WO2010046256A2

WO2010046256A2 - Method for concealing gray hairs

Info

Publication number: WO2010046256A2
Application number: PCT/EP2009/063241
Authority: WO
Inventors: Astrid Kleen; Doris Oberkobusch; Wibke Gross; Laura Stephan
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2008-10-22
Filing date: 2009-10-12
Publication date: 2010-04-29
Also published as: DE102008061863A1; WO2010046256A3; EP2337550A2

Abstract

The present invention relates to a method for permanently dying gray hairs, wherein - in a first step, the entire hairs are treated with an oxidative dye (A) and - the subsequently regrown gray hair roots are treated in one or more further steps with a medium (B) that is obtained from the following by mixing directly before application at least one medium (B1) that contains at least one reactive carbonyl compound in a cosmetic carrier, and at least one medium (B2) that contains at least one C, H acidic compound selected from the compounds of the formula (CH-1) and/or compounds of the formula (CH-2) in a cosmetic carrier, wherein - R6 stands for a linear or cyclic (C1 to C6) alkyl group, a (C2 to C6) alkenyl group, a possibly substituted aryl group, a possibly substituted heteroaryl group, an aryl (C1 to C6) alkyl group, a (C1 to C6) hydroxyalkyl group, a (C2 to C6) polyhydroxyalkyl group, a (C1 to C6) alkoxy (C1 to C6) alkyl group, a group RIRIIN-(CH2)m-, wherein RI and RII stand independently of each other for a hydrogen atom, a (C1 to C4) alkyl group, a (C1 to C4) hydroxyalkyl group, or an aryl (C1 to C6) alkyl group, wherein RI and RII together with the nitrogen atom can form a 5-, 6-, or 7-membered ring and m stands for a number 2, 3, 4, 5, or 6, - R7 stands for a (C1 to C6) alkyl group, particularly for a methyl group, - X- stands for a physiologically acceptable anion, - the cycle of the formula (CH-1) represents all ring structures that can additionally contain heteroatoms such as nitrogen, oxygen, or sulfur and can furthermore carry fused ring structures, wherein all of said ring structures can carry additional substituents, Het stands for an optionally substituted heteroaromatic, and - X1 stands for a direct bond or a carbonyl group.

Description

"U s in g th e c o n t i o n c o n t i o n c o n tio n s"

The present invention relates to a process for the permanent coloring of gray hair, in which the

Hair first oxidatively colored and the re-grown hair roots later with a special aftertreatment agent based on reactive carbonyl compounds and C, H-acidic

Compounds to be post-dyed, a method for coloring gray-haired Asian hair, the

Use of the special aftertreatment agent as well as appropriate dyeing kits.

Human hair is treated today in many ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and

Cures and bleaching, dyeing and shaping of hair with coloring, toning preparations,

Wells and styling preparations. Thereby means for changing or nuancing the color of the

Head hair a prominent role.

The change in the coloring of the hair represents an important area of modern cosmetics.

Thus, the appearance of the hair can be adapted to both current fashion trends and the individual wishes of the individual. In addition, the desire for

Conservation of natural hair color even in old age and thus means for lamination of gray

Hair among consumers more pronounced.

Conventional hair dyes usually contain at least one color-changing active ingredients

Developer and / or at least one coupler components and optionally still substantive

Dyes as Nuanceure. Coupler and developer components are also referred to as oxidation dye precursors.

Before being applied to human hair, hair dyes are usually mixed in solid or pasty form with a dilute aqueous hydrogen peroxide solution. The resulting

Mixture is then applied to the hair and rinsed again after a certain exposure time.

The duration of exposure to the hair to achieve complete coloration is usually between about 30 and 40 minutes.

In order to achieve a sufficient dyeing effect, the ready-to-use colorants are usually adjusted strongly alkaline, the pH is between 8 and 10.5. Such high pH values are required to ensure an opening of the outer cuticle (cuticle) and thus a

Penetrating the active species (hydrogen peroxide) into the hair.

Due to the strongly alkaline conditions as well as the use of hydrogen peroxide it can be used in the

Associated with the color changing process to irritation of the scalp come. These can be observed both during the action of the color-changing agent and also after the treatment.

In addition, the usual hair dyeing techniques have the disadvantage that at the hairline after a few days again a gray offspring occurs, which stands out unpleasantly, especially in the forehead and apex area. Accordingly, various techniques have been developed in the past to conceal the newly regrown gray hairline.

On the one hand, the newly regrown hairline can be specifically subjected to another oxidative dyeing. This technique allows a durable and stable lamination, but is cumbersome and can bring the disadvantages described above (hair damage, scalp irritation) with it.

Another technique, especially popular in Asian countries, is the treatment of the graying

Hairstyles with agents based on substantive dyes. In particular, anionic substantive substances are used. This technique allows easy lamination of gray

Approaches, which, however, has only a very poor authenticity and must be repeated after a few washes. In addition, an intensive staining of the scalp is often observed when using anionic substantive dyes.

Accordingly, there is still the need for a staining technique that is durable

Lamination of gray hair allows without the disadvantages mentioned. This need exists especially for Asian gray hair. For one thing, Asian hair has a different one

Hair structure as European hair on and are much harder to dye. On the other hand, the colorants must allow intensive black nuances with excellent opacity, so that the dyed hair as little as possible in terms of hue of the other areas of the

Distinguish hair.

The object of the present invention was therefore to provide a dyeing process which allows a permanent coloration of gray hair. At the same time, an irritation of the scalp, a

Damage to the hair and staining of the scalp are largely avoided.

As part of the underlying this application, it has now surprisingly been found that a method in which the hair is first dyed oxidatively and the regrowing hair approaches then with a dye based on reactive

Carbonyl compounds and C, H-acidic compounds, does not lead to the above adverse effects.

A first subject of the present invention is therefore a process for the permanent dyeing of gray hair, in which in a first step the entire hair is treated with an oxidative dye (A) and the subsequently regrown gray hair roots in one or more further

Steps are treated with a remedy (B) immediately before the application

At least one agent (B1) containing at least one reactive carbonyl compound in a cosmetic carrier, and

At least one agent (B2) which contains in a cosmetic carrier at least one C, H-acidic compound selected from compounds of the formula (CH-1) and / or compounds of the formula (CH-2),

wherein

R ⁶ represents a linear or cyclic (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (d to C ₆ ) alkyl group , a (C ₁ -C ₆₎ - hydroxyalkyl group, a (C ₂ -C ₆₎ -polyhydroxyalkyl group, a (C ₁ to C ₆₎ alkoxy alkyl (C-ι to C _6), a group

R'R "N- (CH ₂ ) _m -, wherein R ¹ and R ¹¹ independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) hydroxyalkyl group or an AIyI - (C ₁ to C ₆ ) -alkyl group, wherein R ¹ and R "together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, R ⁷ is a (C ₁ to C ₆ ) alkyl group, in particular a methyl group, X ^' is a physiologically acceptable anion, the cycle of the formula (CH-1) represents all ring structures which additionally contain further heteroatoms such as nitrogen, oxygen or may contain sulfur and may further carry fused ring structures, all of which ring structures may carry additional substituents,

Het is an optionally substituted heteroaromatic, and X ¹ is a direct bond or a carbonyl group, obtained by mixing.

The method according to the invention is composed of 2 or more treatment steps. According to the invention, the formulation "the subsequently regrown gray hair roots are treated with an agent (B)" in one or more further steps is such that the second treatment step can not take place until a freshly regrown hairline has already been recognized it is when the time interval between the oxidative dyeing and the treatment of re-grown hair roots is at least 5 days.Furthermore, the phrase "the subsequently regrown gray hairlines in one or more further steps with an agent (B) to be treated" to understand in that, at the time at which a gray hairline re-emerges after the aftertreatment, the treatment with the agent (B) can be repeated.

Also, the time interval between two successive treatments with the agent (B) according to the invention is preferably at least 5 days.

Overall, the treatment with the agent (B) according to the invention in principle can be repeated as often as soon as a gray hairline becomes visible. However, it is preferred according to the invention after 3, 4, 5 or 6 aftertreatments with the agent (B) complete the dyeing process and re-subject the entire fibers to a complete oxidative dyeing. In the context of the method according to the invention, the hair is treated in a first step with an oxidative dye (A).

The oxidative colorant (A) preferably contains at least one oxidation dye precursor.

As oxidation dye precursor, the agent (A) used in the process of the invention preferably contains at least one developer component.

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Very particularly preferred p-phenylenediamine derivatives according to the invention are selected from at least one compound of the group p-

Phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 2- Methoxymethyl-p-phenylenediamine, N- (4-

Amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, as well as the physiologically acceptable salts of these compounds.

It may further be preferred according to the invention to use as developer component compounds containing at least two aromatic nuclei which are reacted with amino and / or

Hydroxyl groups are substituted. Very particularly preferred binuclear developer components are selected from N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol,

Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4 diazacycloheptane, 1, 10-bis- (2,5-diaminophenyl) -1, 4,7,10-tetraoxadecane or one of the physiologically acceptable salts of these compounds.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Very particularly preferred

Compounds are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2-

(α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Furthermore, the developer component may be selected from heterocyclic

Developer components, such as pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine

Derivatives or their physiologically acceptable salts.

Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4 , 5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

Particularly preferred pyrazole derivatives are in particular the compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-

Diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 -phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-

Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-

3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole,

4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-

Diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5- Diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (ß-aminoethyl) amino-1, 3-dimethylpyrazole, and their physiologically acceptable salts.

Very particularly preferred developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) - methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4-aminophenyl) -1, 4-diazacycloheptane, 1, 10-bis- (2, 5-diaminophenyl) -1, 4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine , 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds. The developer components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use agent (A). The agents (A) used in the context of the process according to the invention may contain, in addition to the developer component or else instead of the developer component, at least one coupler component.

Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components. Therefore, it is preferred according to the invention that at least one coupler component is additionally used when using at least one developer component.

Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms a covalent bond between the coupler and the developer component. Couplers are preferably cyclic compounds which carry on cycle at least two groups selected from (i) optionally substituted amino groups and / or (ii) hydroxy groups. When the cyclic compound is a six-membered ring (preferably aromatic), said groups are preferably in ortho position or meta position to each other.

Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:

m-aminophenol and / or its derivatives,

m-diaminobenzene and / or its derivatives,

o-diaminobenzene and / or its derivatives,

o-aminophenol derivatives, such as o-aminophenol,

Naphthalene derivatives having at least one hydroxy group,

Di- or trihydroxybenzene and / or derivatives thereof,

- pyridine derivatives,

- pyrimidine derivatives,

Monohydroxyindole derivatives and / or monoamine indole derivatives,

Monohydroxyindoline derivatives and / or monoaminoindoline derivatives, Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,

Morpholine derivatives such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Mixtures of two or more compounds from one or more of these classes are also within the scope of this embodiment according to the invention.

Particularly preferred m-aminophenol coupler components are selected from at least one compound selected from the group consisting of m-aminophenol, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6 -methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4 -methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1, 3-dihydroxy-5- (methylamino) - benzene, 3-ethylamino-4-methylphenol, 2,4-dichloro-3-aminophenol and the physiologically acceptable salts of all the abovementioned compounds.

Particularly preferred m-diaminobenzene coupler components are selected from at least one compound from the group formed from m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2- ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2 -methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene and the physiologically acceptable salts of all the abovementioned compounds.

Particularly preferred o-diaminobenzene coupler components are selected from at least one compound selected from the group consisting of 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene and the physiologically acceptable salts of all of the aforementioned compounds. Preferred di- or trihydroxybenzenes and their derivatives are selected from at least one compound of the group formed from resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1 , 2,4-trihydroxybenzene.

Particularly preferred pyridine derivatives are selected from at least one compound of the group formed from 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino 6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 3,5-diamino-2, 6-dimethoxypyridine, 3,4-diaminopyridine, 2- (2-methoxyethyl) amino-3-amino-6-methoxypyridine, 2- (4'-methoxyphenyl) amino-3-aminopyridine, and the physiologically acceptable salts of the aforementioned compounds. Preferred naphthalene derivatives having at least one hydroxy group are selected from at least one compound of the group formed from 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 3 Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene. Particularly preferred indole derivatives are selected from at least one compound of the group which is formed from 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole and the physiologically acceptable salts of the abovementioned compounds.

Particularly preferred indoline derivatives are selected from at least one compound of the group formed from 4-hydroxyindoline, 6-hydroxyindoline and 7-hydroxyindoline and the physiologically acceptable salts of the aforementioned compounds.

Preferred pyrimidine derivatives are selected from at least one compound of the group formed from 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2 -Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine and the physiologically acceptable salts of the aforementioned compounds.

Particularly preferred coupler components according to the invention are selected from m-aminophenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol , 5- (2'-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, o-aminophenol, m-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2,4-diaminophenyl) propane, 2,6-bis (2'-bis) hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2 -methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol , 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1, 2,4- Trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridi n, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1, 5-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned Links. The coupler components are preferably used in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the ready-to-use agent (A). In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can stand.

It may be preferred according to the invention to add to the agent (A) of the process according to the invention as further dye precursor a naturally-analogous dye.

The dyestuff precursors of naturally-analogous dyes are preferably indoles and indolines which have at least two groups selected from hydroxy and / or amino groups, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a further embodiment, the colorants contain at least one indole and / or indoline derivative. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent. Especially suitable as precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline. Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxy-indoline and in particular the 5,6-Dihydroxyindolin.

Derivatives of 5,6-dihydroxyindole are also outstandingly suitable as precursors of naturally occurring hair dyes. Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 - Dihydroxyindole.

The indoline or the indole derivatives can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, eg. As the hydrochlorides, sulfates and hydrobromides are used.

Furthermore, in the agent (A) additionally at least one substantive dye may be included. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, based on the total application preparation. The total amount of substantive dyes is preferably at most 20% by weight.

Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes.

Preferred anionic substantive dyes are those under the international designations or trade names Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds. Preferred cationic substantive dyes are included

(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, which is explicitly referred to at this point, are claimed in claims 6 to 11.

The dyes known under the names Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive dyes of group (c). The cationic substantive dyes sold under the trademark Arianor are also very particularly preferred cationic substantive dyes according to the invention. Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- Chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic acid, 6-nitro-1 , 2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid e and 2-chloro-6-ethylamino-4-nitrophenol.

It is not necessary that the substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, minor amounts of other components may be included, as far as these do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

Furthermore, as direct dyes also naturally occurring dyes may be used, as for example in henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

Furthermore, the agent (A) of the invention may also be present in nature dyes such as red henna, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root , contain.

The actual oxidative coloring of the hair can basically be done with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Therefore, in a preferred embodiment of this aspect of the present invention, the agent (A) is prepared immediately prior to use from an agent (A1) containing an oxidation dye precursor and an agent (A2) containing an oxidizing agent.

Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate. However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

The actual oxidative hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent (A2) with the preparation (A1) containing the dye precursors. The resulting ready-to-use hair dye preparation (A) should be preferred have a pH in the range of 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can be in a range between 15 and 40 ⁰ C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, such as a dyeing shampoo was used.

Especially with hair that is difficult to dye, the preparation with the dye precursors can also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes is then rinsed and nachshampooniert if desired. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.

In the second and optionally further steps of the method according to the invention, the hair is treated with an agent (B) which is obtained by mixing directly before application from an agent (B1) and an agent (B2). The agent (B1) contains at least one reactive carbonyl compound.

Reactive carbonyl compounds have in the context of the invention at least one carbonyl group as a reactive group which reacts with the CH-acidic component to form a covalent bond. Preferred reactive carbonyl compounds are selected from compounds which carry at least one formyl group and / or at least one keto group, in particular at least one formyl group. Furthermore, those compounds according to the invention are also suitable as component (Oxo1) in which the reactive carbonyl group is derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the component (Oxo2) is always present. These derivatives are preferably addition compounds a) of amines and their derivatives to form imines or oximes as addition compound b) of alcohols to form acetals or ketals as addition compound c) of water to form hydrates as addition compound (component (Oxo1) is derived in in this case c) from an aldehyde) to the carbon atom of the carbonyl group of the reactive carbonyl compound. In a preferred embodiment of the method according to the invention, the agent (B1) contains a reactive carbonyl compound which is selected from 4-hydroxy-2-methoxybenzaldehyde, 2-chloro-3,4-dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3 , 4-Dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1, 5-dimethyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxaldehyde and 2,4-dimethoxy-benzaldehyde. Particularly preferred have been agents (B1), the 4-hydroxy-2-methoxybenzaldehyde in combination with at least one further reactive carbonyl compound selected from 2-chloro-3,4-dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3,4-Dihydroxy-5-methoxybenzaldehyde, 2,3- Dihydro-1, 5-dimethyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxaldehyde and 2,4-dimethoxy-benzaldehyde.

The reactive carbonyl compound (s) of the agent (B1) are preferably used in an amount of 0.03 to 65.00 mmol, based on 100 g of the agent (B1). The use of 1, 00 to 30.00 mmol, based on 100 g of the agent (B1), is particularly preferred.

The agent (B2) contains at least one CH-acidic compound of the general formula (CH-1) and / or the general formula (CH-2) (v / cfe supra).

As CH-acidic compounds are generally considered those compounds which carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents, activation of the corresponding carbon-hydrogen bond are effected. The compounds of formula (CH-1) and (CH-2) are C, H-acidic compounds. From the cationic compounds of the formula (CH-1), it is possible by targeted addition of a base which effects the cleavage of a proton to represent the corresponding uncharged enamine form. As an example for compounds of the formula (CH-1), the illustration of the enamine form is illustrated below by means of the formulas (CH-1-A) and (CH-1-B) with R ⁷ = CH ₃ . The corresponding enamine forms of the CH-acidic compounds according to formula (CH-1) are also according to the invention.

It is particularly preferred according to the invention to select the compounds of the formula (CH-1) from at least one compound of the formula (CH-3),

wherein

R and R independently of one another represent a linear or cyclic (C ₁ to C ₆ ) -alkyl group, a (C ₂ to C ₆ ) -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl- (C-1 to C ₆₎ alkyl group, a (C ₁ -C ₆₎ - hydroxyalkyl group, a (C ₂ -C ₆₎ -polyhydroxyalkyl group, a (C ₁ to C ₆₎ alkoxy (C-ι-C ₆₎ - alkyl group , a group R'R ^M N- (CH ₂ ) _m -, wherein R ¹ and R ¹¹ independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) hydroxyalkyl group or an aryl (C ₁ to C ₄ ) alkyl group, wherein R ¹ and R ¹¹ together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,

R ¹⁰ and R ¹² independently of one another represent a hydrogen atom or a C 1 -C ₆ -alkyl group, where at least one of the radicals R ¹⁰ and R ¹² denotes a (C ₁ to C ₆ ) -alkyl group, R ¹¹ represents a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group, a (C ₂ to C ₆ ) -polyhydroxyalkyl group, a (C ₁ to C ₆ ) -alkoxy group, a (Ci to _C6) - hydroxyalkoxy group, a group R ^m R ^lv N- (CH ₂₎ _q - wherein R ¹ "and R ^IV are independently a hydrogen atom, a (Ci to _C6) alkyl group, a ( Ci to C ₆ ) - hydroxyalkyl group or an aryl (Ci to C ₆ ) alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ¹¹ together with one of the radicals R ¹⁰ or R ^{12 may form} a 5- or 6-membered aromatic ring optionally substituted with a halogen atom, a (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆ ) hydroxyalkyl group, a (C ₂ to C ₆ ) Polyhydroxyalkyl group, a (C ₁ to C ₆ ) alkoxy group, a (C ₁ to C ₆ ) hydroxyalkoxy group, a nitro group, a hydroxy group, a group

R ^V R ^VI N- (CH ₂ ) _S -, wherein R ^v and R ^vι independently of one another represent a hydrogen atom, a (C ₁ to C ₆ ) -alkyl group, a (C ₁ to C ₆ ) -hydroxyalkyl group or an AIyI - (C ₁ to C ₆ ) -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,

• Y represents an oxygen atom, a sulfur atom or a group NR ^V ", wherein R ^v" stands for a hydrogen atom, an aryl group, a heteroaryl group, a (C ₁ to C ₆₎ alkyl group or an aryl (C-ι to C ₆ ) alkyl group,

• X- stands for a physiologically compatible anion.

At least one group R ¹⁰ or R ¹² according to formula (CH-3) is necessarily a (C ₁ to C ₆ ) -

Alkyl group. This alkyl group preferably carries at least two at the α-carbon atom thereof

Hydrogen atoms. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso

Butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R ¹⁰ and R ¹² independently of one another represent hydrogen or a methyl group, where at least one group R ¹⁰ or R ^{12 is} a

Methyl group.

In a preferred embodiment, Y of the formula (CH-3) is an oxygen or a

Sulfur atom, more preferably an oxygen atom.

The radical R ^{8 of} the formula (CH-3) is preferably selected from a (C ₁ to C ₆ ) -alkyl group (particularly preferably a methyl group), a (C ₂ to C ₆ ) -alkenyl group (in particular an allyl group), a

(C ₂ to C ₆ ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

R ^{11 of} the formula (CH-3) is preferably a hydrogen atom.

Particularly preferred in formula (CH-3) are the radicals R ⁹ , R ¹⁰ and R ^{12 is} a methyl group, the remainder

R ^{11 is} a hydrogen atom, Y is an oxygen or a sulfur atom and the radical R ⁸ is selected from a (C ₁ to C ₆ ) alkyl group (particularly preferably a methyl group), a (C ₂ to

C ₆ ) alkenyl group (especially an allyl group), a (C ₂ to C ₆ ) hydroxyalkyl group (especially a 2-hydroxyethyl group) or an optionally substituted benzyl group.

According to the invention, it has proved to be preferred when the C, H-acidic compound of the agent (B2) is selected from the physiologically acceptable salts of 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxo - pyrimidiniums, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidiniums and 2- (cyanomethyl) benzimidazole.

Particularly preferred according to the invention are agents (B2) which necessarily contain a salt of the 1-allyl-i, 2-dihydroxy

Contain 3,4,6-trimethyl-2-oxo-pyrimidiniums and optionally 2- (cyanomethyl) benzimidazole. The CH-acidic compounds of the formula (CH-1) and / or the formula (CH-2) in the agent (B2) are preferably used in an amount of 0.03 to 65.00 mmol, based on 100 g of the agent ( B2). The use of 1, 00 to 30.00 mmol, based on 100 g of the agent (B2), is particularly preferred. According to the invention, the specific combinations of C, H-acidic compound and reactive carbonyl compound have proven to be particularly advantageous. With regard to these combinations, reference should be made explicitly to the corresponding statements of the associated priority document at this point.

In the context of the work on which this invention is based, it has also been possible to show that the different relevant nuances can preferably be obtained from mixtures of the substances indicated in the following table in the stated mixing ratio (stated in% by weight):

In a further embodiment, in the agent (B1) and / or in the agent (B2) additionally at least one developer component and optionally at least one coupler component may be present as oxidation dye precursors. However, it is preferred to formulate the agents according to the invention free of oxidation dye precursors, in particular if the risk of allergies is to be minimized for allergy sufferers.

With regard to the developers and coupler components which can be used in the compositions (B1) and / or (B2), reference is explicitly made at this point to the above remarks concerning the agent (A). In the context of the work underlying this application, it has further surprisingly been found that a method in which Asian gray hairs are dyed with a colorant based on specially selected reactive carbonyl compounds and C, H-acidic compounds does not lead to the abovementioned adverse effects leads.

A second subject of the present invention is therefore a process for dyeing gray-haired Asian hair, in which the grayed hair parts are treated with an agent (B) immediately before use

at least one agent (B1) which comprises, in a cosmetic carrier, 4-hydroxy-2-methoxybenzaldehyde and at least one further reactive carbonyl compound selected from 2-chloro-3,4- dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1, 5-dimethyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxaldehyde and 2,4-dimethoxybenzaldehyde, and at least one agent (B2) containing in a cosmetic carrier 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide and optionally 2- (cyanomethyl) benzimidazole obtained by mixing.

With regard to the combinations preferred according to the invention, reference is explicitly made at this point to the statements on the first subject of the present invention. Both in the context of the first subject and within the scope of the second aspect of the present invention, the following conditions have been found to be advantageous. During the work on which this invention is based it has been found that the storage stability of the reactive carbonyl compounds can be considerably increased if the agent (B1) contains the reactive carbonyl compound (s) in a cosmetic carrier, the pH of which By means of between 2 and 5 lies.

In addition, it has been found that the stability of the particular CH-acidic compounds can be increased if the agent (B2) contains these in a cosmetic carrier and has a pH of 0.5 to 2.5. By this measure, the stability of the formulation increases to such an extent that there is no significant degradation of the content of CH-acidic compound even when stored for several months.

Particularly storage-stable formulations can be obtained if the agent (B1) has a pH of between 3 and 4.5, therefore this pH range is particularly preferred. Furthermore, it is particularly preferred if the agent (B2) has a pH of 1 to 2 and particularly preferably a pH of 1.1 to 1.9.

The pH values for the purposes of the present invention are pH values which are measured at a temperature of 22 ^° C.

The adjustment of the pH in the agents (B1) and / or (B2) can be carried out with the aid of an organic or inorganic acid such as hydrochloric, sulfuric, hydrobromic, phosphoric, acetic, tartaric, citric, lactic, malic or glycolic acid.

In this connection, the adjustment of the pH values according to the invention with the aid of sulfuric acid, hydrochloric acid, tartaric acid, citric acid, malic acid or lactic acid is particularly preferred. In the context of the method according to the invention, the agents (B1) and (B2) can be intimately mixed with one another shortly before application to the hair fiber.

However, to further improve the staining result, it may be advantageous to carry out the staining even in a pH range of 7 to 10.

Therefore, in a particular embodiment of the method according to the invention, a third component (B3) which comprises at least one alkalizing agent in a cosmetic carrier can be added to the mixture of the agents (B1) and (B2). It is preferred according to the invention if the agent (B3) has a pH of 7 to 10. Furthermore, it is preferred if the ready-to-use agent (B) after addition of the agent (B3) has a pH of 7 to 10.

In the alkalizing agent contained in agent (B3) in a cosmetic carrier, alkalizing agents selected from the group consisting of ammonia, basic amino acids, alkali hydroxides, alkanolamines, alkali metal metasilicates, urea, morpholine, N-methylglucamine, imidazole, alkali phosphates and alkali hydrogen phosphates may be preferably used , are used. The alkali metal ions used are preferably lithium, sodium, potassium, in particular sodium or potassium. The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from L-arginine, D-arginine, D, L-arginine, L-histidine, D-histidine, D, L-histidine, L-lysine, D-lysine, D, L-lysine. L-arginine, D-arginine, D, L-arginine are particularly preferably used as an alkalizing agent according to the invention.

The alkali metal hydroxides which can be used as the alkalizing agent according to the invention are preferably selected from the group formed from sodium hydroxide and potassium hydroxide. The alkanolamines which can be used as alkalizing agents according to the invention are preferably selected from primary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 -Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol , 1-amino-2-methylpropan-2-ol, 3-aminopropane-1, 2-diol, 2-amino-2-methylpropane-1,3-diol. Very particularly preferred alkanolamines according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methylpropane-1,3-diol.

The alkalizing agent is particularly preferably selected from at least one compound from the group formed from ammonia, 2-aminoethanol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propane-1, 3 diol, potassium hydroxide, sodium hydroxide, L-arginine, D-arginine, DL-arginine, N-methylglucamine, morpholine, imidazole and urea.

Very particularly preferred alkalizing agents according to the invention are monoethanolamine, ammonia, sodium hydroxide, potassium hydroxide and / or arginine.

Furthermore, buffer systems adjusted to a pH greater than 7 can also be used in agent (B3).

According to the invention, the pH buffer system is considered to be those chemical compounds or a combination of chemical compounds which, in a solution, cause the pH of the solution to change only slightly when a small amount of acid or alkali is added to a volume of the cosmetic carrier. This change is less pronounced than is the case when the same amount of acid or lye is added to an equal volume of the cosmetic carrier without the pH buffer system.

Such pH buffer systems are preferably selected from at least one member selected from the group consisting of bicarbonate, organic acid (especially citric acid) / monohydrogen phosphate, human acid (especially citric acid) / dihydrogen phosphate, tris (hydroxymethyl) aminomethane / maleic acid / NaOH, Tris (hydroxymethyl) aminomethane / maleic acid / KOH, tris (hydroxymethyl) aminomethane / HCl, monohydrogen phosphate / dihydrogen phosphate, dihydrogen phosphate / NaOH, dihydrogen phosphate / KOH, H ₃ BO ₃ / KCl / NaOH, H ₃ BO ₃ / KCl / KOH, borate / HCl, borate / halide (especially chloride such as potassium chloride) / NaOH, borate / halide (especially chloride such as potassium chloride) / KOH, Theorell and Stenhagen buffer system, Mcllvine buffer system, glycine / NaOH and glycine / KOH. Particularly preferred pH buffer systems are selected from at least one member of the group formed from tris (hydroxymethyl) aminomethane / maleic acid / NaOH, tris (hydroxymethyl) amino methane / maleic acid / KOH, tris (hydroxymethyl) aminomethane / HCl, Borate / HCI and H ₃ BO ₃ / KCl / NaOH. The slotted pH buffer systems from the above list represent mixtures of these compounds separated by the slash. The anionic compounds listed are used in the form of their salts with a corresponding mono- or polyvalent cation. Preferred cations are alkali metal cations (especially sodium or potassium) and ammonium ions.

Useful acids which can be used according to the invention in the buffer systems are, for example, citric acid, tartaric acid or malic acid or mixtures thereof.

The pH buffer system is preferably in an amount of 0.1 to 10.0 wt .-%, particularly preferably from 0.3 to 5.0 wt .-%, most preferably from 0.5 to 3.0 wt. %, in each case based on the weight of the application mixture of agent (B1), agent (B2) and agent (B3), in the ready-to-use colorant.

In this connection, the pH of the final application mixture prepared by mixing the agents (B1), (B2) and (B3) may be from 7.5 to 11. If the pH of the final application mixture is in the range of 7.5 to 9.0, it is preferred. The agents used in the process according to the invention contain the essential components of the invention in a cosmetically acceptable carrier. As such, a suitable aqueous, alcoholic or aqueous-alcoholic carrier is preferably used. For the purposes of the present invention, such carriers are, for example, creams, emulsions, gels or else surfactant-containing foaming solutions, for example shampoos, foam aerosols or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the components essential to the invention into a powdery or tablet-shaped formulation.

For the purposes of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C 1 -C ₄ -alcohol, in particular ethanol or isopropanol. The compositions of the invention may additionally contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1, 2-propylene glycol. Preference is given to all water-soluble organic solvents.

In the context of a first preferred embodiment, the agents (B1), (B2) and optionally (B3) used according to the invention are adjusted to low viscosity. Application preparations which, after mixing components (B1), (B2) and optionally (B3) have a viscosity of from 0 to 2000 mPas (measured at 22 ° C. in a Brookfield viscometer with spindle 4 and a speed of 4 rpm), have proven to be particularly preferred. Viscosity from 0 to 100mPa, measured under the conditions mentioned, is particularly preferred according to the invention. A viscosity of from 50 to 500 mPas (measured at 20 ^° C. (Brookfield viscometer type RV-T, spindle 4 with a rotational speed of 20 rpm) is very particularly preferred according to the invention In the context of this embodiment of the present invention, it has proved to be Advantageously, the application ready means (B) by means of an application device (1) with at least one container (2) for receiving the agent (B), with an application head (3) which is connected to the at least one container (2) and a porous applicator body (31) to apply to human hair by repainting.

An advantageous design of the actual application device provides that the porous applicator has continuous pores to achieve capillary action. The capillary properties of the applicator body wickingly associated with the agent (B) provide for reliable transport of the agent (B) from the at least one container and metered application of the agent (B) by recoating on the fibers. According to a further developed variant of the application device, the application body preferably has a fibrous, sponge, foam, felt or sintered material-like material structure. This material structure causes the desired capillary action of the application body, so that, for example, an unwanted leakage or dripping of the agent (B) from the application body is omitted, but at the same time a reliable fluid delivery is ensured by means of the application body.

As an alternative to a substantially block-shaped design of the porous application body, it can also have a plurality of pin-shaped projections. This increases the effective surface of the application body and thus improves the application of the agent (B). As a result, a better staining result is ensured quantitatively as well as qualitatively by means of the brushing movement of the application body via the hair.

Another useful embodiment of the application device is achieved in that the application head has a plurality of possibly detachably arranged, comb teeth. These comb teeth are arranged in particular adjacent to the application body. The stroking movement of the entire application head during the application ensures by means of the comb teeth initially for a disentanglement of the hair and thus, above all, for a uniform application of the agent (B). Basically, the detachable arrangement of the comb teeth on the application head allows a more versatile use of the application device. It also proves to be advantageous for such an arrangement when the comb teeth protrude from the porous applicator body. A preferred embodiment of the application device is to arrange the comb teeth of the application head in a circle around the application body. Regardless of the respective brushing direction, the hair is first unraveled during use in each case before the actual application of the agent (B) takes place.

Furthermore, it is essential to the invention that the actual agent (B) is prepared only immediately before use by mixing the preparation (B1), (B2) and optionally (B3). In particular, as a result of often insufficient storage stability of the mixture, correspondingly designed storage and mixing containers are required in the context of the overall device. The suitably designed storage and mixing containers guarantee on the one hand before use a sufficient Storage stability for the individual components of the agent (B) and on the other hand ensure an appropriate handling of the overall device during use. For this purpose, different variants of the application device are possible. These different variants have in common that immediately before the application, the already mixed preparation of the application liquid is in the container of the device according to the invention. The container is connected to the application head. For the container, a variety of design options is conceivable. For example, this container can be ergonomically adapted in its shape to the application process in order to facilitate the handling of the application device for the user. The container can be designed both as a separate application container, in which the ready-mixed preparation of the application liquid is filled before starting the application. Similarly, it is also conceivable that the container serves both as an application container, as well as before application as a mixing container. Mixing container and application container are identical in this variant and form the container. For both embodiments, a variety of ways will be described below to design such mixing container constructive.

In order to carry out a mixture of the preparations (B1), (B2) and optionally (B3), there are a number of possibilities, some of which are to be listed here by way of example. Thus, it is possible to provide the user with three or more containers in a first embodiment of the present invention. The first container contains the agent (B1), the second container the means (B2), the third container serves as a mixing container and a fourth container may optionally contain the agent (B3). Further additional storage containers are possible. To prepare the mixture, the desired amount is added from the two or three storage containers in the mixing container, this closed, and the components are mixed together, for example, by subsequent shaking of the mixing container. The mixing process can be accelerated by the fact that internals in the mixing vessel when shaking produce a turbulent flow (high Reynolds numbers) and thus improve and accelerate the mixing process. In the case where one or more of the components are particulate or granular components, it may be advantageous to provide internals in the mixing container in such a way that a mechanical action is aimed at destruction or faster solubility of the granules or component pieces. This is achieved, for example, by projecting into the mixing container tips or barb-like elements. Also internals in the form of stirrers achieve a similar result.

Another embodiment within the scope of the present invention is to provide one or more of the liquid soluble material reservoirs. These soluble storage containers are placed in the mixing container and there dissolved by the respective solvent, preferably a component of the mixture to be prepared. This embodiment has the advantage for the user of never coming into contact with individual components packed in the storage containers during the preparation of the overall preparation. In order to accelerate the dissolution process in addition, it may be advantageous to use here also mechanical installations, which comminution of the described reservoir and a concomitant To increase the speed of the dissolution process. Advantageously, such soluble storage containers are designed as a foil bag.

A further variant for producing mixtures according to the invention is the provision of at least two separate containers for storing the respective component, wherein at least one of the containers simultaneously acts as a mixing container. For such embodiments, all the above examples of the variant with at least three containers are also conceivable within the scope of the present invention.

Both in two storage containers, one of which additionally serves as a mixing container and in the variant with at least three containers (ie a separate mixing container), it may be advantageous to provide Umfüllhilfen, which ensure that when transferring from the storage containers in the mixing container / combined Vorratsmischbehälter no single component is spilled. Such Umfüllhilfen are, for example, extended Ausgießrohre that allow the nesting of reservoir and mixing container and means for fixing the reservoir to the mixing container during Umfüllvorgangs. Such fixing means are for example snap-locking connections, screw or bayonet.

In order to further accelerate transfer, it may be advantageous to provide means which provide pressure equalization between the two containers during the transfer operation. Such means are, for example, arranged within the opening of a reservoir tubes, which can act as a snorkel. Also, one-way valves in the rratsbe container for pressure equalization are conceivable for such functionalities.

It is also helpful for the user if the storage containers are provided with a closure which only opens upon a triggering command. Thus, the user can ensure that the transfer process does not start until the reservoir and mixing container are in the correct position for the mixing process. One possible embodiment of such closures is, for example, a tear-open film which tears open due to an increased internal pressure in the storage container and thus starts the transfer process. The internal pressure in the reservoir can be increased for example by pumping means or by simply squeezing.

Also mechanical destruction of such films by mechanical aids, such as thorns, or by the contained component itself, for example in tablets, is conceivable. For example, it is also conceivable to carry out the container for granules, powders or lumpy goods as a blister pack and additionally to provide auxiliaries which allow these blisters to be placed above the opening of the mixing container. The user of such mixing systems simply presses the component contained in the blister through the sealing film into the mixing container. In addition to the variants with three or more containers, or two or more containers, it is also conceivable to provide only a single container, which serves both as a storage container and as a mixing container. Such containers must be equipped due to the lack of storage stability of the individual components in mixture with a possibility for separation of the components during storage. Such a separation can be generated for example by partitions through which a container is formed with two or optionally three separate chambers. The mixture in such a system is created by the destruction of the Partitions or by the arrangement of valves in the partitions. For destructible partitions, it may be useful to achieve this destructibility either by increasing the internal pressure or by mechanical means that are directly or indirectly operable from outside the container. An embodiment of such mixing containers can be, for example, a storage container whose destructible dividing wall can be destroyed by mechanical means mounted on the applicator head and projecting into the container. The destruction takes place in such a case by screwing or placing the applicator head in the application position. Separate devices for destroying the partition are of course conceivable within the scope of the present invention.

In addition to a destructible partition, it may also be advantageous to provide a fixed partition with a one-way valve. Such a one-way valve could open, for example, by increasing the internal pressure in one of the chambers and thus transfer the component from one chamber to the other chamber. The increase in internal pressure can be achieved by the flexible design of the entire container and its compression by the user's hand. Also, additional pumping means are quite conceivable.

In addition to the design of a mixing device with a single container and different chambers separated by partitions, which serve as a reservoir, it may be advantageous to provide an empty mixing chamber in addition to the storage chambers before the start of the mixing process. In such an embodiment is located between the storage chambers and the mixing chamber, an element for transferring the components from the individual storage chambers in the mixing chamber. Such elements may, as already described above embodiments, destructible walls, but also one-way valves in the direction of the mixing chamber.

The above-described devices for mixing the components (B1), (B2) and optionally (B3) are of course only examples and do not limit the present application. Also, combinations of all of the mixing devices shown above are conceivable within the scope of the present invention.

In the context of a second preferred embodiment of the present invention, the agents (B1), (B2) and optionally (B3) used in the process are adjusted to medium viscosity. Application formulations which have a viscosity of from 0 to 15,000 mPas (measured at 22 ° C. in a Brookfield viscometer with spindle 4 and a speed of 4 rpm) after mixing components (B1), (B2) and optionally (B3) have proved to be particularly preferred. A viscosity of 500 to 5000 mPas, measured under the conditions mentioned, is particularly preferred according to the invention.

In the context of this embodiment, a dispensing system may be used which has at least two containers, each of these containers having at least one outlet opening. The outlet openings of the container or the container itself are arranged so that the outlet openings are insulated from each other.

Within the scope of a very particularly preferred embodiment, the hair color-changing agent delivery system according to the invention comprises exactly two containers, each of these containers having at least one outlet opening. The at least two containers can have all conceivable geometries for this purpose. Even if all conceivable container shapes are to be encompassed according to the invention, those which are of cylindrical design are preferred according to the invention. However, it is also conceivable that containers in the form of figures, such as figures and / or animals, are used. Furthermore, of course, from the combination of the container together and with the outlet openings may result in a different geometry.

The containers, in particular if they are cylindrical, may, for example, have a round, an oval, a square, a triangular, a rectangular or a trapezoidal base. According to the invention, containers are also to be included with such base surfaces, which result from the abovementioned bases by slight modification, such as a rounding of the corners.

According to the invention, all spatial arrangements of the containers should in principle be included. In one embodiment, the delivery system according to the invention may be designed in one piece. In a further embodiment, the hair color changing means dispensing system comprises two containers having a round or square base with rounded corners. The containers are preferably arranged side by side in the context of this embodiment. In the context of a further embodiment of the present invention, the containers have an oval or a rectangular base with rounded corners. In the context of this embodiment, it may be preferred if the containers are arranged such that the respective longer outer sides point towards one another or abut one another.

The preferably two containers may further be geometrically shaped so that they can be inserted against one another or into one another and thus mechanically or firmly releasably connected to each other. This can be achieved, for example, in that one container at least partially surrounds the other in its circumference and clamps it in a defined position. An exact positioning of the container to each other can be brought about, for example, that one of the container has on its surface locking nubs or locking lugs, which engage in corresponding recesses or recesses of the second container and prevent slipping of the container to each other. In a further embodiment, the containers can also be designed such that one of the containers has at least one groove on its surface and the other container has at least one spring engaging therein, so that the containers can be put together in this way. This embodiment with tongue and groove can advantageously be further developed in that the groove or the spring locking nubs and, accordingly, the spring or the groove corresponding thereto locking recesses. This latching means, so the locking knobs and - depressions, lock the connector of the two interconnected containers, so that they can only be separated from each other with increased force.

In a particularly preferred embodiment, the containers may be formed as two identically shaped halves in a substantially geometrically designed as a truncated cone output system, the truncated cone has on its narrow side two each side of the central axis arranged outlet openings. Each of the halves, so the container, thus has a convex outer side, which forms one half of the truncated cone surface, and a substantially planar Outside on, on which the halves abut each other. Each of the halves is formed so that the lower part merges smoothly over the entire height of the truncated cone in each offset from the central axis to the side outlet. The flat outer side of each half furthermore has at least one mechanical connecting element, such as, for example, tongue and groove, so that the halves can be put together and firmly connected to one another.

Furthermore, it may be preferred according to the invention if the at least two containers are made of plastic, plastic-containing multilayer films, metallized films or metal. The spatially isolated outlet openings are arranged according to the invention such that a mixing of the different means is excluded during storage. It may be preferred according to the invention, when the outlet openings are arranged such that the two or more agents intimately mix when applied to the hair. Moreover, according to the invention, it may also be preferable to design the outlet openings in such a way that backmixing following the application is avoided.

In the context of one embodiment, two separate applicator attachments can be installed on the at least two isolated outlet openings. Within the scope of this embodiment, it is inventively preferred if the at least two containers are fixedly or permanently detachably connected to each other and each of them carries an applicator attachment. It is conceivable according to the invention that two identical but also two different applicator attachments are used.

Within the scope of a further embodiment of the present invention, the at least two spatially isolated outlet openings can also carry a common applicator attachment with two separate openings. In the context of this embodiment, it is inventively preferred if the at least two containers are independent of each other and are held together by the common applicator attachment. However, according to the invention it may also be conceivable that the at least two containers are already linked together and the common applicator attachment produces an additional connection.

The outlet openings and their spatial environment according to the invention are designed such that they are suitable for applying the agent to the hair. Although, in principle, the present invention should not be subject to any restrictions, it has proven to be advantageous if the applicator attachment is designed in such a way that bristles, combs or rods surrounded by cotton wool are arranged around the exit opening. Furthermore, it may be preferred according to the invention if, after at least one outlet opening, a sponge is arranged. Likewise, it may be preferred according to the invention if a fiber composite reaches into at least one outlet opening. Furthermore, it may be preferred according to the invention if, after at least one outlet opening, a ball valve is arranged. Very particularly preferred according to the invention is a circular arrangement of bristles around the outlet opening.

Furthermore, it can be very particularly preferred according to the invention if each of the containers has a plurality of outlet openings arranged next to one another. In the context of this embodiment, it may be preferred according to the invention, if further in the region of the further outlet opening Application aids, such as bristles, a sponge, a comb, a cotton-wrapped rod, a ball valve or a fiber composite are arranged.

In a preferred embodiment, the applicator attachment can also be further developed in that the edge of an outlet opening has at least one protrusion protruding from the outlet opening in the direction of flow. This can be applied to the hair on the scalp when applying the means from the associated container on the hair, so that so that a minimum distance between the outlet opening and the scalp is ensured.

Furthermore, the applicator attachment can also be designed so that the edge of the outlet opening has two projections on two opposite sides, so that the outlet opening is arranged between the projections. Thus, such an applicator opening can be placed on the hair so that a strand of hair is separated from the other hairs by the two projections and the agent is applied exactly and exclusively to the detected strand. Finally, such an applicator tip can still be further developed in that the applicator has bristles or an application sponge between the projections in order to ensure a uniform application of the agent to be applied. In the case of the applicator openings thus provided with projections, it has proved to be advantageous if they are arranged spatially so that when touching the applicator over the hair all outlet openings touch the same strand of hair, so that a uniform mixing of the components is ensured on the hair. Also with regard to the delivery mechanism, the present invention should not be limited in any way. Thus, the application can be done for example by gravity, by capillary forces or by pressure application. As examples of the pressure output at this point the exercise of pressure on flexible walls, the internal pressure (aerosol application) and pumping mechanisms are mentioned.

In the context of a third preferred embodiment of the present invention, the agents (B1), (B2) and optionally (B3) used in the process are adjusted to high viscosity. Application formulations which have a viscosity of from 0 to 20,000 mPas (measured at 22 ° C. in a Brookfield viscometer with spindle 4 and a speed of 4 rpm) after mixing components (B1), (B2) and optionally (B3) have proved to be particularly preferred. A viscosity of 1,000 to 5,000 mPas, measured under the conditions mentioned, is particularly preferred according to the invention

In the context of this embodiment, it has proved to be advantageous to package the agents (B1), (B2) and optionally (B3) in tubes.

Laminated aluminum has proved to be particularly suitable as a tube material according to the invention. However, tubes made of plastic laminate (PE, PET, PP) or plastic coextrudates (PE, PET, PP) are also conceivable. As very particularly preferred according to the invention, tubes have proven to be made of aluminum laminate, which is optionally still protected with a lacquer or made of plastic laminate. Under aluminum laminate is understood according to the invention a coated with plastic aluminum layer.

It is conceivable according to the invention that the agents (B1), (B2) and optionally (B3) are each formulated separately in tubes. However, it may also be preferred according to the invention, two of the components to assemble together in a two-chamber tube. It is conceivable to assemble the means (B1) and (B2) as well as the means (B1) and (B3) as well as the means (B2) and (B3) together. Regardless of the distribution on the different tubes, the agents (B1), (B2) and optionally (B3) can be removed from the tubes immediately before use and transferred to a suitable mixing container. After thoroughly mixing the agents (B1), (B2) and, if appropriate, (B3), the resulting application mixture can then be applied to the hair parts to be treated with suitable aids, such as, for example, a brush or a comb.

However, it is also conceivable according to the invention if, from the respective tubes, the means (B1), (B2) and, if appropriate, (B3) are placed next to one another strand-like on a comb. Subsequently, the comb is pulled through the strands to be treated, wherein a thorough mixing of the various agents occurs and thus the coloration is initiated.

In the context of this embodiment, it may be preferred according to the invention to offer the customer a multipart kit consisting of two or optionally three tubes containing the agents (B1), (B2) and optionally (B3) and a suitable comb for application to the hair , Irrespective of the form of the preparation of the individual agents, positive effects, in particular an improved color lift, could be demonstrated if the agents used in the process according to the invention contain at least one alkyl phosphoric acid ester. Particularly preferred according to the invention is the use of the at least one alkylphosphoric acid ester in the agent (B2). Alkylphosphoric acid esters are understood according to the invention to be esters of phosphoric acid, where at least one alcohol is a derivative of a fatty alcohol. It may be preferred according to the invention if the agents of the present application contain at least one alkyl phosphoric acid ester of the formula (V)

wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkali metal cation or a radical of the formula (II)

- ^ C ₂ H ₄ θ] - ^ C ₃ H ₆ O-> R ⁴ m ⁿ (vi), where m and n are each independently an integer between 0 and 20 and R ⁴ is a saturated or unsaturated, branched or unbranched C _{_5-28} -alkyl radical, with the proviso that at least one of the radicals R ^1, R ² or R ³ is a radical of formula (VI). Furthermore, it has proved to be preferred if the agents according to the invention contain at least one alkylphosphoric acid ester of the formula (V) in which one of the radicals R ¹ , R ² or R ^{3 is} a hydrogen atom. Likewise, it has proved to be advantageous if at least one of the radicals R ¹ , R ² or R ^{3 is} a

Alkali metal cation, preferably a sodium cation, a potassium cation or a lithium cation. One

Sodium cation and a potassium cation are most preferred.

Furthermore, it has proved to be preferred if the agents according to the invention at least one

Alkylphosphoric acid esters of the formula (V) include, in which the radical R ⁴ represents a saturated or unsaturated, branched or unbranched C _{_12-22} alkyl group, particularly an unsaturated

Alkyl radical, most preferably for an oleyl radical.

Examples of suitable alkylphosphoric acid esters are the diesters of phosphoric acid and ethoxylated lauryl alcohol (INCI name: Dilaureth-4 Phosphate), which are available under the

Trade name Hostaphat KO ^® 200 sold by the company Clariant mixture of mono- and

Diesters of phosphoric acid and oleyl alcohol (INCI name: Oleyl Phosphate), the triesters

Phosphoric acid and ethoxylated cetearyl alcohol (INCI name: triceteareth-4 phosphates), the

Triesters of phosphoric acid and ethoxylated oleyl alcohol (INCI name: Trioleth-8 phosphates), the triesters of phosphoric acid and oleyl alcohol (INCI name: Trioleyl Phosphate) and the

Phosphorus esters with the INCI names Dicetyl Phosphate, Potassium Cetyl Phosphate, Sodium

Lauryl Phosphates.

Also preferred are alkyl phosphoric acid esters with partially or perfluorinated alkyl groups, for example those of the general formula (V), in which the radicals R ₁ , R ₂ and R ₃ independently of one another in addition to the meanings mentioned above for a group

R _f - (CH ₂ ) χ- (OCH ₂ CH ₂ ) _y - may be, wherein R _{f is} a perfluorinated alkyl radical having 4 to 20, preferably 6 to 18 C-atoms, x is a number from 0 to 4, preferably for 2 and y for a number of

0 to 20 stands.

Suitable fluorinated alkylphosphoric acid esters are the reaction products of the reaction of fluorinated, optionally ethoxylated alcohols with phosphoric acid, POCl ₃ , P ₄ O ₁₀ or

Polyphosphoric acid. For example, the diethanolammonium salt of

Perfluoroalkylethyl phosphate, which is sold under the trade name HOE S 2746 by the company Clariant.

In the context of the work underlying this invention, it has also been found to be advantageous if the means according to the invention at least two different

Alkylphosphorsäureester included.

Compositions according to the invention containing at least one dialkylphosphoric acid ester and / or at least one ethoxylated monoalkylphosphoric acid ester are particularly preferred according to the invention.

If the agents according to the invention contain two different alkylphosphoric acid esters, a

Ratio of ethoxylated Monoalkylphosphorsäureester to Dialkylphoshorsäureester from 1: 5 to 5: 1, in particular from 1: 1 to 2: 1, proved to be particularly suitable.

A very particularly preferred alkylphosphoric acid ester combination according to the invention is a

Combination of oleth-5 phosphate with dioleyl phosphate, as described, for example, under the

Trade name Crodafos ^® HCE sold by the company Croda. Furthermore, it could be demonstrated in the context of the work to the present application that the observed effects can be further enhanced if the inventive compositions additionally contain at least one optionally ethoxylated and / or propoxylated fatty alcohol. According to the invention, adducts of 0 to 30 moles of ethylene oxide, preferably 2 to 25 moles of ethylene oxide, in particular 10 to 20 moles of ethylene oxide, and / or 0 to 5 moles of propylene oxide are added to linear fatty alcohols containing 8 to 22 carbon atoms under optionally ethoxylated and / or propoxylated fatty alcohols. atoms.

Typical examples of fatty alcohols which are preferred according to the invention are caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petrolinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol , Behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, for example incurred in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Particular preference is given to technical fatty alcohols having 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel or tallow fatty alcohol. Very particular preference has been given to the addition of fatty alcohol ethoxylates, such as, for example, ceteareth-12, ceteareth-20 and ceteareth-30.

Furthermore, it has been found to be very particularly preferred according to the invention to use Alkylphosphorsäureesterkombination to which a fatty alcohol ethoxylate has already been added, as for example under the trade names Crodafos ^® CES (INCI name: Cetearyl Alcohol, Dicetyl Phosphate, Ceteth-10 Phosphate) and Crodafos ^® CS -20 (INCI name: Cetearyl Alcohol, Dicetyl Phosphate, Ceteth-20 Phosphate) are sold by the company Croda. The alkylphosphoric acid esters are used in the compositions according to the invention in an amount of preferably from 0.01 to 80% by weight, more preferably in an amount of from 0.1 to 10% by weight, based in each case on the weight of the mixture ready for use.

Furthermore, it has proved to be particularly advantageous according to the invention to achieve the optimum effects, in particular a uniform and intense color lift, when the agents used in the context of the method according to the invention contain a solubilizer. Particularly advantageous dissolving agents according to the invention are a) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products; b) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil and c) addition products of 20 to 30 moles of ethylene oxide and / or 20 to 20 moles of propylene oxide to linear fatty alcohols having 4 to 8 carbon atoms and to alkylphenols having 8 to 15 C atoms in the alkyl group.

Preferred solubilizers of group a) are, for example, ethoxylated sorbitan monoesters of lauric acid or oleic acid, as are known, for example, under the INCI names polysorbate-20 and polysorbate-80. Preferred solubilizers of group b) are, for example, addition products of about 40 moles of Eo hydrogenated castor oil, as for example under the INCI name PEG-40 Hydrogenated Castor

OiI are commercially available.

A preferred solubilizer of group c) is, for example, the adduct of about 26 moles

PPG and about 26MoI PEG of butyl alcohol, as for example under the INCI name PPG-26-

Buteth-26 is commercially available.

It has proved to be advantageous according to the invention if the agents used at least two

Solubilizers from different groups a) to c) included.

In addition, it has proved to be particularly preferred if the solubilizers are used in the middle (B1) containing at least one reactive carbonyl compound.

The solubilizers are contained in the compositions used according to the invention preferably in an amount of from 0.1 to 10% by weight, in particular from 0.5 to 6% by weight, based on the particular agent.

Furthermore, the agents used in the context of the method according to the invention can all be used in such

Preparations known active ingredients, additives and excipients. In many cases, the ready-to-use colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proven to be advantageous, the surfactants from anionic, zwitterionic or nonionic

Select surfactants.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with

10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular

Salts of saturated and in particular unsaturated C ₈ -C ₂₂ -carboxylic acids, such as oleic acid, stearic acid,

Isostearic acid and palmitic acid.

Zwitterionic surfactants are those surface-active compounds which have at least one quaternary ammonium group in the molecule and at least one

-COO ⁽⁾ or -SO ₃ ⁽⁾ group carry. Particularly suitable zwitterionic surfactants are the so-called

Betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammoniumglycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyldimethylammoniumglycinate, and 2-alkyl-3-ylcinate carboxymethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is that under the CTFA designation

Cocamidopropyl betaine known fatty acid amide derivative.

Ampholytic surfactants are surface-active compounds which, apart from a C ₈ -i ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -

COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids,

N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the

Alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate,

Kokosacylaminoethylaminopropionat and the C ₁₂ -i ₈ acylsarcosine. Nonionic surfactants contain as hydrophilic group z. Example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and Polyglykolethergruppe. Such compounds are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear

Fatty alcohols having 8 to 22 carbon atoms, fatty acids having 12 to 22 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C _{_12-22} fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide to

glycerin,

C ₈ _ ₂₂ alkyl mono- and oligoglycosides and ethoxylated analogs thereof,

Addition products of ethylene oxide to fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the kit according to the invention are, in particular, quaternary ammonium compounds. Preference is given to ammonium halides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium 80th).

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", such as the Methylhydroxyalkyldialkoyloxyalkylammonium- marketed under the trademark Stepantex ^® methosulfates.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercially available product Glucquat ^® 100 is, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs which are in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

The constituents of the cosmetic carrier are used to prepare the agent A, the agent (B1), the agent (B2) and optionally also the agent (B3) in amounts customary for this purpose; z. B. emulsifiers are used in concentrations of 0.5 to 30 wt .-% and thickening agents in concentrations of 0.1 to 25 wt .-% based on the respective agent. A third object of the present invention is the use of an agent (B) immediately before use

wherein

R ⁶ is a linear or cyclic (C ₁ to C ₆ ) alkyl group, a (C ₂ to C ₆ ) alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (C ₁ to C ₆ ) alkyl group, a (C ₁ to C ₆₎ hydroxyalkyl group, a (C ₂ -C ₆₎ -polyhydroxyalkyl group, a (C ₁ to C ₆₎ alkoxy alkyl (C-ι to C _6), a group R ' R ^{M is} N- (CH ₂ ) _m -, in which R ¹ and R ¹¹ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -hydroxyalkyl group or an aryl- ( d to C ₆ ) -alkyl group, where R ¹ and R ¹¹ together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,

R ⁷ is a (C ₁ to C ₆ ) -alkyl group, in particular a methyl group, X ^" is a physiologically acceptable anion, the cycle of the formula (CH-1) represents all ring structures which additionally contain further heteroatoms such as nitrogen, oxygen or may contain sulfur and may further carry fused ring structures, all of which ring structures may carry additional substituents,

Het is an optionally substituted heteroaromatic, and X ¹ stands for a direct bond or a carbonyl group, obtained by mixing, for coloring the freshly grown hair roots of hair, which were previously treated with an oxidative dye.

A fourth object of the present invention is to use an agent (B) immediately before use

wherein

R ⁷ is a (C ₁ to C ₆ ) alkyl group, in particular a methyl group, X ^' is a physiologically acceptable anion, the cycle of the formula (CH-1) represents all ring structures which additionally contain further heteroatoms such as nitrogen, oxygen or may contain sulfur and may further carry fused ring structures, all of which ring structures may carry additional substituents,

Het is an optionally substituted heteroaromatic, and X ¹ is a direct bond or a carbonyl group, obtained by mixing, for dyeing graying Asian hair.

With regard to the uses according to the invention, the mutatis mutandis stated for the methods according to the invention apply. A fifth subject of the present invention is a multi-part staining kit for carrying out the method according to the invention, comprising an agent (B1) which, in a cosmetic carrier, is 4-hydroxy

2-methoxybenzaldehyde and at least one further reactive carbonyl compound selected from 2-

Chloro-3,4-dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1, 5-dimethyl-3-oxo-2-phenyl-1H pyrazole-4-carboxaldehyde and 2,4-

Dimethoxy-benzaldehyde, and an agent (B2) containing in a cosmetic vehicle 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide 1, 2-dihydro-1, Contains 3,4,6-tetramethyl-2-oxo-pyrimidiniums and / or 2- (cyanomethyl) benzimidazole.

In a preferred embodiment of this article of the present invention, the multi-part staining kit additionally contains an agent (A1) containing at least one dye precursor and an agent (A2) containing at least one oxidizing agent.

Also with respect to this subject of the present invention, this applies to the first two

Objects said mutatis mutandis.

The following examples are intended to illustrate the subject matter of the present invention without, however, limiting it in any way.

Be it pi le

Unless otherwise indicated, the amounts used in the examples are in percent by weight.

1 Preparation of the preparations

1.1 Production of means (BD

The following agents (B1) containing a reactive carbonyl compound were prepared:

1.1.1 Preparation of the Cremeformulierunqen B1a to B1ae and B1ai to B1ap Lorol ^®, Eumulgin ^® B1 or B2 Eumulgin ^®, ^® Finsolv TN, Elfacos ST9 ^®, Emery ^® 1780 Prisorine ISAC ^® 3505 and / or Hydrenol D ^® were together at 80 ⁰ C melted. In this melt required for the individual formulations, proportions of the components Texapon ^® NSO, Plantacare ^® 1200 were Plantacare ^® 2000, Dehyton ^® K, Cordafos ^® CES, Protelan ^® MST 35, Akypo Soft ^® 45NV, cetearyl glucoside, Crodasinic ^® C, Cordasinic ^® L, Lameform ^® TGI, Tego betaine ^® BS, Amisoft CT12 ^®, ^® AquaCat CG518, Incroquat ^® SDQ25, Crodafos ^® G26a and / or Lamesoft ^® PO incorporated 65th To this mixture, the stated proportions of the carbonyl compounds 4-hydroxy-2-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1, 5-dimethyl-3-oxo 2-phenyl-1H-pyrazole-4-carboxaldehyde, 2,4-dimethoxybenzaldehyde, 2-chloro-3,4- dihydroxybenzaldehyde and / or 2-bromo-3,4-dihydroxybenzaldehyde, dissolved in 80 to 90 ⁰ C hot water, added with stirring. While the mixture slowly cooled to room temperature with stirring, the remaining recipe ingredients were added. The swelling agent Carbomer ^® 134, Antil ^® 141, Amaze XT ^® and / or Cosmedia Ultragel ^® 300 were pre-swollen in water and added depending on the particular formulation. Subsequently, the pH stated for the respective formulation was adjusted by addition of tartaric acid or monoethanolamine. Finally, it was filled up with warm water to 100g. 1.1.2 Preparation of gel formulations B1af to B1ai

4-hydroxy-2-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1, 5-dimethyl-3-oxo-2-phenyl-1H-pyrazole 4-carboxaldehyde, 2,4-dimethoxy-benzaldehyde, 2-chloro-3,4-dihydroxybenzaldehyde and / or 2-bromo-3,4-dihydroxybenzaldehyde were dissolved in 70 g of 80 to 90 ⁰ C hot water with stirring, then were necessary for the individual formulations, proportions of the components Protelan ^® MST 35, Lamesoft ^® PO 65, Tego betaine ^® BS, Amisoft ^® and / or AquaCat CG518 ^® added and filled up with warm water 100g. During the cooling, the previously pre-swollen agent Carbomer ^® 134 and / or Antil ^® 141 was added with continued stirring. The source process was awaited. Subsequently, the remaining recipe ingredients were added. Finally, by adding phosphoric acid or monoethanolamine, the pH stated for the particular formulation was established and made up to 100 g with cold water.

1.2 Production of funds (B2)

The following preparations (B2) containing a C, H-acidic compound were prepared:

1.2.1 Preparation of Cream Formulations B2a to B2d, B2I and B2m

Lorol ^®, Eumulgin ^® B1 and B2 Eumulgin ^® and / or Hydrenol D ^® were melted together at 80 ⁰ C. Into this melt, the necessary for the individual formulations amounts of the components Texapon ^® NSO, Plantacare ^® 2000, Dehyton ^® K and / or Crodafos ^® CES were incorporated.

1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfonate and / or 2- (Cyanomethyl) benzimidazole dissolved in 80 to

90 ⁰ C hot water, were added with stirring. After cooling, the remaining recipe ingredients were added. Subsequently, the pH stated for the particular formulation was adjusted by addition of tartaric acid or monoethanolamine. Finally, it was filled up with warm water to 100g.

1.2.2 Preparation of gel formulations B2e to B2k

1-Allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfonate and / or 2- (Cyanomethyl) benzimidazole were dissolved in 70g

80 to 90 ° C hot water was dissolved with stirring, then the necessary for the individual formulations proportions of the components Texapon ^® NSO, Dehyton ^® K, Plantacare ^® 2000 and / or Crodafos ^® CES were added and made up to 95g with warm water. Then Synthalen® ^® K and / or Carbopol Ultrez ^® 10 were slowly added while continuing to stir. The source process was awaited. Finally, the remaining recipe components were added and adjusted by the addition of tartaric acid or monoethanolamine specified for the respective formulation pH. With warm water was made up to 100g. 1.3 Preparation of the agents (B3) The following agents (B3) containing an alkalizing agent were prepared:

1.4 Preparation of the means A2

The following oxidizer preparation (A2) was prepared:

1.5 Production of funds A1

The following coloring cream (A1) was prepared:

1.6 List of used commercial products

The commercial products used in the examples are defined as follows:

Abil ^® B 8843 polyether-polysiloxane (INCI name: PEG-14

Dimethicone) (Evonik Degussa)

Abil ^® EM 90 modified polyether-polysiloxane (INCI name: Cetyl PEG / PPG-10/1 dimethicone) (Evonik Deguss)

Adinol CT 30 ^® INCI name: Aqua (and) Sodium Methyl Cocoyl Taurate) (Croda) Akypo Soft 45 NV ^® lauryl alcohol 4.5 EO acid sodium salt (at least 21%.

Active substance content; INCI name: sodium laureth-6 carboxylates) (Chem-Y)

Amaze ^® XT Dehydrated xanthan gum (INCI name: Dehydroxanthan Gum) (National Starch) Amisoft ^® CT12 Triethanolamine N-cocoyl-L-glutamate (about 28.32% active substance content; INCI name: TEA-cocoyl glutamate) (Ajinomoto)

Antaron V 220 ^® INCI name: VP / Eicosene copolymer (ISP) Antil ^® 141 Polyoxyethylenpropylenglykoldioleat (ca. 40% active substance content; INCI name: Propylene Glycol, PEG-55 Propylene Glycol Oleate) (Goldschmidt)

AquaCat CG518 ^® guar (about 9.5 to 10.5% solids; INCI name: Guar Hydroxypropyltrimonium Chloride) (Hercules)

Carbomer '134 INCI name: Carbomer (Evonik Goldschmidt)

Carbopol ^® 675 polyacrylic acid powder (INCI name: Carbomer) (Lubrizol)

Carbopol ^® Ultrez 10 polyacrylate (INCI name: Carbomer) (Lubrizol)

(Min. 92Gew.-% solids; INCI name: Polyquaternium-37) Cosmedia Ultragel ^® 300 2- (trimethylammonio) ethyl methacrylate homopolymer (Cognis)

Cremopho r ^® RH40 hydrogenated castor oil with 40-45 EO units (INCI name: PEG-40 Hydrogenated Castor Oil) (BASF)

Grill® 1 INCI name: Sorbitan Laurate (Croda)

Crillet ^® 1 INCI name: Polysorbate 20 (Croda)

Crillet ^® 2 INCI name: Polysorbate 40 (Croda)

Crodafos ^® CES INCI name: Cetearyl Alcohol, Dicetyl Phosphate, Ceteth-10 Phosphate (Croda)

Crodafos ^® G26A ethoxylated glyceryl phosphate (INCI name: Glycereth-26 Phosphate) (Croda)

Crodamol ^® ¹ BS distilled stearic acid butyl ester (INCI name: Butyl Stearate) (Croda)

Crodamol ^® ¹ EO INCI name: Ethyl Oleate (Croda)

Crodasinic ^® c INCI name: Cocoyl sarcosine (Croda)

Crodasinic ® i INCI name: Lauroyl Sarcosine (Croda)

Croquat ^® M approx. 40% active substance content; INCI name: Aqua (and) Lauryldimonium Hydroxypropyl Hydrolyzed Collagen (Croda)

Crosilk Liquid approx. 27 to 31% solids; (INCI name: Aqua, SiIk Amino Acids) (Croda)

Crotein ^® MCAA about 15% active substance content; (INCI name: Aqua (and) Collagen Amino Acids) (Croda)

Dehyton ^® CN, N-dimethyl-N- (C8-18-cocamidopropyl) ammoniumaceto betaine (30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

Dow Corning 245 Fluid Dimethylsiloxane pentamer (95% purity, INCI name:

Cyclomethicones) (Dow Corning) Elfacos ^® ST 9 100% active ingredient content; INCI name: PEG-45 / dodecyl glycol copolymer) (Akzo Nobel)

Elfacos ^® ST 37 INCI name: PEG-22 / Dodecyl Glycol Copolymer (Akzo) Emery ^® 1780 INCI name: Lanolin Alcohol (Cognis) Emulgade ^® F mixture of cetostearyl alcohol, castor oil with about 40 EO units and the sodium salt of Cetylstearylsulfate (INCI name: Cetearyl Alcohol, PEG-40 Castor OiI, Sodium Cetearyl Sulfate) (Cognis)

Eumulgin ^® B 1 cetylstearyl alcohol with about 12 EO units (INCI name: Ceteareth- 12) (Cognis) Eumulgin B2 ^® cetylstearyl alcohol with about 20 EO units (INCI name: Ceteareth- 20) (Cognis) Finsolv ^® TN C ₁₂ -i ₅ -alkyl esters of benzoic acid (INCI name: C12-15 alkyl benzoates) (Innospec)

Hydrenol D ^® C _{_6-18} fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis) Hydrolactin ^® 2500 hydrolysed milk protein (approximately 77-90% protein; INCI name: Hydrolyzed Milk Protein) (Croda) lncroquat ^® 26 Minkamidopropyldimethylhydroxyethylammoniumchlorid ( INCI name: (quaternium-26) Croda) lncroquat ^® SDQ 25 about 25% active substance content; (INCI name: Stearalkonium Chloride) (Croda) Lameform ^® TGI approx. 100% active ingredient content; INCI name: Polyglyceryl-3 Diisostearate (Cognis) Lamesoft PO65 ^® alkylpolyglucoside monoglyceride mixture (about 65-70% solids; INCI name: Coco-Glucoside, Glyceryl Oleate, Aqua (Water)) (Cognis)

Lorol® ^®, tech. C _{_2-18} fatty alcohol (INCI name: Coconut alcohol) (Cognis) myritol ^® PC INCI name: propylene glycol dicaprylate / dicaprate (Cognis) Plantacare® ^® 1200 C ₂ - ₁₆ fatty alcohol-1.4-glucoside (about 50- 53% active ingredient content, INCI name: Lauryl Glucoside, Aqua (Water)) (Cognis)

Plantacare ^® 2000 Cβ- ₁₆ alkyl glucoside (approximately 51-55% active substance content in water; INCI name: Decyl Glucoside, Aqua (Water)) (Cognis) Polymer JR ^® 400 quaternized hydroxyethyl cellulose (INCI name: Polyquaternium-10) (Amerchol ) Polymer ^® W 37194 about 20% by weight of active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen)

Prisorine 3505 isostearic acid ISAC ^® (INCI name: Isostearic Acid) (Croda) Prodew ^® 500 raw material mixture; (INCI names: 15.0 wt% sodium PCA, 12.0 wt% sodium lactate, 8.0 wt% arginine, 5.2 wt% aspartic acid, 4.3 wt% PCA, 1.3 wt% glycine, 1.2% by weight of alanines, 0.8% by weight of serines, 0.6% by weight of valines, 0.4% by weight of proline, 0.4% by weight of threonines, 0.4% by weight of isoleucines, 0, 2% by weight of histidine, 0.2% by weight of phenylalanine, balance Water) (Ajinomoto)

ProtelarT MST 35 mixture of sodium N-Myristoylsarcosinate and sodium N-methyl-N- cocoyltaurate (40 wt .-% of active substance, Zschimmer & Schwartz) Rewoderm LI ^® 63 ethoxylated coconut mono / diglycerides (about 100% active substance; INCI name: PEG -30 Glyceryl Cociate) (Evonik Degussa) Softcat ^® SX quaternized hydroxyethyl cellulose (about 91% purity; INCI name: Polyquaternium-67) (Dow) ^® Solubilisant LRI about 9.5 to 10,5Gew .-% water content; INCI name: PPG-26-Buteth- 26, PEG-40 Hydrogenated Castor OiI (Sensient Cosmetic Technologies) Synthalen ^® K polyacrylic acid (ca. 89% active substance content; INCI name: Carbomer) (3V Sigma) Tego Betaine HS (about 29-32% active ingredient in 63-67% water with 4.5-5.3% sodium chloride, INCI name: Cocamidopropyl Betaine, Glyceryl Laurate) (Evonik Degussa)

Texapon ^® NSO lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: sodium laureth sulfate) (Cognis) Turpinal ^® SL 1-hydroxyethane-1, 1-diphosphonic acid (about 58 - 61% active ingredient content, INCI name : Etidronic Acid, Aqua (water)) (Solutia) Tween ^® 20 ethoxylated sorbitan monolaurate (about 2,5-3Gew .-% water content; INCI name: Polysorbate-20) (Croda) Tween ^® 80 sorbitan monooleate with about 20 EO Units (maximum 3Gew% water, INCI name: Polysorbate-80) (Croda)

2 coloration

2.1 Oxidative staining

Immediately prior to use, 60 ml of the colorant (A1) were mixed with 60 ml of the oxidizing agent preparation (B1) and applied to the hair to be dyed. After a contact time of 30 minutes at 32 ° C, the mixture with water was thoroughly removed from the hair, this cleaned with a commercial shampoo and then dried with a hair dryer.

2.2 Post-treatment

To prepare the ready-to-use dye mixture, the agents (B1) and (B2) were mixed in a weight ratio of 1: 1. Immediately afterwards, so much of the preparation (B3) was added until the pH of the mixture indicated in the following table was reached. The ready-to-use colorant obtained was applied in a ratio of 2 g of color mixture to 1 g of hair (Kerling natural white and / or grayish Asian hair). After a contact time of 30 minutes at 32 ° C, the strands were rinsed with lukewarm water and then dried in a stream of warm air (30 to 40 ⁰ C). The stains were visually assessed under a daylight lamp.

With the dye precursors according to the invention intensive and brilliant dyeings were achieved on European hair.

The more difficult to color white European and especially white Asian hair was dyed intensively, so that with these combinations a good gray coverage was obtained.

In addition, it has been found that the aftertreatment with the agents (B) according to the invention enabled the freshly grown hair roots to be intensively and cover-dyed without the disadvantages of frequent oxidative dyeing.

Claims

Patent claims

1. A process for the permanent dyeing of gray hair, characterized in that in a first step, the entire hair is treated with an oxidative dye (A) and the subsequently regrown gray hairlines are treated in one or more further steps with an agent (B), immediately before the application

wherein

R ⁶ is a linear or cyclic (Ci to _C6) alkyl group, a (C ₂ -C ₆₎ - alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl (Ci to _C6) alkyl group, a (Ci -C ₆₎ - hydroxyalkyl group, a (C ₂ -C ₆₎ -polyhydroxyalkyl group, a (Ci-C ₆₎ - AIkOXy- (C ₁ to C ₆₎ alkyl group, a group

R'R ^M N- (CH ₂ ) _m -, wherein R ¹ and R "independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) hydroxyalkyl group or an aryl - (C ¹ -C ₆ ) -alkyl group, wherein R ¹ and R ^{11 may} together with the nitrogen atom form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,

2. The method according to claim 1, characterized in that the time interval between the oxidative dyeing and the treatment of the regrown hair roots is at least 5 days.

3. The method according to any one of claims 1 or 2, characterized in that the agent (A) immediately before use of a means (A1) containing at least one oxidation dye precursor, and a means (A2) containing at least one oxidizing agent is prepared ,

4. The method according to any one of claims 1 or 2, characterized in that the reactive carbonyl compound of the agent (B1) is selected from 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro- 1, 5-dimethyl-3-oxo-2-phenyl-1H-pyrazole-4-carboxaldehyde, 2,4-dimethoxy-benzaldehyde, 2-chloro-3,4-dihydroxybenzaldehyde and 2-bromo-3,4-dihydroxybenzaldehyde.

5. The method according to any one of claims 1 to 3, characterized in that the C, H-acidic compound of the agent (B2) is selected from 1-allyl-1, 2-dihydro-3,4,6-trimethyl-2 oxo-pyrimidinium, 1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidiniums and 2- (cyanomethyl) - benzimidazole or their physiologically acceptable salts.

6. A process for dyeing graying Asian hair, characterized in that the graying hair parts are treated with an agent (B), the immediately before use of at least one agent (B1), which in a cosmetic carrier 4-hydroxy-2-methoxybenzaldehyd and at least one further reactive carbonyl compound selected from 2-chloro-3,4-dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1, 5-dimethyl-3 -oxo-2-phenyl-1H-pyrazole-4-carboxaldehyde and 2,4-dimethoxy-benzaldehyde, and at least one agent (B2) containing in a cosmetic carrier a physiologically acceptable salt of 1-allyl-1,2 dihydro-3,4,6-trimethyl-2-oxo-pyrimidiniums and optionally 2- (cyanomethyl) benzimidazole, is obtained by mixing.

7. The method according to any one of claims 1 to 6, characterized in that the means (B1) has a pH of 2 to 5.

8. The method according to any one of claims 1 to 7, characterized in that the means (B2) has a pH of 0.5 to 2.5.

9. The method according to any one of claims 1 to 8, characterized in that the agent (B) immediately before use, a further component (B3) is added, which contains at least one alkalizing agent in a cosmetically acceptable carrier.

10. The method according to any one of claims 1 to 9, characterized in that the ready-for-use agent (B) has a pH of 7 to 10.

11. The method according to any one of claims 9 or 10, characterized in that the means (B3) contains as alkalizing monoethanolamine, ammonia, sodium hydroxide, potassium hydroxide and / or arginine.

12. Use of an agent (B) according to any one of claims 1 to 11 for coloring the freshly grown hair roots of hair, which were previously treated with an oxidative dye.

13. Use of an agent (B) according to any one of claims 1 to 11 for the coloring of graying Asian hair.

14. Multi-part staining kit for carrying out the method according to any one of claims 1 to 11, comprising an agent (B1), in a cosmetic carrier 4-hydroxy-2-methoxybenzaldehyde and at least one further reactive carbonyl compound selected from 2-chloro-3,4 dihydroxybenzaldehyde, 2-bromo-3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 2,3-dihydro-1, 5-dimethyl-3-oxo-2-phenyl-1H-pyrazole-4 carboxaldehyde and 2,4-dimethoxy-benzaldehyde, and an agent (B2), which in a cosmetic carrier 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium bromide, 1 , 2-Dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidiniums and / or 2- (cyanomethyl) benzimidazole.

15. Multi-part staining kit according to claim 14, additionally comprising an agent (A1) containing at least one dye precursor, and an agent (A2) containing at least one oxidizing agent.