the Applicant has argued that the various shades obtained in this way show an improved resistance to external factors, in particular the resistance to light and to washing, which is obtained from the compositions containing the abovementioned oxidation dyes or indole derivatives. It was found to be superior to the dyeing obtained. This result is particularly pronounced when the indole derivative is used in a composition containing an oxidation dye. Oxidation dyes themselves give a relatively transparent dyeing upon color development and do not provide much ground color, but a ground color is generally desired in hair dyeing.

SUMMARY OF THE INVENTION The present invention therefore uses 5,6-hydroxyindole or a derivative thereof in combination with at least one oxidation dye selected from the group consisting of so-called "fast" oxidation dyes and couplers. The purpose is to do.

Another object of the invention consists of the composition used during this method.

The present invention is also directed to a device or "kit" having several compartments, which contains various compositions suitable for performing the method of the present invention.

Other objects of the invention will become apparent on reading the following description and examples.

An essential feature of the method for dyeing lactin fibers of the present invention, especially human keratin fibers, is that at least one
Seed composition (A) is applied, wherein composition (A) is at least one selected from the group consisting of at least one indole derivative and a so-called "fast" oxidation dye and a Kupler in a medium suitable for dyeing. An oxidation dye comprising (a) iodine ions or (b) hydrogen peroxide in combination, the application of the composition (A) being carried out before or after the application of the composition (B). And the composition (B) is in a medium suitable for dyeing: (a) when the composition (A) contains iodide ions,
2, and preferably hydrogen peroxide at pH 2-7, or (b) pH 3-11 when composition (A) contains hydrogen peroxide.
And iodine ion.

When the composition (A) contains hydrogen peroxide, the pH of the composition (A) is preferably from 2 to 7, and especially from 2 to 5
It is.

The application of the compositions (A) and (B) is optionally separated by rinsing.

A preferred method consists in applying a composition (A) comprising simultaneously an indole derivative and an oxidation dye in combination with iodine ions onto a fiber, and applying the composition (A) to a composition comprising hydrogen peroxide. May be preceded or followed by the application of (B).

In the method of the present invention, the indole derivative corresponds to the formula:

In the above formula, R ₇ is a hydrogen atom, a lower alkyl group or -SiR ₁₂ R ₁₃ R ₁₄
Represents a group.

R ₈ and R ₉ are the same or different and represent a hydrogen atom or a lower alkyl group, a carboxyl group, a lower alkoxycarbonyl group or a —COOSiR ₁₂ R ₁₃ R ₁₄ group.

R ₁₀ and R ₁₁ are the same or different and are a hydrogen atom, a linear or branched C ₁ -C ₂₀ 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, -SiR ₁₂ R ₁₃ R ₁₄ group, -P (O)
(OR ₁₅ ) ₂ , R ₁₅ OSO ₂ or R ₁₀ and R ₁₁ together with the oxygen atom connecting them, optionally together with a carbonyl, methylene, thiocarbonyl or the following group PO (O) OR ₁₅ or Form a ring containing CR ₁₆ R ₁₇ .

R ₁₅ and R ₁₆ represent a hydrogen atom or a lower alkyl group,
R ₁₇ represents a lower alkoxy group or a mono- or dialkylamino group, R ₁₂ , R ₁₃ and R ₁₄ are the same or different and are linear or branched lower alkyl groups and addition salts with inorganic or organic acids, such as alkali Represents salts of metals, alkaline earths or the corresponding amines.

A lower alkyl or alkoxy group particularly denotes a C ₁ -C ₄ group.

Among the preferred compounds of the present invention are 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 5-methoxy-6-hydroxyindole, (5 or 6) -acetoxy- (6 or 5)- Examples include hydroxyindole or 2-carboxy-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole.

The iodide ions are preferably iodides of alkali metals, alkaline earths or ammonia, and especially potassium iodide.

The so-called "fast" oxidation dyes are intermediates of dyes having the structure of benzene, which, by standing on hair, usually within one hour, produce a color by simply oxidizing to air in the absence of other oxidants. It is a molecule that easily generates a certain compound.
It is especially useful for benzenetrihydroxyl derivatives, diaminohydroxybenzene, aminodihydroxybenzene, triaminobenzene, aminohydroxybenzene and 1,
It is selected from substituted 2-dihydroxybenzenes.

Among the benzenetrihydroxyl derivatives, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxy-5-
Examples thereof include alkylbenzene (where the alkyl group is a lower alkyl group of C ₁ -C ₆ ), 1,2,3-trihydroxybenzene, and salts thereof.

Among diaminohydroxybenzenes, mention may be made of 2,4-diaminophenol, 2,5-diamino-4-methoxy-1-hydroxybenzene and salts thereof.

Among aminodihydroxybenzenes, 2-amino-
1,4-dihydroxybenzene, 1,4-dihydroxy-2-
Mention may be made of diethylaminobenzene, 4-aminoresorcin and their salts.

Among the substituted 1,2-dihydroxybenzenes, one of lower alkyl (C ₁ -C ₆ ) or lower alkoxy (C ₁ -C ₆ ),
2-Dihydroxybenzene is preferred, and 4-methyl-1,
2-Dihydroxybenzene and 3-methoxycatechol are particularly preferred.

Aminohydroxybenzene is, for example, 2-amino-4
-Methoxyphenol, 2-aminophenol, 4,6-
Dimethoxy-3-amino-1-hydroxybenzene, 2,
It is selected from 6-dimethyl-4- (N-p-hydroxyphenyl) amino-1-hydroxybenzene and salts thereof.

Examples of the triaminobenzene include 1,5-diamino-2-methyl-4- (Np-hydroxyphenyl) aminobenzene and a salt thereof.

Nuancers or couplers are compounds known to react with what is also referred to as an oxidizing base or precursor of an oxidation dye, by oxidative condensation reactions, giving the base and the considered coupler a specific coloring compound. is there. This reaction is called "coupling". The cutler is selected from among phenol, ortho-diphenol, metaaminophenol, metaphenylenediamine, mono- and polyhydroxyl derivatives of naphthalene and aminonaphthalene, pyrazolone, benzomorpholine.

Among the couplers or Uniancers, mention may in particular be made of compounds which meet the following formula:

In the above formula, R ₁ is a hydroxyl group, or _one or more C ₁ −
An amino group which may be substituted by a hydroxyalkyl group of C _6, R ₃ and R ₅ are each independently hydrogen, OH, optionally
It can represent a C ₁ -C ₆ lower hydroxyalkyl group or an amino group substituted by a C ₁ -C ₆ lower alkyl group, wherein R ₂ , R ₄ and R ₆ are a hydrogen atom or a C ₁ -C ₆ It can represent an alkoxy group, a C ₁ -C ₆ lower hydroxyalkoxy group or an alkyl group, and R ₃ and R ₄ can also form a methylenedioxy group together.

Among the particularly preferred cutlers, 3-amino-6
Methylphenol, 3-aminophenol, 1,3-dihydroxybenzene 1,2-dihydroxybenzene, 2-methoxy-5-aminophenol, 2-methoxy-5-N
(2-hydroxyethyl) aminophenol, 1,3-diamino-2,6-dimethoxybenzene, 2-methoxy-1
-N-methylamino-4- (2-hydroxyethyloxy) aminobenzene, 1,3-diamino-6-methoxybenzene, 1,3-diamino-4,6-dimethoxybenzene,
6-dimethoxy-1,3-diN (2-hydroxyethyl) aminobenzene, 2,6-dimethoxy-3-N (2-hydroxyethyl) amino-1-aminobenzene, 2,4-dimethoxy-3-N (2-hydroxyethyl) amino-1-
Aminobenzene, 2-methyl-5-N (2-hydroxyethyl) aminophenol, 1,3-di-N (2-hydroxyethyl) amino-4-methoxybenzene, 3-amino-4-methoxyphenol, 3, 4-methylenedioxy-1-aminobenzene, 3,4-methylenedioxy-6
Methoxy-1-aminobenzene, 2,6-dimethyl-3-
N (2-hydroxy) aminophenol, 2,6-dimethyl-6-aminophenol, 4-ethoxy-1-amino-3-N, N- (bis-2-hydroxyethyl) aminobenzene, 2,4- ( Diamino) phenoxyethanol,
Examples thereof include (2-amino-4-N-methylamino) phenoxyethanol, 1-methoxy-2-N- (2-hydroxyethyl) amino-4-aminobenzene, and salts thereof.

Other preferred couplers are 6-amino-benzomorpholine, 6-hydroxybenzomorpholine, 1-naphthol and 1-amino-7-naphthol and their salts.

These various oxidation dyes are used in combination or alone, in combination with iodide ions and indole derivatives.

A particularly preferred use of the present invention is when at least one benzenetrihydroxyl derivative such as 1,2,
4-trihydroxybenzene, 1,2,4-trihydroxy-
5-methylbenzene, or a coupler, such as 1,
3-dihydroxybenzene, 3-aminophenol, 3
-Amino-6-methylphenol, 3,4-methylenedioxy-6-methoxy-1-aminobenzene, 1-naphthol or mixtures thereof.

The results obtained with the combination according to the invention are particularly surprising given the dyeing properties of these oxidation dyes in older systems, in particular in cutlers.
In particular, couplers do not cause coloration by the process of oxidative condensation without the presence of a base or precursor of the oxidation dye.

The subject of the present invention is also a dyeing composition intended for use in a method for dyeing keratin fibres, in particular human hair, which comprises at least 5,6-dihydroxyindole or a derivative of the formula (I), "fast" An oxidation dye and iodine ion selected from the group consisting of an oxidation dye and a coupler are contained in a medium suitable for dyeing. The oxidation dye used in the composition of the present invention is particularly selected from the above-mentioned preferred dyes.

The composition (A) comprises 5,6-dihydroxyindole or a derivative of the formula (I) thereof, an oxidation dye and iodine ion, and generally contains 0.01 to 10% by weight of the oxidation dye, based on the total weight of the composition (A); Preferably, it is contained in a proportion of 0.25 to 5% by weight. 5,6-Dihydroxyindole or its derivative of the formula (I) is generally present in a proportion of from 0.01 to 5% by weight, preferably from 0.03 to 3% by weight, based on the total weight of the composition (A). The proportion of iodide in the same composition is in particular 0.007-4, expressed as I ^- with respect to the total weight of the composition (A).
%, Preferably 0.08-1.5% by weight.

The content of hydrogen peroxide used in the composition (B) is generally 1 to 40 volumes, and preferably 2 to 20 volumes,
And still more particularly 3 to 10 volumes.

With the combination of 5,6-dihydroxyindole and the oxidation dye on one side and iodide on the other side, the ratio between these is preferably 0.05 to 10, and even more particularly 0.5 to 10.
~ 2.

The process according to the invention is prepared in advance and the standing time for the different compositions is 10 seconds to 45 minutes, preferably of the order of 2 to 25 minutes, and especially of the order of 2 to 10 minutes, at each different step. I do.

Applicants have recognized that the process of the present invention is of various colours, very glossy shades, at the same time fast and intense, and does not impair even if it penetrates well into the fibers and especially human keratin fibers. Indeed it has been found that it allows a good staining. These dyes also show an improved resistance to external factors, in particular the resistance to light and to the laundering, when only using 5,6-dihydroxyindole or its color (I) derivative in combination with iodine, Alternatively, they exhibit improved resistance as compared to methods using only oxidation dyes in combination with iodine ions.

Applicants have also compared hair dyed several times after regeneration to hair dyed using methods and compositions of the prior art, thanks to the methods and compositions used in accordance with the present invention. Softer, brighter and had better mechanical properties.

Thanks to the methods and compositions of the present invention, a relatively short time,
That is, relatively strong staining is obtained within about 5 to 15 minutes.

The composition used to carry out the method of the invention may be provided in various forms, for example, in a form that is more or less dense or gelled, a cream, an emulsion, a mousse or any other suitable form for carrying out the dyeing. Can be done.

A dyeing composition defined for use in the method of the present invention, which comprises 5,6-dihydroxyindole or a derivative of its color (I), an oxidation dye in combination with iodine ions, generally comprises water or water. An aqueous medium consisting of a water-solvent mixture, and the solvent is preferably an organic solvent,
For example, ethyl alcohol, propyl or isopropyl alcohol, t-butyl alcohol, ethylene glycol, monomethyl, monoethyl and monobutyl ethers of ethylene glycol, ethylene glycol monoethyl ether acetate, propylene glycol, monomethyl ether of propylene glycol and dipropylene glycol, and It is selected from methyl lactate. Particularly preferred solvents are ethyl alcohol and propylene glycol.

Indole derivatives and oxidation dyes can also be stored in anhydrous solvents with iodide, the composition being mixed with an aqueous medium during use.

When the medium is aqueous, the composition (A) contains 2 to 7
It has a pH, and preferably a pH of 3.5-7.

According to the invention, anhydrous solvents refer to solvents containing 1% or less of water.

If the medium consists of a water-solvent mixture, the solvent is preferably present in a concentration of from 0.5 to 75% by weight, in particular from 2 to 50%, and more particularly from 2 to 20%, relative to the total weight of the composition.

The composition of the present invention may contain other additives conventionally used for dyeing keratin fibers.

These compositions, especially when applied to hair coloring,
Aliphatic amides in proportions of 0.05 to 10%, anions, cations, non-ionics, amphoteric surfactants or mixtures thereof present in proportions of 0.1 to 50% by weight, thickeners, fragrances, sequestering agents, film formation Agents, treating agents, dispersants, conditioning agents, preservatives, opacifiers, keratin fiber swelling agents can be included.

Thickeners are especially sodium alginate, gum arabic,
It can be selected from biopolymers such as guar gum, xanthan gum or scleroglucan, cellulose derivatives such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, sodium salt of carboxymethylcellulose, and polymers of acrylic acid. Similarly, inorganic thickeners such as bentonite can be used. These thickeners, alone or in mixtures, are preferably present in a proportion of from 0.1 to 5% by weight, based on the total weight of the composition, and advantageously from 0.5 to 3%.

Acidifying agents that can be used in a preferred embodiment of the method of using the composition at an acidic pH include lactic acid, acetic acid, tartaric acid,
It can be selected from phosphoric acid, hydrochloric acid, and citric acid.

The pH is also adjusted by means of an alkalizing agent, in particular selected from amines (eg alkanolamines, alkylamines), alkali or ammonium hydroxides or carbonates, eg the precursors are used in the form of salts of strong acids. If so, it can be adjusted.

If the composition is to be used in the form of a mousse, the composition can be prepared under pressure in an aerosol device in the presence of a propellant and at least one mousse generator. The mousse generator can be an anionic, cationic, non-ionic, amphoteric foaming polymer or a surfactant of the type described above.

To use the method of the invention, the various compositions can be prepared in a device having several compartments or in a device called a "kit" or a dyeing toolbox, which device comprises keratin fibers. Above, all the components that are just going to be applied for the dyeing are premixed or contained unmixed for sequential application. Such a device is known per se and comprises a first compartment containing a composition (A) (an indole derivative, comprising an oxidative dye as described above in a medium suitable for dyeing in the presence of iodine) and a filter. A second compartment containing a hydrogen oxide solution can be included.

If the medium containing the indole derivative, the oxidation dye and the iodine ion is an anhydrous medium, it is mixed before use with an aqueous support, optionally present in the third compartment, suitable for dyeing.

Compositions comprising indole derivatives, oxidation dyes and iodide ions in an anhydrous medium can optionally be applied directly to human hair.

If the composition (A) applied over the fibers comprises hydrogen peroxide, the dyeing toolbox is preferably suitable for dyeing the indole derivative and an oxidative dye as defined above in the first compartment. A composition containing (A) in a second medium, a composition (B) containing iodide ions in a second section, an aqueous composition of hydrogen peroxide in a third compartment, and The contents of the third compartment are intended to be mixed with the contents of the first compartment shortly before use.

If the medium suitable for dyeing is aqueous, the composition of the first compartment preferably has a pH of from 2 to 7, and in particular from 3.5 to
Indicates a pH of 7. The pH of the composition comprising hydrogen peroxide is between 2 and 12, but it is preferably between 2 and 7 acidic and more particularly between 2 and 5.

A device with several sections which can be used according to the invention is a mixing means in use and can have equipment known per se and regulated under an inert atmosphere.

The methods and compositions used in accordance with the present invention may be used for natural or already dyed hair, hair with or without permanent or decurled hair, or with strong or light bleaching and optionally permanent. Can be used to dye hair that has fallen. It can likewise be used for dyeing fur or wool.

The following examples are provided to illustrate the invention,
That does not always indicate a restrictive property.

Example 1 The following composition is prepared.

Composition A _{1-5,6-dihydroxyindole} 0.39 g-1,2,4-trihydroxybenzene 1.00 g - Potassium iodide 1.00 g - Ethyl alcohol 10.00 g - guar gum (CELANESE by the company under the name "JAGUAR HP 60" 1.00g-Glycoside alkyl ether ("TRIT" by SEPPIC)
ON CG 110 "sold at a concentration of 60% MA)
5.00 g MA-Preservative required-Natural pH = 5.8-Water sufficient 100.00 g Composition B (containing 12.5 volumes of aqueous hydrogen peroxide)-Hydrogen peroxide 3.75 g-Ammonium lauryl sulfate 6.70 g-Gum arabic 1.00 g- stabilizer 0.03 g - applying stain composition natural hair water qs 100.00 g 90% white hair (a ₁₎ - perfume necessary amount -2-amino-2-methyl-1-propanol required amount pH = 4 Do it.

The composition (A ₁ ) is left for 15 minutes. After rinsing with water, apply 12.5 volumes of hydrogen peroxide composition (B) and apply
Let act for a minute. After rinsing with water and shampooing, the hair turns red and shiny gold into a bright maroon.

Example 2 The following composition is prepared.

Composition A _{2-5,6-dihydroxyindole} 0.60 g-1,3-dihydroxybenzene 0.50 g-3-aminophenol 0.40 g - Potassium iodide 1.00 g - Ethyl alcohol 10.00 g - guar gum (CELANESE Co. than "JAGUAR HP 60 1.00g-glycoside alkyl ether ("TRITON" from SEPPIC)
CG 110 "sold at a concentration of 60% MA) 5.0
0GMA - Preservatives required amount - performed by applying the water qs 100.0 g 90% dyeing composition hair multiplied by the permanent white hairs (A ₂₎ - Natural pH = 6.5.

Leave for 15 minutes. After rinsing with water, apply 12.5 volumes of hydrogen peroxide composition (B) and allow to act for 5 minutes. After rinsing with water and shampooing, the hair dyes a natural shiny dark maroon.

Example 3 The following composition is prepared.

Composition A _{3-5,6-dihydroxyindole} 0.20 g-3-aminophenol 0.10 g - Potassium iodide 1.00 g - Ethyl alcohol 10.00 g - guar gum (sold under the name "JAGUAR HP 60" from CELANESE Co., Ltd.) 1.00g-Glycoside alkyl ether ("TRITON" from SEPPIC
CG 110 "sold at a concentration of 60% MA) 5.0
0GMA - Preservatives required amount - performing water qs 100.0 g 90% natural hair dyeing composition of white hair (A ₃₎ by applying the - natural pH = 7.

Leave for 15 minutes. After rinsing with water, apply 12.5 volumes of hydrogen peroxide composition (B) and allow to act for 5 minutes. After rinsing with water and shampooing, the hair turns into a natural shiny golden blond.

Example 4 The following composition is prepared.

Composition A _{4-5,6-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 (CELANESE Co. than "JAGUAR HP 60 1.00g-glycoside alkyl ether ("TRITON" from SEPPIC)
CG 110 "sold at a concentration of 60% MA) 5.0
0GMA - Preservatives required amount - performed by applying the stain composition of hair over a permanent water qs 100.00 g 90% white hairs (A ₄₎ - Natural pH = 5.4.

Leave for 15 minutes. After rinsing with water, apply 12.5 volumes of hydrogen peroxide composition (B) and allow to act for 5 minutes. After rinsing with water and shampooing, the hair dyes a dark reddish-brown blonde.

Example 5 The following composition is prepared.

Composition A _{5-5,6-dihydroxyindole} 0.50 g-1,3-dihydroxybenzene 0.50 g - Potassium iodide 1.00 g - Ethyl alcohol 10.00 g - guar gum (sold under the name "JAGUAR HP 60" from CELANESE Co. 1.00g-Glycoside alkyl ether ("TRITON" from SEPPIC
5.00 gMA-Preservative required-Triethanolamine required pH = 6-Water sufficient 100.0 g Composition for dyeing 90% white hair, permanent hair ₅ ) Apply by applying.

Leave for 15 minutes. After rinsing with water, apply a composition (B) of 12.5 volumes of aqueous hydrogen peroxide and allow to act for 5 minutes. After rinsing with water and shampooing, the hair turns gray and dark brown.

Example 6 The following composition is prepared.

Composition A _{6-5,6-dihydroxyindole} 0.20 g-3-aminophenol 0.10 g-1,2,4-trihydroxybenzene 0.40 g - Potassium iodide 0.50 g - Ethyl alcohol 10.00 g - guar gum (CELANESE Co. than " JAGUAR HP 60) 1.00g-glycoside alkyl ether ("TRITON" from SEPPIC)
CG 110 "sold at a concentration of 60% MA) 5.0
0GMA - Preservatives required amount - Natural pH = 6.3 - Water qs 100.00 g 90% white hair is carried out by applying SomeNarubutsu the (A ₆₎ staining of natural hair.

Leave for 15 minutes. After rinsing with water, apply a composition (B) of 12.5 volumes of aqueous hydrogen peroxide and allow to act for 5 minutes. After rinsing with water and shampooing, the hair dyes a thin, silvery-white, golden blond.

Example 7 The following composition is prepared.

Composition A _{7-5,6-dihydroxyindole} 0.30 g-3-amino-6-methyl-phenol 0.30 g-1,2,4-trihydroxybenzene 0.30 g - Potassium iodide 0.80 g - Ethyl alcohol 10.00 g - guar gum ( 1.00g-Glycoside alkyl ether (sold by SEPPIC as "TRITON", sold under the name "JAGUAR HP 60" by CELANESE)
CG 110 "sold at a concentration of 60% MA) 5.0
0GMA - Preservatives required amount - performing water qs 100.00 g 90% white hair, using the composition (A ₇₎ Staining of natural hair - Natural pH = 6.7.

Leave for 15 minutes. After rinsing with water, apply a composition (B) of 12.5 volumes of aqueous hydrogen peroxide and allow to act for 5 minutes. After rinsing with water and shampooing, the hair turns reddish-brown into a chestnut brown.

Example 8 The following composition is prepared.

Composition A _{8-5,6-dihydroxyindole} 0.40 g-1-naphthol 0.40 g - Potassium iodide 0.80 g - Ethyl alcohol 10.00 g - guar gum (sold under the name "JAGUAR HP 60" from CELANESE Co., Ltd.) 1.00 g-Glycoside alkyl ether (SEPPIC's “TRITON
CG 110 "sold at a concentration of 60% MA) 5.0
0GMA - Preservatives required amount - performed using water qs 100.00 g 90% white hairs, dyeing compositions of natural hair (A ₈₎ - Triethanolamine required amount pH = 8.5.

Leave for 15 minutes. After rinsing with water, apply a composition (B) of 12.5 volumes of aqueous hydrogen peroxide and allow to act for 5 minutes. After rinsing with water and shampooing, the hair dyes a light maroon with a silvery sheen.

Example 9 The following composition is prepared.

Composition A _{9-5,6-dihydroxyindole} 0.30 g-3,4-methylenedioxy-6-methoxy-1-aminobenzene 0.30 g - Potassium iodide 0.50 g - Ethyl alcohol 10.00 g - guar gum (CELANESE Co. than " JAGUAR HP 60) 1.00g-glycoside alkyl ether ("TRITON" from SEPPIC)
CG 110 "sold at a concentration of 60% MA) 5.0
0GMA - Preservatives required amount - Triethanolamine required amount pH = 6 - Water qs 100.00 g 90% white hair is carried out by applying the stain composition of natural hair (A _9).

Leave for 15 minutes. After rinsing with water, apply 12.5 volumes of hydrogen peroxide composition (B) and allow to act for 5 minutes. After rinsing with water and shampooing, the hair dyes a bright maroon.

Example 10 The following composition is prepared.

Composition A _10- Potassium iodide 0.40 g-Ethyl alcohol 5.00 g-Propylene glycol 5.00 g-Xanthan gum ("RHODOPOL S" from RHONE POULENC)
C "sold under the name) 2.00 g - Preservative required amount - Triethanolamine required amount pH = 6.5 - Deionized water qs 100.00g composition B _{1-5,6-dihydroxyindole} 1.00 g -2, 4-diaminophenoxyethanol dihydrochloride 1.20 g -3-amino-6-methylphenol 0.50 g -glycoside alkyl ether ("TRITON" from SEPPIC
CG 110 ”sold at a concentration of 60% MA) 7.5
0gMA-Xanthan gum (from RHONE POULENC “RHODOPOL S
3.00g-Ethyl alcohol 12.00g-Triethanolamine Required amount pH = 6.5-Deionized water Sufficient amount 100.00g Composition on natural gray hair including 90% gray hair A ₁₀ to 1
Apply for 5 minutes. Perform a rinse. Then 15 minutes, applying an equal weight mixture of the composition B ₁ and pH3 of hydrogen peroxide 20 volumes containing. This mixing is performed just before use.
Then rinse and dry your hair. The hair is thin, silvery and dyed as a natural blonde.

Example 11 The following composition is prepared.

Composition A _{11-5,6-dihydroxyindole} 0.45 g-6-hydroxy-benzomorpholine 0.45 g - ethylene glycol monobutyl ether 8.50 g - Potassium iodide 0.30 g - "NATRO than hydroxyethyl cellulose (AQUALON Inc.
SOL 250HHR) 1.00g-tartaric acid required pH = 5-deionized water sufficient 100.00g 90% natural gray hair with 30% gray hair Composition of pH 3 hydrogen peroxide solution containing 30 volumes It pretreated 10 minutes with the object B _2. After rinsing with water, applying the composition (A ₁₁₎ 20 min. After rinsing and drying, the hair dyes a very silvery and bright blond shade. If the intermediate rinse is omitted, the resulting shade will be a pearly silvery dark blonde.

Example 12 The following composition is prepared.

Composition A _{12-2-methyl-5,6-dihydroxyindole} hydrobromide 0.70 g - resorcin 0.40 g-2-aminophenol 0.10 g-3-amino-6-methyl-phenol 0.25 g - Potassium iodide 0.60g -Ethyl alcohol -Guar gum (sold under the name "JAGUAR HP 60" by CELANESE) 1.00g -Glycoside alkyl ether ("TRITON" by SEPPIC
CG 110 "sold at a concentration of 60% MA) 5.0
0gMA-triethanolamine required pH = 6-preservative required-deionized water sufficient 100.00g These compositions were applied on 90% natural gray natural hair
Apply for 20 minutes. After rinsing, pH 3 containing 12.5 volumes
Applying composition B ₃ of hydrogen peroxide for 10 minutes. After rinsing and drying, the resulting shade is an off-white, bright golden blond.

Example 13 Example 12 is repeated, but with the aqueous hydrogen peroxide used.
The pH is brought to 8.5 with 2-amino-2-methyl-1-propanol before use. A very bright blonde with a golden hue and grayish luster in the finished shade.

Example 14 The following composition is prepared.

Composition A _{13-5-acetoxy-6-hydroxyindole} 0.60 g 6-amino-benzomorpholine hydrochloride 0.80 g-1,2,4-trihydroxybenzene 0.40 g - Potassium iodide 1.00 g - Ethyl alcohol 15.00 g - glycoside Alkyl ethers (SEPPIC's “TRITON
CG 110 "sold at a concentration of 60% MA) 5.00g
MA-Xanthan gum (from RHONE POULENC "RHODOPOL S
1.50 g-Preservative 0.15 g-Triethanolamine Required pH = 7-Deionized water Sufficient 100.00 g Apply this composition for 12 minutes, 90% natural gray hair Apply on top and then rinse. Furthermore the composition B ₃ of pH3 hydrogen peroxide in the hair 12.5 volume containing processing 8 minutes. After rinsing and drying, the hair dyes a thin, golden, grayish, shiny natural light blonde shade.

Example 15 Example 14 is repeated, but with the aqueous hydrogen peroxide used.
The pH is brought to 8 with triethanolamine before use.
The same finish dyeing result as in example 14 is obtained, that is to say a pale golden and grayish-white shiny natural light blond shade.

Example 16 The following composition is prepared.

Composition A _{14-5,6-dihydroxyindole} 0.50 g-1,2,4-trihydroxybenzene 0.50 g-3-aminophenol 0.15 g - Potassium iodide 0.40 g - ethylene glycol monoethyl ether 7.50 g -2 mol Sodium lauryl ether sulfate with ethylene oxide ("SACTIPON 8533" by LEVER)
30% is sold as an aqueous solution) 3.00GMA - HCl required amount pH = 5 - preservatives required amount - composition containing H ₂ O ₂ in deionized water qs 100.00 g 12.5 volume B ₄ - hydrogen peroxide 3.75g-Ammonium lauryl sulfate 6.70g-Thickener 1.00g-Stabilizer 0.03g-Fragrance required-Monoethanolamine required pH = 8.5-Water sufficient 100.00g 90% 15% on natural gray hair with gray hair Apply composition A ₁₄ for a minute. Rinse and then hydrogen peroxide composition B ₄
Apply for 10 minutes. After rinsing and drying, a light grayish-brown, natural light blonde stain is obtained.

Example 17 The following composition is prepared.

Composition A _{15-5,6-dihydroxyindole} 0.10 g-4-methyl-1,2-dihydroxybenzene 1.00 g - Potassium iodide 1.00 g - Ethyl alcohol 10.00 g - guar gum (the name "JAGUAR HP 60" from CELANESE Co. 1.00g-Glycoside alkyl ether (SEPPIC "TRITON
CG 110 "sold at a concentration of 60% MA) 5.00g
MA - Triethanolamine required amount pH = 7 - Preservative required amount - natural gray hair water qs 100.00 g 90% white hairs performed by applying the composition A _15, left for 15 minutes. After rinsing with water, pH 3.8 10
Application of the composition B ₅ volume aqueous hydrogen peroxide, to act for 5 minutes. After rinsing with water and shampooing, the hair dyes a reddish-brown, gray blond.

Claims (8)

(57) [Claims] 1. A method according to claim 1 wherein at least one indole derivative and at least one oxidation dye, which is a fast oxidation dye or a coupler, in a medium suitable for dyeing,
Or (b) a composition (A) comprising a combination of hydrogen peroxide at pH 2 to 7 and a medium suitable for dyeing,
(A) When the composition (A) contains iodine ions, pH 2 to 12
And (b) a composition containing iodine ions at pH 3 to 11 when the composition (A) contains hydrogen peroxide.
Is applied to keratin fibers in an arbitrary order. 2. The indole derivative is 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 5-methoxy-6-hydroxyindole, (5 or 6) -acetoxy- (6 or 5) -hydroxy. The method according to claim 1, which is indole or 2-carboxy-5,6-dihydroxyindole. 3. Formula I (Wherein, R ₇ represents a hydrogen atom, a lower alkyl group or a —SiR ₁₂ R ₁₃ R ₁₄ group, and R ₈ and R ₉ are the same or different, and represent a hydrogen atom or a lower alkyl group, a carboxyl group, a lower alkoxycarbonyl group or -COOSiR ₁₂ R ₁₃ R ₁₄ represents a group, wherein R ₁₀ and R ₁₁ are the same or different and are a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl group, a formyl group, a linear or branched C ₂ -C ₂₀ acyl group, linear or branched C ₃ -C
₂₀ alkenoyl group, -SiR ₁₂ R ₁₃ R ₁₄ group, -P (O) (O
R _{15) 2} group, represents R ₁₅ OSO ₂ group, or R ₁₀ and R _11, are,
Together with oxygen atoms and carbon atoms they are attached, a carbonyl group, a methylene group, forms a ring which may be substituted by a thiocarbonyl group, or the following group PO (O) OR ₁₅ or CR ₁₆ R _17, R ₁₅ and R ₁₆ are The same or different, each represents a hydrogen atom or a lower alkyl group, and R ₁₇ is a lower alkoxy group or a mono-alkyl group;
Or a dialkylamino group, R ₁₂ , R ₁₃ and R
₁₄ is the same or different and represents a linear or branched lower alkyl group) a composition suitable for keratin fiber dyeing, comprising an indole derivative and an addition salt with an inorganic or organic acid, and a fast oxidation dye or coupler in the presence of iodine ion . 4. A coupler comprising 3-aminophenol, 1,3
-Dihydroxybenzene, 1,2-dihydroxybenzene, 3-amino-6-methylphenol, 2-methoxy-5-aminophenol, 1,3-diamino-4,6-methoxybenzene, 2-methoxy-5- [N (2-hydroxyethyl) amino] phenol, 1,3-diamino-2,6-dimethoxybenzene, 2-methoxy-1- (N-methylamino) -4- (2-hydroxyethyloxy) aminobenzene, 3-diamino-6-methoxybenzene, 4,6-
Dimethoxy-1,3-di [N- (2-hydroxyethyl)
Amino] benzene, 2,6-dimethoxy-3- [N- (2
-Hydroxyethyl) amino] -1-aminobenzene,
2,4-dimethoxy-3- [N- (2-hydroxyethyl) amino] -1-aminozenbene, 2-methyl-5
[N- (2-hydroxyethyl) amino] phenol,
4-methoxy-1,3-di [N- (2-hydroxyethyl) amino] benzene, 3-amino-4-methoxyphenol, 3,4-methylenedioxy-1-aminobenzene, 3,4-methylenedi Oxy-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) amino] benzene, 2,4- (diaminophenoxy) ethanol, [2-
Amino-4- [N-methylamino) phenoxy] ethanol, 1-methoxy-2- [N- (2-hydroxyethyl) amino] -4-aminobenzene and salts thereof,
The composition according to claim 3, comprising 6-aminobenzomorpholine, 6-hydroxybenzenemorpholine, 1-naphthol, 1-amino-7-naphthol or a salt thereof. 5. The high-speed oxidation dye is 1,2,4-trihydroxybenzene, 1,2,4-trihydroxy-5-alkyl (C ₁ -C
₆ ) Benzene, 1,2,3-trihydroxybenzene, 4-aminoresorcin, 2-amino-1,4-dihydroxybenzene, 2-amino-4-methoxyphenol, 2,4-diaminophenol, 2-amino- Phenol, 4-methyl-1,2-dihydroxybenzene, 3-methoxycatechol, 1,4-dihydroxy-2-diethylaminobenzene, 2,5-diamino-4-methoxy-1-hydroxybenzene, 4,6-dimethoxy- 3-amino-1-hydroxybenzene, 2,6-dimethyl-4- [N- (p-hydroxyphenyl) amino] -1-hydroxybenzene, 1,
5. The composition according to claim 3, which is 5-diamino-2-methyl-4- [N- (p-hydroxyphenyl) amino] benzene and a salt thereof. 6. The 5,6-dihydroxyindole or indole derivative according to claim 3, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxy-5-methylbenzene, 1,3-dihydroxy 4. An oxidation dye comprising benzene, 3-aminophenol, 3-amino-6-methylphenol, 3,4-methylenedioxy-6-methoxy-1-aminobenzene or 1-naphthol, and iodine ions. Composition. 7. Formula I (Wherein, R ₇ represents a hydrogen atom, a lower alkyl group or a —SiR ₁₂ R ₁₃ R ₁₄ group, and R ₈ and R ₉ are the same or different, and represent a hydrogen atom or a lower alkyl group, a carboxyl group, a lower alkoxycarbonyl group or -COOSiR ₁₂ R ₁₃ R ₁₄ represents a group, wherein R ₁₀ and R ₁₁ are the same or different and are a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl group, a formyl group, a linear or branched C ₂ -C ₂₀ acyl group, linear or branched C ₃ -C
₂₀ alkenoyl group, -SiR ₁₂ R ₁₃ R ₁₄ group, -P (O) (O
R _{15) 2} group, represents R ₁₅ OSO ₂ group, or R ₁₀ and R _11, are,
Together with the oxygen and carbon atoms to which they are attached, a carbonyl group, a methylene group, a thiocarbonyl group or a next group PO (O) OR ₁₅ or CR ₁₆ R ₁₇ form a ring which can be substituted by R ₁₇ , wherein R ₁₅ and R ₁₆ are The same or different, each represents a hydrogen atom or a lower alkyl group, and R ₁₇ is a lower alkoxy group or a mono-alkyl group;
Or a dialkylamino group, R ₁₂ , R ₁₃ and R
₁₄ is the same or different and represents a linear or branched lower alkyl group) a composition suitable for dyeing keratin fibers, comprising an indole derivative and an addition salt with an inorganic or organic acid, and a fast oxidation dye or coupler in the presence of iodide ions And a kit for staining, comprising a plurality of compartments, and an aqueous composition of hydrogen peroxide in the second compartment. 8. Iodine ions in an anhydrous solvent, of the formula I (Wherein, R ₇ represents a hydrogen atom, a lower alkyl group or a —SiR ₁₂ R ₁₃ R ₁₄ group, and R ₈ and R ₉ are the same or different, and represent a hydrogen atom or a lower alkyl group, a carboxyl group, a lower alkoxycarbonyl group or -COOSiR ₁₂ R ₁₃ R ₁₄ represents a group, wherein R ₁₀ and R ₁₁ are the same or different and are a hydrogen atom, a linear or branched C ₁ -C ₂₀ alkyl group, a formyl group, a linear or branched C ₂ -C ₂₀ acyl group, linear or branched C ₃ -C
₂₀ alkenoyl group, -SiR ₁₂ R ₁₃ R ₁₄ group, -P (O) (O
R _{15) 2} group, represents R ₁₅ OSO ₂ group, or R ₁₀ and R _11, are,
Together with the oxygen and carbon atoms to which they are attached, a carbonyl group, a methylene group, a thiocarbonyl group or a next group PO (O) OR ₁₅ or CR ₁₆ R ₁₇ form a ring which can be substituted by R ₁₇ , wherein R ₁₅ and R ₁₆ are The same or different, each represents a hydrogen atom or a lower alkyl group, and R ₁₇ is a lower alkoxy group or a mono-alkyl group;
Or a dialkylamino group, R ₁₂ , R ₁₃ and R
₁₄ is a first compartment containing a composition comprising the same or different indole derivative representing a linear or branched lower alkyl group and an addition salt with an inorganic or organic acid, and at least one oxidation dye or coupler; A second compartment containing an aqueous medium suitable for the second compartment, and a third compartment containing from 1 to 40 volumes of an aqueous composition of hydrogen peroxide at a pH of from 2 to 12, wherein the composition contained in the second compartment comprises: An apparatus or kit having a plurality of compartments for dyeing keratin fibers, which is intended to be mixed with the contents of the first compartment at the time of use.