WO2007090527A2

WO2007090527A2 - Oxidative hair treating agent having a ginseng extract

Info

Publication number: WO2007090527A2
Application number: PCT/EP2007/000662
Authority: WO
Inventors: Anja Reichert; Konstantin Goutsis
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2006-02-07
Filing date: 2007-01-26
Publication date: 2007-08-16
Also published as: WO2007090527A3; EP1986592A2; DE102006005767A1

Abstract

The invention relates to oxidation-stable compositions which contain, in addition to at least one oxidation agent, a ginseng extract in a cosmetic support. Said compositions are used to reduce hair damage, skin-ageing and skin irritations induced by the oxidation agent, in addition to improving the elasticity of the skin. The effects of the extracts can be obtained during the oxidative hair treatment in the presence of an oxidation agent.

Description

"Oxidative Hair Treatment with Ginseng Extract"

The invention relates to compositions which additionally comprise ginseng extract in a cosmetic carrier in addition to at least one oxidizing agent, a hair treatment method with this composition, and the use of these agents for reducing the hair damage caused by the oxidizing agent, skin aging, skin irritation and the decrease in skin elasticity.

Oxidative agents find a wide range of applications in hair cosmetics. In addition to the induced by oxidation color change of the hair by Oxidationshaarfärbemittel or hair bleach oxidizing agent-containing cosmetics are used in the context of the application form of a perm as a shape fixation.

For the dyeing of keratin fibers, in particular of hair, furs and skins, the so-called oxidation dyes play a preferential role because of their intense colors and good fastness properties. Such hair dyes contain oxidation dye precursors in a cosmetic carrier. The oxidation dye precursors used are developer substances and coupler substances. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components.

A particular developer substance can also form very different color shades by combination with different couplers. Nevertheless, it often fails to come with the help of a single developer substance to a variety of natural shades. In practice, therefore, a combination of different developer required components and coupler components to obtain a single, natural-looking color.

Good oxidation dye precursors must fulfill the following prerequisites in the first place: In the case of the oxidative coupling, they must form the desired color shades with sufficient intensity and authenticity. When used in hair dyes they should already have a good absorption on human hair at temperatures below 40 ⁰ C, with no significant differences may exist between strained and freshly regrown hair (leveling ability). They should be resistant to light, heat and the influence of hair shampoos and chemical reducing agents, eg. B. against perming fluids. After all, they should not stain the scalp too much and above all, they should be harmless from a toxicological and dermatological point of view.

In addition to an oxidizing agent, hair bleaches usually contain bleach boosters that support the oxidative decolorization of the natural pigment melanin and thus improve the lightening result.

Disulfide bridges of the hair keratin are cleaved by the reductive acting wave agent of a permanent wave treatment. Oxidizing agent-containing fixative, make it possible to re-tie these disulfide bridges elsewhere after hair shaping and fix in this way the shape of the new hairstyle. '

Unfortunately, the oxidative cosmetics do not affect exclusively the change in the target parameters aimed at within the respective application. Sometimes more, sometimes less, other cosmetic parameters can be adversely affected. On the one hand, these further parameters are assigned to the target substrate itself (here: the keratin-containing fiber), on the other hand, parameters of all other substrates are affected whose contact with the oxidative cosmetic can not be avoided in the course of use (here: the skin). The possible damage to the hair structure, as well as a deterioration of the conditioning of the hair on the one hand and the irritation of the hair Skin and a loss of elasticity of the skin on the other hand are undesirable possible side effects.

Therefore, more and more frequently combination preparations are offered, which in addition to the desired oxidative effect suppress or reduce the unwanted side effects already during the application. In the provision of such preparations, there is the difficulty that the active ingredients must be incorporated stably into a cosmetic carrier and the active principle should be inert to oxidizing agents. A success of known active ingredients in combination with oxidative systems is difficult predictable bar.

Cosmetic carriers in gel form are perceived by the consumer as a particularly aesthetic form of offering. The term "gel" is further characterized in "Faraday discussions of the Chemical Society, No. 57, 1974 (Gels and Gelling Processes), PJ. Flory, pages 7-18". Accordingly, gels are divided into 4 subgroups:

1. gels with lamellar ordering structures including gel mesophases, e.g. Surfactant gels, in particular soap gels.

2. Gels composed of polymeric, three-dimensional, covalently bonded networks that are insoluble in the solvent without destroying the covalent bonds.

3. Gels of polymeric networks with local regulatory structures held together by physical forces, e.g. Gelatin, homo- and copolymers of acrylic and methacrylic acid, alginates, carrageenan.

4. Gels formed from finely divided components, such as precipitates, which generally have a large geometric anisotropy, for example, V ₂ O ₅ -GeIe or gels that form by aggregation of proteins. Gels in the sense of the invention described below are those which fall under item 1 and item 3 of the above list. As "gel" within the meaning of the present invention, transparent gels are also to be understood as described, for example, in US Pat. Nos. 3,101,300 and 3,101,301. These transparent gels are referred to as microemulsion gels. A general definition of microemulsion gels is given in "Happi: Household Pers., Prod. Ind. 30 (1993), No. 2, pp. 58-64".

The gel should not necessarily but preferably be flowable and be characterized by a high intrinsic viscosity, i.e., these compositions appear relatively highly viscous under the influence of low shear forces, such as intrinsic weight, but may be applied using higher shear forces, e.g. stir very easily when stirred. It is particularly important that after mixing with an oxidative hair color causing aqueous oxidizing agent composition, the intrinsic viscosity of the dyeing is maintained and the ready dyeing can be easily distributed on the hair, but does not run off the hair and the scalp or the face stains.

Compared to cosmetics in cream form, gel-form cosmetics offer some performance advantages. Thus, the production of creams (i.a., C7W emulsions) is generally more problematic and expensive; Creams often thicken. The gels preferably used as cosmetic carriers within the scope of the invention, however, retain their once-adjusted viscosity over a relatively long period of time and are easier to distribute on the head hair.

Oxidative compositions containing at least one oxidizer and ginseng extract in a cosmetic carrier reduce the above-mentioned adverse side effects of conventional oxidative cosmetics. The abovementioned combination of active ingredients can be incorporated particularly well into gelatinous cosmetic carriers and is particularly effective and easy to use.

Object of the present invention is therefore to reduce the above-mentioned side effects of oxidative cosmetics already during their use and a preferably to provide stable and effective application form of the active ingredients found as a solution to this problem.

It has now surprisingly been found that ginseng extract achieves the task in an outstanding degree.

A first object of the invention is a cosmetic agent which contains in a cosmetic carrier at least one oxidizing agent and ginseng extract.

According to the invention, cosmetic creams, emulsions, gels or surfactant-containing foaming solutions, for example shampoos, foam aerosols or other preparations which are particularly suitable for use on the hair, are particularly suitable as cosmetic carriers. But it is also conceivable to integrate the ingredients in a powdered or tablet-like formulation, which is dissolved in water before use. A gelatinous cosmetic carrier is particularly preferred. The cosmetic carriers may in particular be aqueous or aqueous-alcoholic.

An aqueous cosmetic carrier contains at least 50% by weight of water.

For the purposes of the present invention, aqueous-alcoholic cosmetic carriers are to be understood as meaning aqueous solutions containing from 0.1 to 70% by weight of a C ₁ -C ₄ -alkyl 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.

The oxidizing agents according to the invention are different from atmospheric oxygen and have such an oxidation potential that makes it possible to link disulphide bridges within or between the proteins of the hair keratin, oxidatively lighten the natural color pigment melanin and / or to oxidize a developer-type oxidation dye precursor.

The oxidizing agent used is in particular hydrogen peroxide and / or at least one addition product thereof, in particular to inorganic or organic compounds, such as, for example, sodium perborate, sodium percarbonate, Magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide in question.

According to the invention, the cosmetic composition can also be applied to the hair together with a catalyst which activates the oxidation of the substrate, such as, for example, oxidation dye precursors. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of a color can be accelerated and the color shade can be specifically influenced.

Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention, which generate in situ small amounts of hydrogen peroxide with the aid of atmospheric oxygen and in this way biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g.

Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose,

Glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts,

Alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and their salts,

- Tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and amino acids. The oxidizing agent is preferably in an amount of 1, 0 to 15 wt .-%, in particular from 3.0 to 12.0 wt .-%, each based on the weight of the ready-to-use agent, in the inventive composition.

According to the invention, ginseng is understood to mean the root of a plant from the family Araliaceae of the genus Ginseng. These plants include, among others, the Araliacee Panax ginseng C.A. Meyer, the so-called real ginseng, as well as Panax japonicus and Panax pseudoginseng.

It is preferred according to the invention that the ginseng extract contains at least one sapogenin. These are preferably sapogenins which are selected from at least one compound of the formula (I) and / or at least one glycosidic derivative thereof

wherein

R ¹ and R ² independently represent a hydrogen atom or a hydroxy group.

When the compound of formula (I) is present as a glycosidic derivative, the carbohydrate moiety will bind to one of the hydroxy groups of the molecule of formula (I). The glycosidic derivatives of the compounds of the formula (I) are preferably derived from glucopyranose, arabinopyranose, arabinofuranose, xylofuranose, xylopyranose and / or rhamnopyranose. In each case L- or D-stereomers are possible. The glycosidic derivatives of the compounds of the formula (I) are particularly preferably derived from D-glucopyranose, L-arabinopyranose, L-arabinofuranose, D-xylofuranose, D-xylopyranose and / or L-rhamnopyranose. Particularly preferred compounds of the formula (I) or their glycosidic derivatives are betulafolientriol, protopanaxadiol and / or protopanaxatriol.

As usable extracts of ginseng are for example the commercial products Extrapone ^® ginseng (INCI name: Aqua (Water), ethoxydiglycol, Propylene Glycol, Butylene Glycol, Panax Ginseng Root Extract, Lactic Acid, glucose) from the company Symrise or Nova Plant ^® ginseng (INCI Name: Aqua (Water), Butylene Glycol, Panax Ginseng Root Extract) from Crodarom.

A particularly preferred ginseng extract is sold by Cosmetochem under the trade name Herbasol® extract ginseng (INCI name: isopropyl myristate, Panax ginseng root extract) as an oil-soluble ginseng extract.

Particular preference is given to compositions according to the invention in which at least one protein or protein hydrolyzate, selected from at least one member of the group formed from pea protein, soy protein, almond protein, acacia protein, collagen and keratin and their hydrolyzates, is contained.

It is inventively preferred if the agent according to the invention additionally contains at least one color-changing component.

The color-changing component is again preferably selected

(A) from at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or

(b) from oxo dye precursors and / or

(c) from at least one direct dye and / or

(D) from at least one precursor of natural dyes and / or

(e) at least one bleach booster. The developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-amino pyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its Derivatives used.

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. Particular preference is given to p-phenylenediamine derivatives of the formula (Ent1)

in which

G ¹ is a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄

Monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) -

AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -

Alkyl radical containing a nitrogen-containing group, a phenyl or a 4 ¹ -

Aminophenylrest is substituted;

G ² is a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

AIkOXy- (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or

Fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a

C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to

C ₄ -acetylaminoalkoxy, C ₁ - to C ₄ -mesylaminoalkoxy or C ₁ - to C ₄ -carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or, when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group , Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C 1 -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ to C ₄ hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (Ent1) are in particular the amino groups, C ₁ to C ₄ monoalkylamino groups, C ₁ to C ₄ dialkylamino groups, C ₁ to C ₄ trialkylammonium groups, C ₁ to C ₄ monohydroxyalkylamino groups, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (Ent1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2- methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro -p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N (Ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acet ylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particularly preferred according to the invention p-phenylenediamine derivatives of formula (Ent1) are p-phenylenediamine, p-toluenediamine, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis- (β-hydroxyethyl) -p-phenylenediamine.

It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

Among the binuclear developer components that can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (Ent2) and their physiologically tolerated salts:

in which:

Z ¹ and Z ² independently of one another, are a hydroxyl or NH ₂ radical, which, by a C ₁ is optionally substituted by a Ci to _C4 alkyl group - is / or substituted hydroxyalkyl radical, and by a bridge Y, or - to C ₄ which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, Sulfur or nitrogen atoms may be interrupted or terminated and may be optionally substituted by one or more hydroxyl or C ₁ - to C ₈ -Al koxyreste, or a direct bond, G ⁵ and G ⁶ are independently a hydrogen or halogen atom , a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y, G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that

- The compounds of formula (Ent2) contain only one bridge Y per molecule and

- The compounds of formula (Ent2) contain at least one amino group which carries at least one hydrogen atom.

The substituents used in formula (Ent2) are inventively defined analogous to the above statements.

Preferred binuclear developer components of the formula (Ent2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N- ^l bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4 ^l -aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N ₁ N ¹ - diethyl-N, N ' bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p- phenylenediamine and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4, 7, 10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (Ent 2) are N, N'-bis (β-hydroxyethyl) -N, N ¹ -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 and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4, 7, 10-tetraoxadecane or one of their physiologically acceptable salts.

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. Particular preference is given to p-aminophenol derivatives of the formula (Ent3)

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a

(C ₁ - to C ₄ ^ alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a

Hydroxy (C _r to C ₄ ) -alkylamino, a C ₁ - to C ₄ -hydroxyalkoxy, a C ₁ - to C ₄ -hydroxyalkyl (C _r to C ₄ ) aminoalkyl or a (di-C ₁ - bis C ₄ alkylamino) -

(C ₁ - to C ₄ ) -alkyl radical, and

G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a

C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy (C _r to C ₄₎ alkyl group, a C ₁ - to C ₄ -aminoalkyl or a C ₁ to C ₄ cyanoalkyl radical,

G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (Ent3) are defined according to the invention analogously to the above statements.

Preferred p-aminophenols of the formula (Ent3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino 2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically acceptable salts. Very particularly preferred compounds of the formula (Ent3) 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.

Further, the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

Preferred pyridine derivatives are, in particular, the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-

Methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 2 359 399, Japanese Laid-Open Patent Publication JP 02019576 A2 or in the published patent application WO 96/15765, such as 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.

Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 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- (2-aminoethyl) amino-1,3-dimethylpyrazole , 3,4,5- Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-ajopyrimidine of the following formula (Ent4) and its tautomeric forms, if a tautomeric equilibrium exists:

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl a (C ₁ - to C ₄ ) alkoxy (C _r to C ₄ ) alkyl, a Ci to C ₄ -Aminoalkylrest, which may optionally be protected by an acetyl-ureide or a sulfonyl radical a (C ₁ - to C ₄₎ alkylamino (Ci to C ₄₎ - alkyl group, a di - [(C _r to C ₄₎ alkyl] - (Ci to _C4) aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C _r to C ₄ ) aminoalkyl, the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl a C ₁ to C ₄ aminoalkyl radical en (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl, a di-I (C ₁ to C ₄ ) alkyl] (C ₁ to C ₄ ) aminoalkyl, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a C ₁ - to C ₄ -alkyl or di (C ₁ to C ₄ -hydroxyalkyl) amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is other than 0 when p + q is 2, n is O, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (Ent4) are defined according to the invention analogously to the above statements.

When the pyrazolo [1,5-a] pyrimidine of the above formula (Ent4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium which is shown, for example, in the following scheme:

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) may be mentioned in particular:

Pyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;

Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

2,7-dimethyl-pyrazolo [1,5-a] pyrimidine-3,5-diamine;

3-aminopyrazolo [1,5-a] pyrimidin-7-ol;

3-aminopyrazolo [1,5-a] pyrimidin-5-ol;

2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;

2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;

2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine; 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

The pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives and heterocyclic compounds are generally used.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 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 and 2,4 dichloro-3-aminophenol,

o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 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-yl-phenyl) -amino] -ethanol, 3-amino-4- (2-methoxy ethoxy) -5-methylphenylamine and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene,

o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, Pyridine derivatives such as 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 and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2- Methyl 1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7- Dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 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, or

Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts.

Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically acceptable salts of the abovementioned compounds.

The cosmetic agents contain the developer components preferably in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the total agent.

The cosmetic compositions contain the coupler components preferably in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the total agent. The agent can be used as color-modifying component in the form of Oxofarbstoffvorprodukte at least one combination of at least one compound of the component

1 compounds containing a reactive carbonyl group with at least one compound of the component

2 compounds selected from (a) CH-acidic compounds, (b) compounds containing primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component 1) have at least one carbonyl group as reactive group which reacts with the compounds of component 2 to form a chemical bond linking both components. Further, according to the invention, those compounds are also included as component 1 in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to the component 2 is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and their derivatives to form imines or oximes as a condensation compound b) alcohols to form acetals or ketals as a condensation compound c) water to form hydrates as a condensation compound of aldehydes.

Component 1 is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone non, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4- Morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2- Aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, Chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3 -Hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-

Methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6- dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4- Hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6- Diethoxy-4-hydroxy-benzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4- Ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3, 5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-

Trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4- Dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2, 5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2- Morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1 - naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2, 4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-n aphthaldehyde, 4- Hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxycinnamaldehyde, 4- Dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylaminocinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) -benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy 1 H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde), 2-indolaldehyde, 3 -indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindlyne, 2- (1 ', 3', 3 ^l Trimethyl-2-indolynylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridinealdehyde, 2-Py 3-pyridinealdehyde, 3-pyridinaldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitofurfural, 2-thenoyl- trifluoro-acetone, chromone-3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 1, 3-diacetylbenzene, 1 , 4-Diacetylbenzene, 1, 3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) - acetophenone and 2- (3'-pyridoyl) acetophenone, benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylidene acetone, 3,4-methylenedioxybenzylideneacetone, 4 Pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-

Diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-

Benzylidenecyclohexanone, 2- (4'-hydroxybenzylidene) cyclohexanone, 2- (4'-

Dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1, 3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) -1, 3-cyclohexanedione, 2-benzylidene-5 , 5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3-methoxybenzylidene) -5.5 dimethyl-1, 3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) -cyclopentanone, 2- (4' -Dimethylaminobenzylidene) cyclopentanone, 5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal , 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-Piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-Dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (4-piperidinophenyl) hexa -3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5-dien-2-one, 5 - (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxybenzaldehyde. 3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3- nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5- n itrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4- Nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, S.Θ-diacetyl-θ- ethylcarbazole, S-acetyl-θ-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-Formyl-i-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1, 2-dimethylpyridinium, 4-formyl -1, 3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-i methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-Ph methyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium -, 6-formyl-1-benzyl-quinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7 Formyl-1-allyl-quinolinium and 8-formyl-1-allyl-quinolinium, 5-acetyl-1-methyl-quinolinium, 6-acetyl-1-methyl-quinolinium, 7-acetyl-1-methyl-quinolinium, 8-acetyl-1-methyl-quinolinium , 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6 Acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5-acetyl-1-allylquinolinium, 6-acetyl-1-allylquinolinium, 7-acetyl-1-allylquinolinium and 8-acetyl-1-allylquinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1, 3-dimethyl-2- (4'-formylpheny l) -benzimidazo- lium, 1,3-dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium , 2- (4'-Formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2 ¹ -furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl ) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1) naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3,5-dimethylbenzothiazolium salts, preferably with benzenesulfonate, p-toluenesulfonate , Methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate or tetrafluoroborate as counterion, isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5 - Methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfoisoisine, 5-carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures of the above n connections.

As CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected. According to the invention, CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.

The CH-acidic compounds of component 2 are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p- toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3 acetic acid, 1, 4-dimethylquinolinium iodide, 1, 2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylacetate, 2- Coumaranone, 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1, 2-dione, indan-1, 3-dione, indanine 1-one, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethyl cyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methyl-benzoxazolium iodide, 3-ethyl-2-methyl-benzothiazolium iodide, i-ethyl-4-methyl quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1, 2,3- Trimethylquinoxalinium iodide, 3-ethyl-2-methyl-benzoxazolium-p-toluenesulfonate, 3-ethyl-2-methyl-benzothiazolium-p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate.

Preferred primary or secondary aromatic amines of component 2 are selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N- Bis (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2,5-dichloro p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4- aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5-diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethol, 4-amino-3-methylphenol, 2- 2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4- Methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethyl lamino) phenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, A-amino-2- hydroxymethylphenol, 2- (diethylaminomethyl) -4-aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1-hydroxy-2-amino-5-methylbenzene, 1-hydroxy-2- amino-6-methylbenzene, 2-amino-5-acetamido-phenol, 1, 3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino) 2-methylphenol, 5-amino-4-methoxy 2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino 5- (2-hydroxyethoxy) toluene, 2,4-diamino-5-methylphenol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) -anisole, 2, 6-bis (2-hydroxyethylamino) -1-methylbenzene, 1, 3-diamino-2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenylacetic acid, 3-amino-phenylacetic acid, 4-aminophenylacetic acid, 2,3-diaminobe nanoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxybenzoic acid, 4-amino-3 -hydroxybenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfone - acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3, 5-triaminobenzene, 1, 2,4-triaminobenzene, 1, 2,4,5-tetraaminobenzene, 2,4,5-triamino-phenol, penta-aminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobenzene catechol, 4,6-diaminopyrogallol, 1- (2-hydroxy-5-aminobenzyl) -2-imidazolidinone, A-amino-2 - ((4 - [(5-amino-2-hydroxyphenyl) methyl] piperazinyl) methyl ) phenol, 3,5-diamino-4-hydroxy-catechol, 1,4-bis (4-aminophenyl) -1, 4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile , A-aminobenzonitrile, 2,4-diaminobenzonitrile, nitro-containing amino compounds, such as 3-amino-6-methylamino-2-nitro-pyridine, picric acid, [8 - [(4-amino-2-nitrophenyl) -azo] - 7-hydroxy-naphth-2-yl] -trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) -azo) -7-hydroxy-naphth-2-yl] -trimethyl-ammonium chloride (Basic Brown 17), 1 -Hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2-nitro-4- [bis (2-hydroxyethyl) amino] benzene, 1-amino-2 - [(2-hydroxyethyl) amino] 5-nitrobenzene (HC Yellow No. 5), 1-amino-2-nitro-4 - [(2-hydroxyethyl) amino] benzene (HC Red No. 7), 2-chloro-5-nitro-N- 2-hydroxyethyl-1,4-phenylenediamine, 1 - [(2-hydroxyethyl) amino] -2-nitro-4-aminobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4- Amino-2-nitrophenol, 6-nitro-o-toluidine, 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), 1-amino- 2-nitro-4 - [(2,3-dihydroxypropyl) amino] -5-chlorobenzene (HC Red No. 10), 2- (4-amino-2-nitroanilino) benzoic acid, 6-nitro 2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid disodium salt (Acid blue No. 29 ), 1-amino-2- (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5- nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (gallium), 4-amino-4 '-nitrostilben-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ^1, 5'-dinitro-2 ^{1-hydroxy-5-methyl-azobenzene} (Mordant brown 4), 4'-amino-4-nitrodiphenylamine 2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) -benzene, 2- [2-

(Diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5 Amino-6-nitrobenzo-1,3-dioxole, anilines, in particular nitro-group-containing anilines, such as A-nitroaniline, 2-nitroaniline, 1, 4-diamino-2-nitrobenzene, 1, 2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro-1-aminobenzene 4- [bis (2-hydroxyethyl) amino] benzene, A-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2- Nitrobenzene, aromatic anilines or phenols with another aromatic radical, as shown in the formula II

in the

R ^{7 represents} a hydroxy or an amino group represented by C _1-4 -alkyl, C _1-4 -hydroxyalkyl, C _1-4 -alkoxy or C _1-4 -alkoxy-Ci. _4- alkyl groups may be substituted,

R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² independently of one another represent a hydrogen atom, a hydroxy or an amino group represented by C ₁ -C ₄ -alkyl, C ₁ -C -hydroxyalkyl, C ₁ -C ₄ - Alkoxy, C _r C ₄ -Aminoalkyl- or C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl groups may be substituted, and

P is a direct bond, a saturated or unsaturated, optionally substituted by hydroxyl groups carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group having the formula III

-O '- (CH ₂ -Q-CHrQ ¹¹ J ₀ - (III)

in the

Q signifies a direct bond, a CH ₂ or CHOH group,

• Q 'and Q "independently represent an oxygen atom, an NR ¹³ group, wherein R ^{13 represents} a hydrogen atom, a C _1-4 alkyl or a hydroxy C _1-4 alkyl group, both of which together with the remainder of the molecule can form a 5-, 6- or 7-membered ring, the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p -O, where p and p ^{1 are} 2 or 3, stand and

O is a number from 1 to 4,

such as 4,4 ^I diaminostilbene and its hydrochloride, 4,4'-diaminostilbene disulfonic acid 2.2 ¹ mono- or di-Na salt, 4-amino-4 -dimethylaminostilben ¹ and its hydrochloride, 4, 4'-diaminodiphenylmethane, 4,4 ^I -Diaminodiphenylsulfid, 4,4' Diaminodiphenylsulfoxid, 4.4 ^I -Diaminodiphenylamin, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-tetraamino-diphenyl, S.S' ^^ '- tetraamino-benzophenone, 1, 3-bis- (2 , 4-diaminophenoxy) -propane, 1, 8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1, 3-bis (4-aminophenylamino) propane, 1, 3-bis (4 -aminophenylamino) -2-propanol, 1,3-bis [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis [2- (4-aminophenoxy) -ethyl ] -methylamine, N-phenyl-1, 4-phenylenediamine and bis (5-amino-2-hydroxyphenyl) -methane.

The abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.

Suitable nitrogen-containing heterocyclic compounds are, for. B. 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-amino-pyridine, 2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6- Dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4-dimethylpyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N - (5-amino-2-pyridyl) -amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) -amine, 2,4-dihydroxy-5,6- diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino 4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6-methylpyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1, 2,4-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl- 4,5-diaminopyrazole, 4-amino 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline, 4-aminoquinaldine , 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino aniline and indole and indoline derivatives such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Furthermore, as heterocyclic compounds, the hydroxypyrimidines disclosed in DE-U 1-299 08 573 can be used according to the invention. The aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used. Suitable aromatic hydroxy compounds are, for. 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, brenzkazethine, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4- Methoxyphenol, 3-dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxy-phenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid , 2,4,6-trihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6 Dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

The compounds of component 1 and the compounds of component 2 are preferably used in the cosmetic compositions in each case in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total Nuanciermittels used. The molar ratio of the compound of component 1 and the compound of component 2 may range from 0.5 to 2.0, preferably using equimolar amounts. The ready-to-use agent is prepared by separate mixing of components 1 and 2 immediately prior to application.

As precursors of naturally-analogous dyes, preference is given to using as oxidation dye precursor of the developer type such indoles and indolines which have at least one hydroxyl or amino group, 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 second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

Particularly suitable precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IVa),

in the independently of each other

R ¹ is hydrogen, a C 1 -C 4 -alkyl group or a C 1 -C -hydroxy-alkyl group,

R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation, R ³ is hydrogen or a C 1 -C 4 -alkyl group,

R ⁴ is hydrogen, a C ^ C ^ alkyl group or a group -CO-R ⁶ in which R ⁶ represents a CrC _t -alkyl group, and R ⁵ represents one of the groups mentioned for R ^4, and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6 dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

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-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IVb),

R ¹ (IVb) in the independently of each other

R ¹ is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,

R ³ is hydrogen or a C 1 -C ₄ -alkyl group,

R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ in which R ⁶ represents a -C ₄ alkyl group, and

R ⁵ represents one of the groups mentioned under R ⁴ , - and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

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 -Dihydroxyindol.

Preferred substantive dyes which are used in the cosmetic compositions as a color-changing component are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis- (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- 2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) arnino-5-chloro-2 nitrobenzene, 4-amino-3-nitrophenol, 1- (2'- Ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic 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 and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Further, the cosmetic agents may contain a cationic substantive dye. Particularly preferred are

(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 incorporated herein by reference, in claims 6 to 11.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

Cl ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct dyes.

The cosmetic compositions contain the substantive dyes preferably in an amount of 0.01 to 20 wt .-%, based on the ready-to-use agent.

Furthermore, the cosmetic compositions according to the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, seder and alkano root are included.

It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the cosmetic products, due to the production processes for the individual dyes, minor amounts of other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

With regard to further optional components and the amounts of these components used, reference is expressly made to those relevant to the person skilled in the art Manuals, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

The actual oxidative color changing agent is prepared by separate storage of the dye precursors or the bleach booster and the oxidizing agent immediately before use by mixing. In a preferred embodiment, the cosmetic agent is therefore mixed before application from a composition comprising at least one color-modifying component in a cosmetic carrier and a further composition containing at least one oxidizing agent in a cosmetic carrier.

When an oxidizing agent is used, the ready-to-use preparation is expediently prepared immediately before use by mixing a composition 1 comprising, in a cosmetic carrier, the oxidizing agent with the composition 2 containing the color-changing components in a cosmetic carrier. The resulting ready-to-use hair preparation should preferably have a pH in the range from 6 to 12, in particular from pH 7.5 to 10. The ginseng extract is preferably contained in the composition 1.

For a color change by means of lightening or bleaching of the hair, in addition to the oxidizing agent, at least one bleaching booster is preferably used in the cosmetic compositions according to the invention.

Bleach boosters are preferably used in bleaching agents for increasing the bleaching action of the oxidizing agent, in particular the hydrogen peroxide.

As bleach amplifiers, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI) ₁ acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- Diacetoxy-2,5-dihydrofuran.

As bleach booster, carbonate salts or bicarbonate salts can preferably be used according to the invention. These are preferably selected from the group of ammonium, alkali (especially sodium and potassium), and alkaline earth (especially calcium), carbonate salts or bicarbonate salts. Particularly preferred carbonate or bicarbonate salts are ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, disodium carbonate,

Potassium bicarbonate, dipotassium carbonate and calcium carbonate. These particularly preferred salts can be used alone or in their mixtures of at least two representatives as bleaching amplifiers.

As bleach booster of the type of monoalkyl carbonates and their derivatives, at least one carbonic acid monoester and / or at least one carbonic acid monoamide are preferably used in the process according to the invention. Preferred carbonic acid monoesters are the carbonic acid monoesters of the formula (V),

R-O-C-O-H (V)

Where each O is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (V), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a C _1-6 alkyl group. Examples For CrCe-alkyl groups according to the invention, the groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Compositions particularly preferably used according to the invention are characterized in that the radical R in formula (V) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, terf-butyl - As well as hydroxymethyl and Hyd roxyethy I residues.

As an alternative to the carbonic acid monoester or in conjunction with it, carbonic acid monoamides can be used as bleach boosters in the anhydrous compositions. In this case, it is preferred according to the invention to use at least one carbonic acid monoamide of the formula (VI),

R-NH-C-O-H (VI)

O in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (VI), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably, R is a C _1-6 alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Bleach enhancers of the formula (VI) which are particularly preferred according to the invention are characterized in that the radical R in formula (VI) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl , tert-butyl and hydroxymethyl and hydroxyethyl radicals. The acidic H atom of the carbonic acid monoester or monoamide can also be present in neutralized form, ie according to the invention it is also possible to use salts of carbonic acid monoesters or carbonic acid monoamides. Carbonic acid monoesters or the carbonic acid monoamides which are present in completely or partially neutralized form, preferably in the form of the alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt, are preferred according to the invention.

As bleach boosters of the type of silyl carbonates and derivatives thereof, at least one silyl carbonate and / or at least one silyl carbamate are preferably incorporated into the compositions according to the invention. Preference is given to using silyl carbonates of the formula (VII)

R ²

R ¹ -Si-OCOR ⁴ (VII)

R ³ O

in which the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radical R ^{4 is} a chemical bond to the Si atom or one of the radicals R ¹ , R ² or R ³ , is a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted SiIyI or Aluminylgruppe or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (VII) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among them, the alkyl groups having 1 to 5 carbon atoms and the hydroxyalkyl groups are preferred, so that preferred anhydrous compositions of the present invention are characterized in that the radicals R ¹ , R ² and R ³ in formula (VII) are selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert-butyl Butyl and hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ in the abovementioned formula (VII) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

As bleach booster, at least one silyl carbamate of the formula (VIII) may be present in the anhydrous composition according to the invention,

R ² R ¹ -Si-OC-NR ⁴ R ⁵ (VIII)

where the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or for a trialkylsilyl group, preferably a trimethylsilyl group or for a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radicals R ⁴ and R ⁵ independently of one another for a chemical bond to the Si atom or to one of the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or for a substituted or unsubstituted SiIyI or alumino group or for a substituted or unsubstituted aryl group or a substituted or unsub substituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (VIII) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among them, the alkyl groups having 1 to 5 carbon atoms and the hydroxyalkyl groups are preferred, so that preferred compositions are characterized in that the R ¹ , R ² and R ³ in formula (VIII) are selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, terf-butyl and hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ and R ⁵ in the abovementioned formula (VIII) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

As further additional bleach boosters, in the compositions according to the invention preferably at least one compound selected from acetic acid, lactic acid, tartaric acid, citric acid, salicylic acid and ortho-phthalic acid may be contained.

Bleach amplifiers are preferably peroxo compounds. Among the bleach-enhancing peroxy compounds according to the invention there are no addition products of hydrogen peroxide to other components and also not hydrogen peroxide itself. Moreover, the choice of peroxo compounds is subject to no restrictions. Preferred peroxo compounds are peroxydisulfate salts, monopersulfate salts, (in particular ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium monopersulfate, potassium monopersulfate, sodium monopersulfate,

Potassium peroxide phosphate) and peroxides (such as barium peroxide and magnesium peroxide). Among these peroxo compounds, which can also be used in combination, the inorganic compounds are preferred according to the invention. Particularly preferred are the Peroxidisulfatsalze, in particular ammonium peroxydisulfate.

The bleach boosters are contained in the cosmetic compositions preferably in amounts of 5-30 wt .-%, in particular in amounts of 8-20 wt .-%.

The agents according to the invention preferably have a pH of from pH 2 to pH 11, in particular from pH 8 to pH 11.

As a cosmetic carrier preferred according to the invention, a gel carrier is selected. This gel carrier preferably contains 1, 0 to 15 wt .-% of a saturated or unsaturated, linear or branched alcohol having 8 to 36 carbon atoms,

0.1 to 15 wt .-% of a liquid fatty acid having 16 to 22 carbon atoms in the form of a water-soluble soap.

0.5 to 10 wt .-% of an adduct of 1 to 5 moles of ethylene oxide to a linear fatty alcohol having 8 to 22 carbon atoms and

0 to 10 wt .-% of an adduct of 15 to 100 units of ethylene oxide per molecule of a linear fatty alcohol having 8 to 22 carbon atoms,

0 to 20 wt .-% of a low molecular weight, water-soluble monoalcohol.

The saturated or unsaturated, linear or branched alcohols having 8 to 36 C atoms to be used according to the invention are preferably fatty alcohols and / or Guerbet alcohols.

Fatty alcohols are to be understood as meaning primary aliphatic alcohols of the formula (IX)

R ¹ OH (IX)

in which R ^{1 is} an aliphatic, linear or branched hydrocarbon radical having 8 to 22 carbon atoms which is saturated or may contain up to 3 double bonds.

Typical examples are 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and technical mixtures thereof for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Preference is given to technical fatty alcohol mixtures having 12 to 18 carbon atoms, for example coconut, palm, palm kernel or tallow fatty alcohol, in particular coconut and / or tallow fatty alcohol.

Guerbet alcohols are to be understood as alcohols which are prepared by alkaline condensation of alcohols to higher molecular weight, branched iso alcohols. This implementation was first published by Guerbet in 1899. Machemer presented 1952 essential steps of the reaction (Angewandte Chemie 64 (1952) 213-20): In addition to the dehydrogenation to ketone, in which hydrogen is split off, and the aldol condensation is the crotonization, in which water is split off, an important step in the reaction process , The prior art is a reaction at atmospheric pressure and a reaction temperature of 240 to 260 ⁰ C. The branched alcohols thus obtained are referred to as Guerbet alcohols. In the meantime, a large number of other processes are known from the prior art according to which Guerbet alcohols can be obtained.

Suitable adducts of 1 to 4 or 15 to 100 mol of ethylene oxide with a linear fatty alcohol having 12 to 22 carbon atoms are all adducts obtainable by the known industrial ethoxylation processes. Preference is given to the addition products which contain only a small amount of free fatty alcohol and have a narrow homolog distribution (so-called narrow-rank ethoxylates), as described, for example, in US Pat. are accessible according to the method described in DE 38 43 713 A1.

It is preferred according to the invention to use addition products of 15 to 100 moles of ethylene oxide, in particular from 15 to 50 moles of ethylene oxide, to a linear fatty alcohol having 8 to 22 carbon atoms in the gel compositions. These are very particularly preferably ceteareth-15 or ceteareth-50, which are marketed as Eumulgin ^® CS 15 and CS Eumulgin ^® 50 by Cognis Germany GmbH.

The fatty acids suitable for soap formation are preferably liquid or low-melting unsaturated linear fatty acids having 16 to 22 carbon atoms such as palmitoleic, oleic, elaidic, myristic, petroselic, petroselaidic, gadoleic, erucic, brassidic and mixtures of these fatty acids with each other and optionally with lower levels of saturated linear Fatty acids with 12 to 22 carbon atoms. Also suitable are liquid or low-melting branched fatty acids are branched fatty acids having 16 to 22 carbon atoms, for example, the 2-hexyldecanoic acid, isostearic acid and 2-octyldodecanoic acid.

For the conversion of fatty acids into water-soluble soaps are alkali metal hydroxides and alkali metal carbonates, ammonia, mono-, di- and trialkanolamines having 2 to 4 carbon atoms in the alkanol group and alkaline amino acids such as arginine, ornithine, lysine and / or histidine.

It is preferred according to the invention for adjusting the viscosity of the gelatinous composition additionally at least one low molecular weight, water-soluble monoalcohol, more preferably in an amount of 0.5 to 20 wt .-% based on the weight of the total composition to add. For the purposes of the present invention, low-molecular weight monoalcohols are to be understood as meaning water-miscible alcohols having 1 to 5 C atoms. These monoalcohols carry only one hydroxy group. It is preferably ethanol, propanol and / or isopropanol.

Furthermore, the compositions according to the invention may additionally contain at least one polyol. For the purposes of the invention, polyols carry at least two hydroxyl groups, preferably two to four hydroxy groups. As polyols, especially those having 2 to 6 C atoms are preferred. It is suitable e.g. Ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, erythritol, trimethylolpropane, diethylene glycol and dipropylene glycol. 1,2-Propylene glycol is particularly preferred.

Suitable water-soluble synthetic surfactants are preferably anionic, amphoteric, zwitterionic and nonionic surfactants having good water solubility and good lime soap dispersibility. Such surfactants typically have a lipophilic linear alkyl or acyl group of 12 to 18 carbon atoms and a highly dissociated ionic group or nonionic water-solubilizing polyether group. Suitable examples are sulfuric acid semi-salts of linear fatty alcohols having 12 to 18 carbon atoms or of fatty alcohol polyglycol ethers having 12 to 16 carbon atoms in the alkyl group and 1 to 10 glycol ether groups. Further suitable anionic surfactants are, for example, linear alkanesulfonates and α-olefin sulfonates having 12 to 18 C atoms. Suitable nonionic surfactants are, for example, the addition products of 5 to 14 moles of ethylene oxide with linear fatty alcohols having 12 to 18 carbon atoms, with fatty acids having 12 to 18 carbon atoms and with fatty acid monoglycerides and with fatty acid sorbitan monoesters. Preferably suitable nonionic surfactants are the fatty alkylamine oxides and in particular the fatty alkyl glycosides, preferably fatty alkyl glucosides. The fatty alkyl group may have 12 to 18 C atoms in the products mentioned.

For the purposes of the present invention, it is also possible to use amphoteric surfactants, for example N-fatty-alkyl-dimethyl-glycine or N-fatty-alkylaminopropionic acid and / or zwitterionic surfactants, e.g. N-Fettalkyl- dimethylammoniumglycinat or N-Fettacylaminopropyldimethylglycinat. Also preferred are cationic surfactants, such as quaternary ammonium compounds (QACs), in particular quaternized trialkylammonium compounds with alkyl radicals having a chain length of C8 to C22.

It has been found that thickening of the oxidation dye preparation and in particular of the dye formulation prepared immediately before application is achieved by the addition of further, limited water-soluble, nonionic surfactants.

In addition, the agents of the invention may contain addition products of from 1 to 4 moles of ethylene oxide onto a fatty alkylamine. As addition products of 1 to 4 moles of ethylene oxide to a linear fatty alkylamine having 12 to 22 carbon atoms are all accessible by known technical methods adducts, which are also commercially available. Particularly suitable is the adduct of 2 moles of ethylene oxide to a C ₁₂ -

C ₁₈ cocoalkylamine.

Suitable compounds of the formula X.

R ⁵ - (OC ₂ H ₄ ) _χ -A- (C ₂ H ₄ O) _y -R ⁶ (X)

in which A is an oxygen atom, are dialkyl ethers having 12 to 18 carbon atoms in the alkyl groups. Such products are known from the literature. Even more suitable are the products of formula X in which x or y or both = 1. Such Dialkyloxyethyl ethers can be prepared from fatty alcohols and fatty alkoxyethanols by etherification processes known from the literature. The products of the formula X in which A is a group

HO-C ₂ H ₄ -N is, for example, from triethanolamine by O-alkylation with 2 moles of a sulfuric acid half-salt of a

^{win by the} method described ^{in DE} 35 04 242 for the preparation of ether amines.

Particularly preferred compounds of formula X are e.g. Dicetylstearyl ether, dicetylstearyldioxyethyl ether and N, N-bis (2-cetyl / stearyl-oxyethyl) aminoethanol.

While with addition products of 1 to 5 moles of ethylene oxide to a linear fatty alcohol, the required thickening is usually achieved solely by this component, it may be advantageous when using the addition products of 1 to 4 moles of ethylene oxide to a linear fatty alkylamine, these in combination with 1 to 10 Wt .-% of a compound of formula X to use.

With regard to the dyes which can be used in the compositions according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", Issued by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.

Xanthan gum, agar agar, linear and crosslinked polyacrylates, nonionic and anionic cellulose derivatives and amphiphilic polymers can be contained in the compositions according to the invention as additional thickeners.

The agents according to the invention may additionally contain at least one cationic polymer. Cationic polymers are polymers which have groups in the main and / or side chain which may be "temporary" or "permanent" cationic. As "permanently cationic" according to the invention such Denotes polymers which have a cationic group regardless of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C _1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

Homopolymers of the general formula (XI),

wherein R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from C _1-4 alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4 , n is a natural number and X ^"is a physiologically acceptable organic or inorganic anion, and copolymers consisting essentially of the monomer units listed in formula (XI) and nonionic monomer units are particularly preferred cationic polymers Within the scope of these polymers, those are preferred according to the invention for which at least one of the following conditions applies:

R ¹ is a methyl group - R ² , R ³ and R ⁴ are methyl groups m is 2.

Suitable physiologically tolerated counterions X- include, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preference is given to halide ions, in particular chloride.

A particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylene bisacrylamide, diallyl ether, polyallyl polyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are available under the names Salcare ^® SC 95 (about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1-Trideceth- 6)), and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl polyoxypropylene polyoxyethylene ether (INCI name: PPG-1-Trideceth-6)) commercially available.

Copolymers having monomer units of the formula (XI) contain, as nonionic monomer units, preferably acrylamide, methacrylamide, acrylic acid C _1-4 -alkyl esters and methacrylic acid-C 1. _4- alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

Further preferred cationic polymers are, for example

- Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® commercially available. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^® ^® 400 are preferred quaternized cellulose derivatives

cationic alkyl polyglycosides according to DE-PS 44 13 686,

- cationized honey, for example the commercial product Honeyquat ^® 50,

- cationic guar derivatives, in particular those sold under the trade names Cos media ^® Guar and Jaguar ^® products, - Polysiloxanes with quaternary groups, such as those commercially available

Products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).,

polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylarnmoniumchlorid)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755 commercially, vinylpyrrolidone-vinyl imidazolium copolymers, such as those offered under the names Luviquat ^® FC 370, FC 550, FC 905 and HM 552, quaternized polyvinyl alcohol, as well as the under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.

Can be used as cationic polymers (. B. commercial product, Quatrisoft ^® LM 200) under the designations Polyquaternium-24, known polymers. Also usable in the invention are the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (manufactured by ISP), Gaffix ^® VC 713 (manufactured by ISP), Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 available are. Other cationic polymers of the invention are the "temporarily cationic" polymers. These polymers usually contain an amino group present at certain pH values as a quaternary ammonium group and thus cationic are preferred, for example, chitosan and its derivatives, such as, for example, under the trade designations Hydagen ^®. , Hydagen® ^® HCMF, Kytamer ^® PC and Chitolam ^® NB / 101 are freely available commercially CMF. chitosans are deacetylated, in different degrees of deacetylation and varying degrees of degradation (molecular weights) are commercially available. Their preparation is, for example, in DE 44 40 625 A1 and described in DE 1 95 03 465 A1.

Particularly useful chitosans have a degree of deacetylation of at least 80% and a molecular weight of 5 ^■ 10 ⁵ to 5 ^• 10 ⁶ (g / mol).

For the production of preparations according to the invention, the chitosan must be converted into the salt form. This can be done by dissolving in dilute aqueous acids. As acids, both mineral acids, e.g. Hydrochloric acid, sulfuric acid and phosphoric acid as well as organic acids, e.g. low molecular weight carboxylic acids, polycarboxylic acids and hydroxycarboxylic acids suitable. Furthermore, higher molecular weight alkyl sulfonic acids or alkyl sulfuric acids or

Organophosphoric acids are used, provided that they have the required physiological compatibility. Suitable acids for converting the chitosan into the salt form are e.g. Acetic acid, glycolic acid, tartaric acid, malic acid, citric acid, lactic acid, 2-pyrrolidinone-5-carboxylic acid, benzoic acid or salicylic acid. Preferred are low molecular weight hydroxycarboxylic acids such as e.g. Glycolic acid or lactic acid.

Furthermore, hair cosmetic auxiliaries may be contained, in particular bisabolol, plant extracts, vitamins such as preferably niacinamide, tocopherol, vitamin A, vitamin B ₆ , biotin and vitamin D.

A preferred embodiment of the first subject of the invention is an oxidative hair dye. This is immediately before use by mixing an oxidizing agent preparation comprising in a cosmetic carrier at least one oxidizing agent having a composition comprising in a (preferably gel) cosmetic carrier (i) ginseng extract as well

(ii) at least one oxidation dye precursor in the form of developer and / or

Coupler components prepared in a weight ratio of 1: 2 to 2: 1. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12, in particular from 8 to 11. 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 usually 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.

The oxidizing agent preparation particularly preferably contains

3 to 24 wt .-% hydrogen peroxide

0.1 to 5 wt .-% of a water-soluble, synthetic surfactant and

1 to 5 wt .-% of a dispersed acrylic acid and / or

Methacrylic acid polymer or copolymer

in the aqueous carrier in addition to the usual stabilizing aids in such preparations. But it can also consist in the simplest case of water alone, so that the oxidation is brought about by the atmospheric oxygen.

The water-soluble synthetic surfactants which may be used in the oxidizing agent preparation are the anionic, amphoteric, zwitterionic and nonionic surfactants already mentioned for the carrier composition of the invention or mixtures thereof. Preference is given to anionic surfactants, for example sulfuric monoester salts of linear fatty alcohols having 12 to 18 carbon atoms or of fatty alcohol polyglycol ethers having 12 to 16 carbon atoms in the alkyl group and 1 to 10 glycol ether groups in the form of their alkali metal, magnesium, ammonium or alkanolammonium salts used. The oxidizing agent preparation also preferably contains complexing agents and buffer salts for adjusting a pH of from 2 to 5. In this weakly acidic medium, the acrylic acid and / or methacrylic acid polymer dispersions remain highly fluid and stable. When mixed with the alkaline carrier medium according to the invention, which contains ammonia and buffer salts to set a pH of 8 to 10, the pH of the mixture increases and the carboxyl groups of the polymer or copolymer are converted into the salt form. The polymers begin to dissolve in the aqueous medium and raise the viscosity of the solution.

The content of dispersed acrylic acid and / or methacrylic acid polymer or copolymer in the oxidizing agent preparation is particularly favorable for the viscosity build-up after mixing of the composition according to the invention and of the oxidizing agent preparation. Such dispersions of copolymers, for example from at least 10% by weight of acrylic acid lower alkyl ester, from 25 to 70% by weight of methacrylic acid and optionally up to 40% by weight of a further comonomer, are described, for example, in GB 870 994. From DE 11 64 095, copolymers of 50 to 75% by weight of ethyl acrylate, 25 to 35% by weight of acrylic acid and 0 to 25% by weight of other comonomers are known. Suitable dispersions of this type are commercially available, for example under the trade name Latekoll D ^® (BASF). Particularly suitable are the copolymers described in DE 34 45 549 from 50 to 60 wt .-% ethyl acrylate, 30 to 40 wt .-% methacrylic acid and 5 to 15 wt .-% acrylic acid, crosslinked with ethylene glycol dimethacrylate.

A second subject of the invention is the use of a cosmetic agent of the first subject of the invention for reducing oxidative-induced skin irritation during oxidative hair treatment.

A third subject of the invention is the use of a cosmetic agent of the first subject of the invention for reducing oxidative-induced skin elasticity impairment during the oxidative hair treatment.

A fourth subject of the invention is the use of a cosmetic agent of the first subject of the invention for reducing the oxidizing agent induced impairment of hair conditioning during oxidative hair treatment. In particular, the moisture balance of the hair is improved by the use of ginseng extract according to the invention, so that the hair is less brittle.

A fifth subject of the invention is a method for treating keratin-containing fibers, in particular human hair, in which a cosmetic product of the first subject of the invention is applied to the hair and rinsed off again after a contact time.

The following examples are intended to explain the subject matter of the invention in more detail:

B e i s p e e l e

All amounts are, unless otherwise indicated, weight percent of the individual components based on the weight of the corresponding composition.

1.0 Determination of moisture regulation in the hair

For the determination of the moisture, human hair strands from Kerling (Nuance 8-0, dark blonde, weight 2.0 g, length 11 cm) were first washed with 30 ml of Texapon NSO UP, rinsed with water and dried in the air for 24 hours and then conditioned for 24 hours at 25 ⁰ C and a relative humidity of 40%.

The zero value measurement of the moisture in the test hair strand is carried out according to the microwave method {vide infra).

For each hair dye to be tested 5 of these hair strands were dyed and measured as follows:

First, the cream formulations listed below in Table 1 were provided using the usual manufacturing method.

Table 1: Dye carrier

Ci ₂ -C ₁₄ fatty alcohol with 2 units of ethylene oxide (INCI name: Laureth-2) (manufacturer: COGNIS)

2 C ₁₂ -C ₁₈ fatty alcohol (INCI name: Coconut Alcohol) (manufacturer: COGNIS)

3 potassium oleate (manufacturer: COGNIS)

4 sodium lauryl ether sulfate (27% active ingredient, INCI: Sodium Laureth Sulfate) (manufacturer: COGNIS)

5 C ₁₆ -C ₁₈ fatty alcohol with approx. 50 units of ethylene oxide (INCI name: Ceteareth-50) (manufacturer: COGNIS)

6 1-Hydroxyethane-1, 1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (Manufacturer: Solutia) 7 keratin hydrolyzate (active substance 20% by weight) (INCI name: Aqua (Water), Hydrolyzed Keratin, Phenoxyethanol, Methylparaben, Butylparaben, Ethylparaben, Propylparaben) (Manufacturer: COGNIS)

8 oil-soluble extract from Panax ginseng (active substance 1% by weight) (INCI name: Isopropyl myristate, Panax ginseng root extract) (manufacturer: Chosmetochem)

10.0 g of one of the dye carriers from Table 1 were mixed with 10.0 g of the oxidizer composition shown in Table 2 to give the ready-to-use colorant. Dye carrier V1 was used to obtain a colorant not according to the invention which was compared with the colorant of the invention obtained by using dye carrier E1.

Table 2: Oxidizing agent composition

Wt .-%

Dipicolinic acid 0.62

Sodium pyrophosphate 0.03

Turpinal SL ^® 1, 50

Texapon ^® NSO UP 2.00

Aculyn ^® 33 A ⁹ 12.00

Hydrogen peroxide (50% aqueous solution) 12.00

Water ad 100

9 Acrylic acid copolymer (30% active ingredient, INCI name: Acrylates

Copolymer) (manufacturer: Rohm & Haas)

The application mixture was applied in each case in the liquor ratio of 1.0 g of hair to 2.0 g of dye on the hair strand. After a reaction time of 5 minutes, the application mixture was rinsed from the hair strand with running 30 ⁰ C warm water.

The rinsed hair was air dried for 24 hours and then conditioned for 24 hours at 25 ⁰ C and a relative humidity of 40%. Subsequently, the moisture content of the treated hair strands was determined by the microwave method (vide infra). The moisture in the hair after treatment is calculated from the measurements as follows:

Moisture [in%] = (average _Fe UCHT _lg keιtdes treated hair / mean _Nu || _m easurement) 100

The hairs treated with the colorant according to the invention had a higher moisture content with a humidity of 109.0% than the hair treated with the reference colorant (106.8).

Humidity measurement according to microwave method

To carry out the moisture measurement, a moisture meter from TEWS Elektronik GmbH, Hamburg was used (microwave radio-frequency field with 2 to 3 GHz with a microwave power of less than 10 mW). The measuring method is described in detail in the publication WO-A1-91 / 12518, to which reference is expressly made and full content.

The strand of hair to be measured is introduced into the measuring tube of the measuring device. There are five measurement points per hair strand. The measured value of the moisture of the measuring hair strand is calculated as the arithmetic mean of the individual measured values of these five measuring points.

2.0 more sample recipes

Table 3: Dye carrier

1 Ci ₂ -Ci ₄ fatty alcohol with 2 units of ethylene oxide (INCI name: Laureth-2) (manufacturer: COGNIS)

3 potassium oleate (manufacturer: COGNIS)

5 C ₁₆ -C ₁₈ fatty alcohol with approx. 50 units of ethylene oxide (INCI name: Ceteareth-50) (manufacturer: COGNIS) 6 1-Hydroxyethane-1, 1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (Manufacturer: Solutia)

10 Wheat protein hydrolyzate (active substance 40% by weight) (INCI name: Aqua (Water), Hydrolyzed Wheat Protein, Sodium Benzoate, Phenoxyethanol, Methylparaben, Propylparaben) (Manufacturer: Gelita)

Immediately prior to application to the hair, a dye carrier according to Table 3 was mixed with the oxidizer preparation according to Table 2 (vide supra) in a weight ratio of 4 to 5 to give a ready-to-use gel colorant.

Claims

Patent claims

1. Cosmetic composition containing in a cosmetic carrier at least one oxidizing agent and ginseng extract.

2. Cosmetic composition according to claim 1, characterized in that the oxidizing agent is hydrogen peroxide and / or at least one addition product thereof.

3. Cosmetic composition according to one of claims 1 or 2, characterized in that the ginseng extract contains at least one sapogenin.

4. Cosmetic composition according to claim 3, characterized in that the sapogenin is selected from at least one compound according to formula (I) and / or at least one glycosidic derivative thereof

wherein

R ¹ and R ² independently represent a hydrogen atom or a hydroxy group.

5. Cosmetic agent according to one of claims 1 to 4, characterized in that the glycosidic derivatives of the compounds of formula (I) are derived from glucopyranose, arabinopyranose, arabinofuranose, xylofuranose, xylopyranose and / or rhamnopyranose.

6. Cosmetic composition according to one of claims 1 to 5, characterized in that it additionally contains at least one protein or protein hydrolyzate selected from at least one member of the group, which is formed from pea protein, soy protein, almond protein, acacia protein, collagen and keratin and their Hydrolysates, contains.

7. Cosmetic composition according to one of claims 1 to 6, characterized in that it is gel-like.

8. Cosmetic composition according to claim 7, characterized in that it additionally

1, 0 to 15 wt .-% of a saturated or unsaturated, linear or branched alcohol having 8 to 36 carbon atoms,

0.1 to 15% by weight of a liquid fatty acid having 16 to 22 carbon atoms in the form of a water-soluble soap,

0.5 to 10 wt .-% of an adduct of 1 to 5 moles of ethylene oxide to a linear fatty alcohol having 8 to 22 carbon atoms,

0 to 10 wt .-% of an adduct of 15 to 100 moles of ethylene oxide on a linear fatty alcohol having 8 to 22 carbon atoms and

Contains 0 to 20 wt .-% of a low molecular weight water-soluble monoalcohol.

9. Cosmetic composition according to claim 8, characterized in that it contains as saturated or unsaturated, linear or branched alcohol having 8 to 36 carbon atoms technical fatty alcohols having 12 to 18 carbon atoms such as coconut, palm, palm kernel or Taigfettalkohol.

10. Cosmetic composition according to one of claims 8 or 9, characterized in that it additionally contains a water-soluble synthetic surfactant selected from the group of cationic, amphoteric, zwitterionic surfactants and fatty alkyl glycosides.

11. Cosmetic composition according to one of claims 8 to 10, characterized in that it additionally contains dicetylstearyl ether, Dicetylstearyloxiethylether, Dicetylstearyldioxiethylether and / or N, N-bis (2-Cetylstearyloxiethyl) aminoethanol.

12. Cosmetic composition according to one of claims 1 to 11, characterized in that it additionally contains at least one color changing agent.

13. Cosmetic composition according to one of claims 1 to 12, characterized in that it additionally contains a cationic polymer.

14. Use of a cosmetic composition according to any one of claims 1 to 13 for reducing the oxidant-induced skin irritation during the oxidative hair treatment.

15. Use of a cosmetic agent according to any one of claims 1 to 13 for reducing the oxidizing agent-induced impairment of the elasticity of the skin during the oxidative hair treatment.

16. Use of a cosmetic agent according to any one of claims 1 to 13 for reducing the oxidizing agent-induced impairment of hair conditioning during the oxidative hair treatment.

17. A process for the treatment of keratin fibers, in particular human hair, in which a cosmetic agent according to any one of claims 1 to 13 applied to the hair and rinsed again after a contact time.