NL8803075A - METHOD FOR DYEING KERATIN FIBERS WITH OXIDATION DYES IN THE PRESENCE OF INDOOL DERIVATIVES AND DYE COMPOSITION USED THEREIN. - Google Patents

Description

it:

Process for dyeing keratin fibers with oxidation dyes * in the presence of indole derivatives and paint composition used therewith.

The invention relates to a new method for dyeing keratin fibers, in particular of human keratin fibers such as hair, with indole derivatives in the presence of certain so-called "fast" oxidation dyes and coupling compounds and also to the compositions used in that method.

Dutch patent application 88.01318 describes a method for dyeing keratin fibers, the main feature of which is to apply to the fibers at least one composition (A) which, in a medium suitable for dyeing, combines at least one oxidation dye with iodide ions preceded or followed by application of a composition (B) containing hydrogen peroxide in a suitable medium at a pH between 2 and 12.

Numerous methods of dyeing keratin fibers, especially hair, are known in which 5,6-dihydroxyindole is used. For example, French patent application 2,593,061 discloses a method for dyeing hair in two steps in which a composition containing 5,6-dihydroxyindole and iodide in a suitable medium is preceded or followed by the application of hydrogen peroxide.

It has been found that special, bright colors from a wide range of colors, in particular shades ranging from maroon to blond, which are particularly desirable when dyeing hair, can be obtained by using certain oxidation dyes mentioned in Dutch patent application 88.01318 in combination with 5 , 6-dihydroxyindole or derivatives thereof.

It has further been found that the varied shades thus obtained have improved resistance to external influences to, in particular, increased lightfastness and / or washfastness to the color obtained with the previously described compositions containing either the oxidation dye or the indole derivative.

This result is especially surprising because the indole derivative is used in compositions containing oxidation dyes which themselves give fairly light colors that have little depth during development, while depth is generally desirable when dyeing hair.

88030757 * 2 * The invention therefore relates to the use of 5,6-dihydroxyindole or a derivative thereof in combination with at least one oxidation dye belonging to a group of the "fast" oxidation dyes and the coupling compounds.

The invention also relates to the compositions used in this method.

The invention further relates to multi-departmental devices or "kits" containing the compositions suitable for use in the method of the invention. The main characteristic of the method for dyeing keratin fibers, in particular of human keratin fibers, according to the invention is that on the fibers at least one composition (A) is applied which in at least one indole derivative and in a medium suitable for dyeing contains at least one oxidation dye belonging to the group of the "fast" oxidation dyes and the coupling compounds, combined with either (a) iodide ions or (b) hydrogen peroxide, the application of this composition (A) being preceded or followed by the application of a composition (B) containing in a dyeing medium: 20 - either (a) hydrogen peroxide at a pH between 2 and 12 and preferably between 2 and 7, when composition (A) contains iodide ions, - or (b) iodide ions at a pH between 3 and 11 when composition (A) contains hydrogen peroxide.

The pH of the composition (A) when it contains hydrogen peroxide is preferably between 2 and 7 and in particular between 2 and 5. Between the application of the compositions (A) and (B), the fibers can optionally be rinsed .

Preferably, a composition (A) is applied to the fibers which contains both an indole derivative and the oxidation dye in combination with the iodide ions, for which or after which a hydrogen peroxide-containing composition (B) is applied.

In the method of the invention, the indole derivative satisfies formula 1 of the formula sheet, wherein: represents a hydrogen atom, an alkyl group or a trialkylsilyl group; and R 1 independently represents a hydrogen atom or an alkyl, carboxyl, alkoxycarbonyl or trialkylsilyloxycarbonyl; R 1 and R 4 independently a hydrogen atom, a straight or branched C 2 -C 2 alkyl group, a formyl group, 8803 0757 3 a straight or branched C 2 -C 20 acyl group, a straight or branched C 3 -C 20 alkenoyl group, a trialkylsilyl group, a group -P0 (0R ^) 2, or a group -SO2ORI2 or R ^ and ^ and RH together with the oxygen atoms to which they are attached form part of a ring optionally containing a carbonyl group, a thiocarbonyl group, optionally containing an alkoxy group or a mono- or dialkyl-amino group substituted alkylidene group or a group ^ P (0) 0r12, wherein r @ 1 represents a hydrogen atom or an alkyl group, and it may also be an acid addition salt thereof or an alkali metal, alkaline earth metal or amine salt thereof.

Alkyl and alkoxy groups, if no further details are given, are understood to mean branched or unbranched groups, preferably with 1 to 6 carbon atoms.

Of said indole derivatives, preferred are 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole , 5-acetoxy-6-hydroxyindole, 6-acetoxy-5-hydroxyindole and 5,6-dihydroxy-2-indole carboxylic acid.

The iodide ion is preferably present as an iodide of an alkali metal, alkaline earth metal or ammonium and in particular as potassium iodide.

The so-called "fast" oxidation dyes are benzene compounds which are precursors of dyes, which can yield colored compounds by oxidation in air during the action in the hair, i.e. generally within 1 hour and then in the absence of any other oxidizing agent. These compounds preferably belong to the trihydroxyl derivatives of benzene, the diamino hydroxybenzenes, amino dihydroxybenzenes, triaminobenzenes, amino hydroxybenzenes and substituted 1,2-dihydroxybenzenes.

Among the trihydroxybenzene derivatives can be mentioned 1,2,4-tri-hydroxybenzene, 5-alkyl-1,2,4-trihydroxybenzene, the alkyl group having 1 to 6 carbon atoms, 1,2,3-trihydroxybenzene and its salts.

Among the diamino hydroxybenzenes, mention can be made of 2,4-diamino-phenol, 2,5-diamino-4-methoxyphenol and its salts.

Among the amino dihydroxybenzenes, mention can be made of 2-amino-1,4-dihydroxybenzene, 2-diethylamino-1,4-dihydroxybenzene, 4-amino-resorcinol and salts thereof.

Of the substituted 1,2-dihydroxybenzenes, the 1,2-dihydroxybenzenes with a C 1 -C 6 alkyl or a C 1 -C 8 alkoxy substituent are preferred, with 4-methyl- particularly preferred. 8803 075: 4 4-pyrocatechol and 3-methoxy-pyrocatechol.

Of the amino hydroxybenzenes, 2-amino-4-metho-xyphenol, 2-aminophenol, 4,6-dimethoxy-3-aminophenol, 2,6-dimethyl-4- (p-hydroxyphenylamino) phenol and its salts are preferred.

Among the triaminobenzenes can be mentioned 1,5-diamino-2-methyl-4- (p-hydroxyphenylamino) benzene and its salts.

The nuancing or coupling compounds are compounds which are known to react with oxidation bases, also called oxidation dye precursors, in an oxidative condensation to form colored compounds specific for the base and the coupling compound. This reaction is referred to as "coupling." These compounds are selected from the phenols, resorcinols, metamino phenols, pyrocatecbol, metaphenylenediamines, mono- and polyhydroxy derivatives of naphthalene and aminonaphthalene, pyrazolones and benzomorpholines.

Of the coupling compounds or nuancing compounds, particular mention can be made of the compounds of formula 2, wherein: R 1 represents a hydroxyl group or an amino group optionally substituted with one or more C 1 -C 8 20 alkyl group, and R 1 independently represents a hydrogen atom a hydroxyl group, an amino group optionally substituted with a C 1 -C 8 hydroxyalkyl group or a C 1 -C 8 alkyl group, and R 1, R 1 and R 6 a hydrogen atom or a C 1 -C 8 alkoxy group, C 1 -C 8 - hydroxyalkoxy-25 group or C 1 -C 8 -alkyl group, where R 1 and R 2 may also together form a methylenedioxy group.

Particularly preferred coupling compounds can be mentioned 3-aminophenol, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 3-amino-6-methylphenol, 2-methoxy-5-aminophenol, 2-methoxy-5- (2- hydroxy-30ethylamino) phenol, 1,3-diamino-2,6-dimethoxybenzene, 2-methoxy-1-methyl-amino-4- (2-hydroxyethoxy) -3-aminobenzene, 1,3-diamino-6-methoxybenzene 1,3-diamino-4,6-dimethoxybenzene, 4,6-dimethoxy-1,3-bis (2-bydroxyetbyl-amino) benzene, 2,6-dimetboxy-3- (2-hydroxyetbylamino) -1-aminobenzene, 2.4 - dimethoxy-3- (2-bydroxyetbylamino) -1-aminobenzene, 2-methyl-5- (2-by-35-hydroxyethylamino) -phenol, 1,3-bis (2-bydroxyetbylamino) -4-metboxybenzene, 3-amino -4-methoxyphenol, 3,4-methylenedioxy-1-aminobenzene, 3,4-methylenedioxy-6-metboxy-1-aminobenzene, 2,6-dimethyl-3- (2-hydroxyethylamino) -phenol, 2 6-dimethyl-3-aminophenol, 4-ethoxy-1-amino-3- [bis (2-hydro-xyethyl) amino] benzene, (2,4-diaminophenoxy) ethanol, (2-amino-4-methyl- 40 aminophenoxy) ethanol, 1-methoxy-2- (2-hydroxyethylamino) -4-aminobenzene 8803 075: * 5 and its salts. *

Other preferred coupling compounds are 6-aminobenzomorpholine, 6-hydroxybenzomorpholitte, 1-naphthol and 1-amino-7-naphthol and its salts.

The different oxidation dyes are used individually or mixed, combined with iodide ions and the indole derivatives used.

According to a preferred embodiment of the invention, together with 5,6-dihydroxyindole and iodide ions, at least one trihydroxybenzene derivative such as 1,2,4-trihydroxybenzene, 5-methyl-1,2,4-10 trihydroxybenzene or coupling compounds such as 1.3 are used dihydroxybenzene, 3-aminophenol, 3-amino-6-methylphenol, 3,4-methylenedioxy-6-methoxyaniline, 1-naphthol or mixtures thereof.

The result of the method according to the invention is particularly surprising in view of the color properties of these oxidation dyes in conventional systems, in particular of the compounds which produce only one color in the presence of an oxidation base or an oxidation dye precursor of an oxidation condensation.

The invention also relates to paint compositions intended for use in the dyeing of keratinous fibers, in particular of human hair, which compositions contain at least 5,6-hydroxyindole or a derivative thereof of formula 1, an oxidation dye group of "fast" oxidation dyes and coupling compounds, as well as iodide ions in a paintable medium. The oxidation dyes to be used in these compositions are preferably the above-mentioned dyes.

Composition (A) containing an indole derivative of formula 1, the oxidation dye and the iodide ions generally contains the oxidation dye in amounts between 0.01 and 10% by weight and preferably between 0.25 and 5% by weight. The indole derivative of the formula 1 is generally present in an amount between 0.01 and 5, preferably between 0.03 and 3% by weight. The amount of iodide in these compositions is preferably between 0.007 and 4 and preferably between 0.08 and 1.5% by weight expressed in iodide.

The hydrogen peroxide content in the compositions (B) is generally between 0.3 and 12%, preferably between 0.6 and 6% and particularly preferably between 0.9 and 3%.

The ratio between the indole derivatives of the formula 1 combined with the oxidation dyes on the one hand and the iodide ions on the other hand is preferably between 0.05 and 10 and particularly preferably between 0.5 and 40 2.

& 803075 "► 6

In the method according to the invention, the different applied compositions are allowed to act for 10 sec to 45 min, preferably 2 to 25 min and particularly preferably 2 to 10 min.

It has been found that with the method according to the invention a variety of colors can be obtained over a wide range, the shades being particularly fast and powerful and can be very shiny and penetrate well into the fibers in particular in the human hair without the to affect her. The obtained color also has an improved resistance to external influences very in particular to light and washings, compared to the methods in which only the 5,6-dihydroxyindole or a derivative thereof combined with iodide ions or only the oxidation dyes combined with iodide- ions are used.

It has also been found that hair dyed several times after regrowth by the method and compositions of the invention is softer and shinier and has better mechanical properties than hair dyed by a prior art method.

Thanks to the method and the compositions according to the invention, deep colors are obtained in a relatively short time, on the order of 5 to 15 minutes.

The compositions which can be used in the method of the invention can have various shapes such as more or less thickened or gelled liquids, creams, emulsions, foams and other forms suitable for dyeing.

The paint compositions intended for use in the method of the invention containing an indole derivative of formula 1, an oxidation dye combined with iodide ions, generally comprise an aqueous medium based on water or a mixture of water with other solvents, which solvents are preferably selected from organic solvents such as ethyl alcohol, propyl alcohol, isopropyl alcohol, tert-butyl alcohol, ethylene glycol, 2-methoxy, 2-ethoxy and 2-butoxyethanol, 2-ethoxyethyl acetate, propylene glycol, monomethyl ethers of propylene glycol and dipropylene glycol and methyl 35 lactate. Especially preferred are ethyl alcohol and propylene glycol.

The indole derivatives and the oxidation dyes can also be stored with the iodides in a medium formed by anhydrous solvents, this composition being mixed with an aqueous medium just before use.

40 When the medium is water-containing, the pH of composition axis 03 07 is 5; % 7 (A) between 2 and 7, and preferably between 3.5 and 7. An anhydrous solvent is here understood to mean a solvent containing less than 1% water.

When the medium is formed by a mixture of water and solvents, these solvents are preferably present in a concentration between 0.5 and 75% by weight, in particular between 2 and 50% by weight and more in particular between 2 and 20% by weight relative to the total composition.

The compositions of the invention may contain other conventional adjuvants used in dyeing keratin fibers.

When used for dyeing hair, these compositions may contain, in particular, fatty acid amides in amounts between 0.05 and 10%, and further anionic, cationic, nonionic and / or amphoteric surfactants in amounts between 0.1 and 50 wt%, thickeners, perfumes, sequestering agents, film-forming agents, treating agents, dispersants, conditioners, preservatives, cloudings, foaming agents and keratin fibers.

In particular, the thickeners can be selected from sodium alginate, gum arabic, guar gum, biopolymers such as xanthan or scleroglucans, cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, carboxymethyl cellulose sodium salt and acrylic acid polymers. Inorganic thickeners such as bentonite can also be used. These thickeners are used individually or mixed and are preferably present in amounts between 0.1 and 5 and advantageously between 0.5 and 3% by weight of the composition.

Also, in the preferred embodiment using acidic pH compositions, acidifying agents may be present such as lactic, acetic, tartaric, phosphoric, hydrochloric and citric acids.

The pH can also be adjusted, if necessary, with alkalizing agents, in particular in the form of amines such as alkanolamines and alkyl amines and alkali metal or ammonium hydroxides or carbonates, especially when the dye intermediates are used in the form of salts of strong acids.

When the composition is used as a foam, it may be packaged under pressure in the presence of a propellant and at least one foaming agent in an aerosol. The foaming agents can be anionic, 8803075.

8 are cationic, nonionic or amphoteric foaming polymers or surfactants of the above type.

For use in the method according to the invention, the compositions may be packaged in a multi-departmental device, also referred to as a "kit" or paint set, containing all ingredients which are successively used, whether or not after pre-mixing, in the same paint treatment of Keratin Fibers Such devices are known per se and may contain a first compartment containing composition (A) containing the indole-10 derivative, the oxidation dye as mentioned above and the iodide ions in a suitable medium and a second compartment containing a hydrogen peroxide solution .

When the medium containing the indole derivative, the oxidation dye and the iodide ions is an anhydrous medium, this mixture is mixed before use with any water-containing carrier suitable for painting in a third compartment.

The composition containing the indole derivative, the oxidation dye and the iodide ions in anhydrous medium can optionally be applied directly to moist keratin fibers.

When composition (A) applied to the fibers contains hydrogen peroxide, the packaging device preferably in a first compartment comprises a composition (A) containing the indole derivative and the oxidation dye in a dye-suitable medium, in a second compartment composition (B) containing the iodide ions and in a third compartment a solution of hydrogen peroxide in water, the contents of the third compartment being intended to be mixed with the contents of the first compartment just before use.

When the paint medium is water-containing, the composition of the first compartment preferably has a pH between 2 and 7 and in particular between 3.5 and 7. The pH of the hydrogen peroxide composition is between 2 and 12, but this composition is preferably acidic with a pH between 2 and 7 and in particular between 2 and 5.

The device with different compartments which can be used according to the invention can be provided with mixing agents known per se and packaged under an inert atmosphere.

The method and the compositions according to the invention can be used for dyeing natural hair or already dyed, permed or not curled or more or less bleached and optionally permed hair. They can also be used for dyeing 8803 075/9 fur and wool.

Example I

They prepare the following compositions: 5 COMPOSITION ΑΊ: - 5,6-dihydroxyindole 0.30 g - 1,2,4-trihydroxybenzene 1.00 g - potassium iodide 1.00 g 10 - ethyl alcohol 10.00 g - guar gum, trade name " JAGUAR HP 60 ”from CELANESE 1.00 g - glycoside alkyl ether, 15 with a concentration of 60% active substance (WS), trade name

"TRITON CG 110" from SEPPIC 5.00 g WS

- preservative as required - pH measured * 5.8 20 - water up to 100.00 g COMPOSITION B with 3.75% hydrogen peroxide: - hydrogen peroxide 3.75 g 25 - ammonium lauryl sulfate 6.70 g - gum arabic 1.00 g - stabilizer 0.03 g - perfume as required - 2-amino-2-methyl-1-propanol as required to pH = 4 30 - water up to 100.00 g

Of course, 90% gray hair is dyed by applying composition (A ^).

This composition is allowed to act for 15 minutes. After rinsing, the composition (B) is applied and allowed to act for 5 minutes. After rinsing and shampoo treatment, the hair has a light golden chestnut color with reddish shine.

Example II

40 The following composition is prepared: 8803 075.

10 COMPOSITION A? : - 5,6-dihydroxyindole 0.60 g - 1,3-dihydroxybenzene 0.05 g 5 - 3-aminophenol 0.40 g - potassium iodide 1.00 g - ethyl alcohol 10.00 g - guar gum 1.00 g

glycoside alkyl ether 5.00 g WS

10 - preservative as required - pH measured = 6.5 - water up to 100.00 g

Permanent, 90% gray hair is dyed by applying composition (A2)

These are allowed to act for 15 minutes. After rinsing with water, the composition (B) is applied and left to act for 5 minutes. After rinsing with water and shampoo treatment, the hair has a dark chestnut color with natural shine.

20

Example III

The following composition is prepared: COMPOSITION A: 25 - 5,6-dihydroxyindole 0.20 g - 3-aminophenol 0.10 g - potassium iodide 1.00 g - ethyl alcohol 10.00 g - guar gum 1.00 g

30 - glycoside alkyl ether 5.00 g WS

- preservative as required - pH measured = 7 - water up to 100.00 g 35 Natural, 90% gray hair is dyed by applying composition (A3).

This composition is allowed to act for 15 minutes. After rinsing, composition (B) is applied and left to act for 5 min. After rinsing with water and shampoo treatment, the hair has a golden blonde color with 40 natural shine.

8803075.

11

Example IV

The following composition is prepared: COMPOSITION Aa: 5 - 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 1.00 g

10 - glycoside alkyl ether 5.00 g WS

- preservative as required - pH measured = 5.4 - water up to 100.00 g 15 Permed, 90% gray hair is dyed by applying composition (A4).

These are allowed to act for 15 minutes. After rinsing with water, the composition (B) is applied and left to act for 5 minutes. After rinsing with water and shampoo treatment, the hair has a dark blond mahogany color.

20

Example V

The following composition is prepared: COMPOSITION Ag: 25 - 5,6-dihydroxyindole 0.50 g - 1,3-dihydroxybenzene 0.50 g - potassium iodide 1.00 g - ethyl alcohol 10.00 g - guar gum 1.00 g

30 - glycoside alkyl ether 5.00 g WS

- preservative as required - triethanolamine to pH = 6 - water to 100.00 g 35 Permanent, 90% gray hair is dyed by applying composition (A5).

These are allowed to act for 15 minutes. After rinsing with water, composition (B) is applied and left to act for 5 minutes. After rinsing with water and shampoo treatment, the hair has an ash-like dark chestnut-40 color.

05030757 * 12 4

Example VI

They prepare the following composition: COMPOSITION Af, i 5 - 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 10 - guar gum 1.00 g

glycoside alkyl ether 5.00 g WS

- preservative as required - pH measured = 6.3 - water up to 100.00 g 15

Of course, 90% gray hair is dyed by applying composition (Ag).

These are allowed to act for 15 minutes. After rinsing with water, the composition (B) is applied and left to act for 5 minutes. After rinsing with water and shampoo treatment, the hair has a slightly ash-colored golden blonde color.

Example VII

The following composition is prepared: COMPOSITION A7: - 5,6-dihydroxyindole 0.30 g - 3-amino-6-methylphenol 0.30 g - 1,2,4-trihydroxybenzene 0.30 g 30 - potassium iodide 0.80 g - ethyl alcohol 10.00 g - guar gum 1.00 g

glycoside alkyl ether 5.00 g WS

- preservative as required 35 - pH measured = 6.7 - water up to 100.00 g

Of course, 90% gray hair is dyed by applying composition (A7).

40 These are allowed to act for 15 minutes. After rinsing with water, 6803075 Γ 13 composition (B) is applied and left to act for 5 min. After rinsing with water? and shampoo treatment the hair has a rosy chestnut color.

Example VIII

The following composition is prepared: COMPOSITION Ar: - 5,6-dihydroxyindole 0.40 g - 1-naphthol 0.40 g 10 - potassium iodide 0.80 g - ethyl alcohol 10.00 g - guar gum 1.00 g

glycoside alkyl ether 5.00 g WS

- preservative as required 15 - triethanolamine up to pH * 8.5 - water up to 100.00 g

Of course, 90% gray hair is dyed by applying composition (Ag).

20 These are allowed to act for 15 minutes. After rinsing with water, the composition (B) is applied and left to act for 5 minutes. After rinsing with water and shampoo treatment, the hair has a light chestnut color with ash-colored shine.

Example IX

The following composition is prepared: COMPOSITION Aq: - 5,6-dihydroxyindole 0.30 g 30 - 3,4-methylenedioxy-6-methoxyaniline 0.30 g - potassium iodide 0.50 g - ethyl alcohol 10.00 g - guar gum 1, 00 g

glycoside alkyl ether 5.00 g WS

35 - preservative as required - triethanolamine to pH = 6 - water to 100.00 g

Of course, 90% gray hair is dyed by applying composition (Ag) 88030757 14 'It is allowed to act for 15 minutes. After rinsing with water, the composition (B) is applied and left to act for 5 minutes. After rinsing with water and shampoo treatment, the hair has a light chestnut color.

5 Example X

The following composition is prepared: COMPOSITION Am: - sodium iodide 0.40 g 10 - ethyl alcohol 5.00 g - propylene glycol 5.00 g

- xanthan gum, trade name RH0D0P0L SC

from the company RHONE POULENC 2.00 g 15 - preservatives as required - triethanolamine up to pH = 6.5 - demineralized water up to 100.00 g 20 COMPOSITION Βη: - 5,6-dihydroxyindole 1.00 g - 2,4-diaminophenoxyethanol dihydrochloride 1.20 g, 3-amino-6-methylphenol, 0.50 g

25 - glycoside alkyl ether 7.60 g WS

- xantham gum, RH0D0P0L SC 3.00 g - ethyl alcohol 12.00 g - triethanolamine up to pH = 6.5 - demineralized water up to 100.00 g 30

Natural, 90% gray hair is applied in 15 min. After rinsing, a mixture of equal parts by weight of composition and 6% hydrogen peroxide with pH = 3 is applied in 15 min, which mixture is prepared just before use. The hair is then rinsed and dried. It has a slightly ash-like natural blonde color.

Example XI

The following composition is prepared: 8803075.

15 COMPOSITION Α1Ί: - 5,6-dihydroxyindole 0.45 g - 6-hydroxybenzomorpholine 0.45 g 5 - 2-butoxyethanol 8.50 g - potassium iodide 0.30 g

hydroxyethyl cellulose, trade name NATROSOL 250 HHR

from AQUALON 1.00 g 10 - tartaric acid up to pH * 5 - distilled water up to 100.00 g

Naturally, 90% gray hair is treated for 10 min with a composition B2 containing 9% hydrogen peroxide with pH * 3. After rinsing, composition Au is applied in 20 minutes. After rinsing and drying, the hair has a very ash-colored light blond shade. If the intermediate rinse is omitted, the shade is iridescent ash-like dark blond.

Example XII

20 The following composition is prepared: COMPOSITION A1? : - 2-methyl-5,6-dihydroxyindole hydrobromide 0.70 g - -resorcinol 0.40 g 25 - 3-aminophenol 0.10 g - 3-amino-6-methylphenol 0.25 g - potassium iodide 0.60 g - ethyl alcohol 10.00 g - guar gum 1.00 g

30 - glycoside alkyl ether 5.00 g WS

- triethanolamine up to pH * 6 - preservatives as required - demineralized water up to 100.00 g 35 This composition is applied to natural, 90% gray hair for 20 minutes. After rinsing, composition B3 of 3.75% hydrogen peroxide with pH = 3 is applied for 10 min. After rinsing and drying, the hair has an ash-like golden light blond shade.

8803075: Λ 16

Example XIII

Example XII is repeated except that the pH of composition B3 is adjusted to 8.5 with hydrogen peroxide for use with 2-amino-2-methyl-1-propanol. The final shade is very light-5 blonde with a golden gray sheen.

Example XIV

The following composition is prepared: COMPOSITION Au: - 5-acetoxy-6-hydroxyindole 0.60 g - 6-aminobenzomorpholine dihydrochloride 0.80 g - 1,2,4-trihydroxybenzene 0.40 g - potassium iodide 1.00 g 15 - ethyl alcohol 15.00 g

glycoside alkyl ether 5.00 g WS

- xanthan gum RH0D0P0L SC 1.50 g - preservatives 0.15 g - triethanolamine up to pH = 7 20 - demineralized water up to 100.00 g

This composition is applied to natural, 90% gray hair for 12 minutes. After rinsing, the hair is treated with a composition B3 of 3.75% hydrogen peroxide with pH = 3 for 8 min. After rinsing and drying, the hair has a natural light blond shade with a slightly golden gray sheen.

Example XV

Example XIV is repeated except that the pH of composition B3 with hydrogen peroxide is adjusted to 8 for use with triethanolamine. The same final paint result is obtained, i.e. a natural light blond shade with a slightly golden gray sheen.

Example XVI

The following composition is prepared: 8803075.Ί 17 COMPOSITION Α1Δ: - 5,6-dihydroxyindole 0.50 g - 1,2,4-trihydroxybenzene 0.50 g - 3-aminophenol 0.15 g 5 - sodium iodide 0.40 g 2-ethoxyethanol 7.50 g. Sodium lauryl sulfate with

2 mol ethylene oxide, 30% in water with the trade name SACTIPON 8533 10 from LEVER 3.00 g WS

- hydrochloric acid to pH = 5 - preservatives as required - demineralized water up to 100.00 g 15 COMPOSITION B4 with 3.75% hydrogen peroxide: - hydrogen peroxide 3.75 g - ammonium lauryl sulfate 6.70 g - thickener 1.00 g - stabilizer 0, 03 g 20 - perfume as required - monoethanolamine up to pH s 8.5 - water up to 100.00 g

Composition A ^ 4 is applied to natural, 90% gray hair for 15 minutes. After rinsing, composition B4 is applied in 10 minutes. After rinsing and drying, a natural light blond color with a slightly ash-colored gloss is obtained.

Example XVII

The following composition is prepared: 30 COMPOSITION At s - 5,6-dihydroxyindole 0.10 g - 4-methyl-1,2-dihydroxybenzene 1.00 g - potassium iodide 1.00 g 35 - ethyl alcohol 10.00 g - guar gum 1.00 g

glycoside alkyl ether 5.00 g WS

- triethanolamine up to pH - 7 - preservative as required 40 - water up to 100.00 g 8803075.

i 18

Of course, 90% gray hair is dyed by applying composition A ^ 5 and left to act for 10 minutes. After rinsing with water, a composition B5 with 3% hydrogen peroxide and a pH of 3.8 is applied and left to act for 5 minutes. After rinsing with water and sham-5 poobe treatment, the hair has an ash blonde mahogany color.

88030757

Claims (31)

A method for dyeing keratin fibers, characterized in that at least one composition (A) is applied to the fibers, which in a suitable medium contains at least one indole derivative and at least one oxidation dye belonging to the group of fast oxidation dyes and coupling compounds, combined with either (a) iodide ions or (b) hydrogen peroxide with a pH between 2 and 7 and preferably 10 between 2 and 5, and that before or after the application of composition (A) a composition (B ) which in a suitable medium: - either (a) contains hydrogen peroxide with a pH between 2 and 12 and preferably between 2 and 7 when composition (A) contains iodide ions, - or (b) iodide ions at a pH between 3 and 11 when composition (A) contains hydrogen peroxide. 2. Process according to claim 1, characterized in that composition (A) contains iodide ions and composition (B) contains hydrogen peroxide. A method according to claim 1 or 2, characterized in that the indole derivative satisfies formula 1, wherein; represents a hydrogen atom, an alkyl group or a trialkylsilyl group, R ** and R 1 independently represent a hydrogen atom or an alkyl group, carboxyl group, alkoxycarbonyl group or trialkylsilyloxycarbonyl group, r 10 and r H independently represent a hydrogen atom, a straight or branched C 1 -C 2q alkyl group, a formyl group, a straight chain or branched C 2 -C 20 acyl group, a straight or branched C 3 -C 20 alkenoyl group, a trialkylsilyl group, a group -P0 (0R12) 2, or a group -S0 £ 0R ^ 2 or R · ^ and R * ^ · together with the oxygen atoms to which they are attached form part of a ring optionally containing a carbonyl group, a thiocarbonyl group, an alkylidene group optionally substituted with an alkoxy group or a mono- or dialkylamino group, or a group P (O) ORl2, wherein R Represents a hydrogen atom or an alkyl group, or is an acid addition salt thereof or an alkali metal, alkaline earth metal or amine salt thereof. 4. A method according to any one of claims 1-3, characterized in that 88 03 075. the indole derivative 5,6-dihydroxyindole, 2-methyl-5,6-dihydroxyindole, 3-methyl-5,6-dihydroxyindole, 2,3-dimethyl-5,6-dihydroxyindole, 5-methoxy-6-hydroxyindole, 5- acetoxy-6-hydroxyindole, 6-acetoxy-5-hydroxyindole or 5,6-dihydroxy-2-indole carboxylic acid. Process according to claim 2, characterized in that the in-derivative derivative is 5,6-dihydroxyindole. Process according to any one of claims 1 to 5, characterized in that the iodide ions are present as alkali metal, alkaline earth metal or ammonium iodides. A process according to any one of claims 1-6, characterized in that first composition (A) containing the indole derivative, the oxidation dye and alkali metal, alkaline earth metal or ammonium iodide is applied in a suitable medium and then composition (B) containing hydrogen peroxide in contains a suitable medium. 8. Process according to any one of claims 1-7, characterized in that aqueous compositions of hydrogen peroxide with a concentration of 0.3 to 12 and preferably of 0.16 to 6% are used. Process according to any one of claims 1 to 8, characterized in that the different compositions are allowed to act for 10 sec to 45 min and preferably 20 to 25 min. 10. A composition for dyeing keratin fibers, characterized in that it contains at least one indole derivative as defined in claim 3, at least one oxidation dye belonging to the group of the fast oxidation dyes and the coupling compounds and iodide ions. Composition according to claim 10, characterized in that the fast oxidation dyes are selected from trihydroxy, aminodihydroxy, aminohydroxy, diaminohydroxy, triamino and substituted 1,2-dihydroxybenzene compounds and their salts. Composition according to claim 11, characterized in that the fast oxidation dyes are selected from 1,2,4-trihydroxybenzene, 5- (Οχ-Cg) alkyl-1,2,4-trihydroxybenzene, 1,2,3-trihydroxybenzene , 4-amino-1,3-dl-hydroxybenzene, 2-amino-1,4-dihydroxybenzene, 2-amino-4-methoxyphenol, 2,4-diaminophenol, 2-aminophenol, 4-methyl-1,2-dihydroxy- 35 benzene, 3-methoxy-1,2-dihydroxybenzene, 1,4-dihydroxy-2-diethylamino-benzene, 2,5-diamino-4-methoxyphenol, 4,6-dimethoxy-3-aminophenol, 2,6-dimethyl- 4- (p-hydroxyphenylamino) phenol, 1,5-diamino-2-methyl-4- (p-hydroxyphenylamino) benzene and its salts. 13. A composition according to claim 10, characterized in that it contains only coupling compounds as oxidation dyes. 8503 075. § 14. A composition according to any one of claims 10-13, characterized in that the coupling compounds are selected from phenols, resorcinols, pyrocatechols, meta-aminophenols, meta-phenylenediamines, mono- or polyhydroxynaphthalenes, aminonaphthalenes, pyrazolones and benzomorpholines and their salts . 15. A composition according to any one of claims 10-14, characterized in that the coupling compounds comply with formula 2, wherein: B.1 represents a hydroxy group or an amino group optionally substituted with one or more C 1 -C 6 hydro-xyalkyl groups, R 1 and independently represent a hydrogen atom, a hydroxyl group, an amino group optionally substituted with a C 1 -C 8 alkyl group or a C 1 -C 6 hydroxyalkyl group, and R 1, R 1 and R® independently represent a hydrogen atom, a C 1 -C 8 -alkoxy group, C 1 -C 8 alkyl group or a C 1 -C 8 hydroxyalkyl group, wherein and R 1 may also together form a methylenedioxy group or be a salt thereof. 16. A composition according to claims 14 and 15, characterized in that the coupling compounds of formula 2 are selected from 3-aminophenol, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 3-amino-6-methylphenol, 2- * methoxy-5-aminophenol, 1,3-diamino-4,6-dimethoxybenzene, 2-methoxy-5- (2-hydroxyethylamino) phenol, 1,3-diamino-2,6-dimethoxybenzene, 2-metho-xy-1 -Methylamino-4- (2-hydroxyethoxy) -3-aminobenzene, 1,3-diamino-6-methoxybenzene, 4,6-dimethoxy-1,3-bis (2-hydroxyethylamino) benzene, 2,6-dimethoxy -3- (2-hydroxythylamino) -1-aminobenzene, 2,4-dimethoxy-3-25 (2-hydroxyethylamino) -1-aminobenzene, 2-methyl-5- (2-hydroxyethylamino) phenol, 1,3 bis (2-hydroxyethylamino) -4-methoxybenzene, 3-amino-4-metho-xyphenol, 3,4-methylenedioxy-1-aminobenzene, 3,4-methylenedioxy-6-metho-xy-1-aminobenzene, 2, 6-dimethyl-3- (2-hydroxyethylamino) -phenol, 2,6-dimethyl-3-aminophenol, 4-ethoxy-1-amino-3- [bis (2-hydroxyethyl) amino] benzene, (2,4-diaminophenoxy) ethanol, (2-amino-4-methylaminophenoxy) ethanol, 1-methoxy-2- (2 -hydroxyethylamino) -4-aminobenzene and its salts. 17. A composition according to any one of claims 10-14, characterized in that the coupling compound is selected from 6-aminobenzomorpholine, 6-hydroxybenzomorpholine, 1-naphthol, 1-amino-7-naphthol and its salts. A composition according to claim 10, characterized in that the oxidation dyes are selected from 1,2,4-trihydroxybenzene, 1,2,4-trihydroxy-5-methylbenzene, 1,3-dihydroxybenzene, 3-aminophenol, 3-ami -no-6-methylphenol, 3,4-methylenedioxy-6-methoxyaniline, 1-naphthol and its 40 salts. 8603075. A composition according to any one of claims 10-18, characterized in that the oxidation dye is present in an amount of 0.01 to 10% by weight and preferably 0.25 to 5% by weight and the indole derivative is present in amounts between 0.01 and 5% by weight, preferably between 0.03 and 3% by weight. A composition according to any one of claims 10-19, characterized in that the amount of iodide ions is between 0.007 and 4% by weight and preferably between 0.08 and 1.5% by weight of the composition, expressed in iodide ions. A composition according to any one of claims 1-20, characterized in that the weight ratio between the indole derivative and the oxidation dye on the one hand and the iodide on the other hand is between 0.05 and 10 and preferably between 0.5 and 2. 22. A composition according to any one of claims 10-21, characterized in that the medium is an aqueous medium formed by water or a mixture of water and other solvents with a pH between 2 and 7 and preferably between 3, 5 and 7. 23. A composition according to any one of claims 10-22, characterized in that it is in the form of a solution in one or more anhydrous solvents. Composition according to claim 22 or 23, characterized in that the solvents are selected from ethyl alcohol, propyl alcohol, isopropyl alcohol, tert-butyl alcohol, ethylene glycol, the monomethyl, the monoethyl and monobutyl ether of ethylene glycol, (ethyl ethoxy) acetate, propylene glycol, monomethyl ethers of propylene glycol and dipropylene glycol and methyl lactate. Process for dyeing keratin fibers according to any one of Claims 1 to 9, characterized in that the composition (A) uses a composition according to any one of Claims 10 to 24. 26. Process according to any one of claims 1-9 and 25, characterized in that use is made of compositions comprising one or more auxiliaries selected from fatty acid amides in amounts between 0.05 and 10%, anionic, cationic, non-ionic and / or amphoteric surfactants in amounts between 0.1 and 50 wt%, thickeners in amounts between 0.1 and 5 wt%, perfumes, sequestering agents, film formers, treating agents, dispersants, conditioning agents, preservatives, cloud agents, agents for making the keratin fibers contain spheres. 27. A method according to any one of claims 1-9, 25 and 26, characterized in that the keratin fibers are human hair. 8803075? I. · 28. Device with different compartments or "kit" for "dyeing", characterized in that it contains in a first compartment a composition according to any one of claims 10-24 and in a second compartment a water-containing composition of hydrogen peroxide. 5 29 * Device according to claim 28, characterized in that the pH of the hydrogen peroxide composition is between 2 and 12 and preferably between 2 and 7. 30. Device with different compartments or "kit" for dyeing, characterized in that in a first compartment it comprises a composition according to claim 23 or 24, in a second compartment a water-containing medium suitable for dyeing and in a third compartment contains an aqueous composition of 0.3-12% hydrogen peroxide with a pH between 2 and 12 and preferably between 2 and 7, the contents of the second compartment being intended to be used immediately before use with the contents of the first compartment. be mixed. 31. Device with different compartments, characterized in that it comprises in a first compartment a composition of an indole derivative according to any one of claims 3-5 and a fast oxidation dye and / or a coupling compound in a medium suitable for dyeing, in 20 a second compartment contains a composition of iodide ions in a medium suitable for dyeing and in a third compartment a hydrogen peroxide composition in a water medium, the contents of the third compartment being intended to be mixed with the contents of the first compartment just before use. 25 ------ 8803075.