DE10100928A1 - Coupler / developer and coupler / coupler hybrid dyes and hybrid dye intermediates - Google Patents

Abstract

Coupler / developer and coupler / coupler hybrid dyes and hybrid dye precursors of structure (I), DOLLAR AX - S - Y DOLLAR A in the X stands for a group which is derived from an oxidation dye precursor of the coupler type, DOLLAR AY stands for a group , which is derived from DOLLAR A - an oxidation dye precursor of the developer type or DOLLAR A - an oxidation dye precursor of the coupler type and DOLLAR AS stands for a direct bond or at least one spacer group, DOLLAR A are ideal for dyeing keratin fibers, especially human hair. By using dyes with these dyes, a number of problems that occur when using complex dye mixtures can be avoided or significantly minimized.

Description

The invention relates to new coupler / developer and coupler / coupler hybrid dyes and hybrid dye precursors, which are particularly suitable for dyeing keratin fibers are, the use of these dyes and dye precursors as well as these dyes and / or dyes containing dye precursors.

In the context of the products that are provided for the cosmetic treatment of the human body, agents for changing or shading the color of the scalp hair play an outstanding role. Apart from the bleaching agents, which bring about an oxidative lightening of the hair by breaking down the natural hair dyes, there are essentially three types of hair dye in the area of hair coloring:
So-called oxidation dyes are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components.

For temporary coloring, colorants or tints are usually used contain so-called direct draw as a coloring component. This is Dye molecules that pull directly onto the hair and do not have an oxidative process Need more color training. These dyes include, for example Henna known from antiquity for coloring body and hair.  

Furthermore, a novel dyeing process has received great attention recently. In this process, precursors of the natural hair dye melanin, in particular Special derivatives of indole or indoline, applied to the hair and form in the frame oxidative processes in hair practically nature-identical dyes. Such a process Ren with 5,6-dihydroxyindolines as dye precursors was in EP-B1-530 229 described. With, in particular multiple, use of agents with 5,6-dihydroxyin dolin, it is possible for people with gray hair to restore the natural hair color ben. Coloring can take place with atmospheric oxygen as the only oxidizing agent, so that no further oxidizing agents have to be used.

In principle, it is possible to use colorants with only one dye or one color formulate preliminary stage. With the exception of a few products, e.g. B. Forerunner of Containing melanins, such dyes are of little importance in practice obtained.

Rather, commercial hair dye products typically contain a mixture of about 3 to 8 different dyes and / or dye precursors. The single ones However, dyes usually have different absorbency, light, sweat, Rub and wash fastnesses, which also strongly depend on the structural properties and may depend on the condition of the hair. These differences are before particularly pronounced when, as has so far been indispensable for many nuances, direct Dyes are used to adjust the shade in oxidation dyes.

Therefore, extensive ver is often required when developing new hair dyes not only to achieve certain nuances, but above all to ensure that the coloring over the desired period in both the shade and in the Intensity is stable.

It has now surprisingly been found that many of the above problems can be completely or at least partially avoided if substances are used be on the properties of an oxidation dye intermediate of the coupler type as well as the properties of an oxidation dye precursor of the developer type or another oxidation dye intermediate of the coupler type.  

In particular, it has been shown that the dyes have a very good, with known Hair dyes or hair dye precursors comparable absorption on the Have hair and lead to brilliant, intensive hair coloring. Due to the molecular linkage, the problem can be different Fastness properties of the corresponding dye precursors in many cases largely overcome.

Such substances which can be used in hair dyes and which are further referred to as "hybrid dyes" are new.

A first subject of the present invention are therefore coupler / developer and coupler / coupler hybrid dyes and hybrid dye precursors, in particular for dyeing keratin fibers, of structure (I),

XSY (I)

in the
X represents a group derived from a coupler type oxidation dye precursor;
Y stands for a group derived from

• - a developer type oxidation dye precursor or
• - a coupler-type oxidation dye precursor; and

S stands for a direct bond or at least one spacer group, with the proviso that X, Y and S are not chosen such that they correspond to one of the compounds of the general formulas (II), (III) or (IV) listed below :

where the compounds of the general formulas (II) and (III) R ¹ to R ¹⁰ independently of one another are H, (C ₁ -C ₄ ) -alkyl, hydroxy- (C ₂ -C ₃ ) -alkyl, (C ₁ -C ₄ ) alkoxy- (C ₂ - C ₃ ) alkyl, amino- (C ₂ -C ₃ ) alkyl or 2,3-dihydroxypropyl and n represents an integer from 1 to 6 and the groups -NR ¹ R ² and -NR ⁷ R ^{8 are} either in positions 4 and 4 'or in positions 5 and 5';

where for the compounds of the general formula (IV) X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ are nitrogen or CR ⁶ , CR ⁷ , CR ⁸ , CR ⁹ , CR ¹⁰ , at least one and at most three of the Radicals X ⁶ to X ^{10 can} denote nitrogen and optionally the radicals R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ independently of one another hydrogen, a halogen atom, a cyano group, a hydroxyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ alkylthioether group, a mercapto group, a nitro group, an amino group, a C ₁ -C ₄ alkylamino group, a di (C ₁ -C ₄ ) alkylamino group, a trifluoromethane group , a -C (O) H group, a -C (O) CH ₃ group, a -C (O) CF ₃ group, a -Si (CH ₃ ) ₃ group, a -C (O) -NH ₂ group, a C ₁ -C ₄ hydroxyalkyl group, a C ₃ -C ₄ dihydroxyalkyl group, a -CH = CHR ¹¹ group, a - (CH ₂ ) _p -CO ₂ R ¹² group or one - (CH ₂ ) _p -R ¹³ group with p = 1, 2, 3 or 4, a -C (R ¹⁴ ) = NR ¹⁵ group or a C (R ¹⁷ ) Mean H- NR ¹⁸ R ¹⁹ group; R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group, a C ₂ -C ₄ -dihydroxyalkyl group or a C ₁ -C ₄ -alkoxy - (C ₁ -C ₄ ) alkyl group, or R ¹ and R ² or R ³ and R ^{4 form} a four-membered to eight-membered aliphatic ring, at least two of the radicals R ¹ to R ^{4 being} hydrogen; R ⁵ is hydrogen, a hydroxy group, a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group or a C ₁ -C ₄ alkoxy group; R ¹¹ is hydrogen, a hydroxy group, an amino group, a CO ₂ R ¹² group or a -C (O) CH ₃ group; R ¹² , R ¹⁴ and R ^{17 are} independently hydrogen or a C ₁ -C ₄ alkyl group; R ¹³ is an amino group or a nitrile group; R ¹⁵ , R ¹⁸ and R ¹⁹ independently of one another are equal to hydrogen, a hydroxy group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₃ -C ₄ dihydroxyalkyl group or a radical of the formula

is; R ¹⁶ is hydrogen, an amino group or a hydroxy group.

The compounds according to structure (I) are organic using conventional synthetic methods Chemistry accessible.

As already explained above, the structural principles of known dye classes form the Basis for the newly developed hybrid dyes.

Group X is derived from connections belonging to the class of Oxidation dye intermediates of the coupler type are assigned.

As coupler components are usually m-phenylenediamine derivatives, naphthols, Re sorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are used.

Preferred classes of coupler-type oxidation dye precursors from which Group X can be derived are:

• - 3-aminophenol and its derivatives;
  Preferred representatives are 5-amino-2-methylphenol, 5- (3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 3-amino-6- methoxy-2-methylaminophenol, 2,6-dimethyl-3-aminophenol, 3-tri-fluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy- 2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3-dimethylamino-phenol, 3-diethylamino-phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol;
• - 2-aminophenol and its derivatives;
• - 1,3-diaminobenzene and its derivatives;
  Preferred representatives are 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 1,3-bis- (2nd , 4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, 1,2-bis (2,4 -diaminophenoxy) benzene and 1,3-bis (2,4-diaminophenoxy) benzene;
• - 1,2-diaminobenzene and its derivatives;
  Preferred representatives are 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene;
• - Di- and trihydroxybenzenes and their derivatives;
  Preferred representatives are resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chloro-resorcinol, 4-chloro-resorcinol, pyrogallol and 1,2,4-trihydroxybenzene as well as resorcinol dimethyl ether;
• - pyridine derivatives;
  Preferred representatives are 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-3,4-diaminopyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6 -dimethoxypyridin;
• - naphthalene derivatives;
  Preferred representatives are 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy naphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxy naphthalene and 2,3-dihydroxynaphthalene and also 1-aminonaphthalene;
• - morpholine derivatives;
  Preferred representatives are 6-hydroxybenzomorpholine and 6-aminobenzomorpholine;
• - quinoxaline derivatives;
  A preferred representative is 6-methyl-1,2,3,4-tetrahydroquinoxaline;
• - pyrazole derivatives;
  A preferred representative is 1-phenyl-3-methylpyrazol-5-one;
• - indole derivatives;
  Preferred representatives are 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole;
• - methylenedioxybenzene derivatives;
  Preferred representatives are 3,4-methylenedioxyphenol, 1-amino-3,4-methylenedioxy benzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene;
• - pyrimidine derivatives;
  Preferred representatives are 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;
• Heterocyclic compounds, as described in WO 97/35550, WO 97/35552, WO 97/35553, WO 98/08485 and WO 98/08486, to which expressly Reference is disclosed.

Particularly preferred coupler substances are 3-aminophenol, 5-amino-2- methylphenol, 2,4-dichloro-3-aminophenol, 2-chloro-6-methyl-3-aminophenol, 2-methyl-4- chloro-5-aminophenol, 1,3-phenylenediamine, 1,3-bis (2 ', 4'-diaminophenoxy) propane, Resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylre sorcinol, 2-chloro-resorcinol, 4-chloro-resorcinol, 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, 1-phenyl-3-methyl-pyrazol-5-one, 2-amino-3-hydroxypyridine and 2,6-dihydroxy-3,4-dimethylpyridine.

Regarding further coupler-type oxidation dye precursors, of which the Group X can derive, is further expressly based on the known monographs, z. B. Ch. Zviak, The Science of Hair Care, Chapter 8 (pages 264-267), published as a volume 7 of the series "Dermatology" (Ed .: Ch., Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in diskette form from Federal Association of German Industry and Trade Companies for Medicines, Reform goods and personal care products e. V., Mannheim, referred to.

Group Y stands for a group derived from

• - a developer type oxidation dye precursor or
• - a coupler-type oxidation dye precursor

According to a first, preferred, embodiment of the present invention the group Y ab from a developer type oxidation dye precursor.  

Primary aromatic amines with a. Are usually used as developer components further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4- Aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

Preferred classes of developer type oxidation dye precursors from which Group Y can be derived are:

• - 1,4-diaminobenzene and its derivatives;
  Preferred representatives are p-phenylenediamine, p-toluenediamine, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis- (2-hydroxy-ethyl) -p-phenylenediamine, bis- (4- aminophenyl) amine, 2- (2,5-diaminophenoxy) ethanol, 1,3-bis (N (2-hydroxyethyl) - N (4-aminophenylamino)) - 2-propanol, 1,10-bis- (2, 5-diaminophenyl) -1,4,7,10-tetraoxadecane and N, N'-bis- (4'-aminophenyl) -1,4-diazacycloheptane and corresponding compounds with one or more halogen atoms, especially chlorine and fluorine, on the benzene ring ;
• - 1,2-diaminobenzene and its derivatives;
• - 1,2,4-triaminobenzene and its derivatives;
• - 4-aminophenol and its derivatives;
  Preferred representatives are p-aminophenol, 2-chloro-4-aminophenol, 4-amino-3-methylphenol, 2-hydroxyethylamino-4-aminophenol, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2 Hydroxymethyl-4-aminophenol, 4-amino-2- ((diethylamino) methyl) phenol, bis (2-hydroxy-5-aminophenyl) methane, 4-amino-2- (2-hydroxyethoxy) phenol ;
• - 2-aminophenol and its derivatives;
  Preferred representatives are o-aminophenol and 2-amino-5-methylphenol;
• - diaminopyridine derivatives;
  Preferred representatives are 2,5-diaminopyridine, 2,5-diamino-4-methylpyridine, 2,5-diamino-4,6-dimethylpyridine;
• - triaminopyridine derivatives;
  a preferred representative is 2,3,5-triaminopyridine;
• - heterocyclic hydrazones;
• - 4-aminopyrazole derivatives;
  Preferred representatives are 4,5-diamino-1,3-dimethylpyrazole, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5 and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94/08970 such as z. B. 4,5-diamino-1- (2'-hydroxyethyl) pyrazole and 4,5-diamino-1- (4'-chlorobenzyl) pyrazole;
• - pyrimidine derivatives;
  Preferred representatives are 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triamino pyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diamino pyrimidine and 2-dimethylamino-4,5,6-triaminopyrimidine.

Particularly preferred developer substances are p-phenylenediamine and p-Toluy lendiamine, 1,2,4-phenylenetriamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-dia minobenzene, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) - ethanol, N, N'-bis- (2'-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, 2- (2 ', 5'-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 4-amino-2 - ((diethylamino) - methyl) phenol, 2-aminomethyl-4-aminophenol, 2,5-diaminopyridine, 2,5-diamino-4- methylpyridine, 2,5-diamino-4,6-dimethylpyridine, 2,3,5-triaminopyridine, 2,4,5,6-tetra aminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine and 4,5-diamino-1,3- dimethylpyrazole, 4,5-diamino-1- (2'-hydroxyethyl) pyrazole.

Regarding other developer type oxidation dye precursors, of which the Group Y can be derived, is further expressly based on the known monographs, z. B. Ch. Zviak, The Science of Hair Care, Chapter 8 (pages 264-267), published as a volume 7 of the series "Dermatology" (Ed .: Ch., Culnan and H. Maibach), publisher Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the European Community, available in diskette form from Federal Association of German Industry and Trade Companies for Medicines, Reform goods and personal care products e. V., Mannheim, referred to.

It can also be preferred according to the invention that the group Y is derived from a developer component which is a p-phenylenediamine derivative or one of its physiologically tolerable salts. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

• G ¹ represents 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 ) alkoxy (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G ² represents 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 ) alkoxy (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, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ to C _4- polyhydroxyalkyl, a C ₁ to C ₄ hydroxyalkoxy, a C ₁ to C ₄ acetylaminoalkoxy, a C ₁ to C ₄ mesylaminoalkoxy or a 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
• - If G ³ and G ⁴ are ortho to each other, they can together form a bridging α, ω-alkylenedioxo group, such as a methylene or ethylenedioxy group.

Examples of the C ₁ -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 to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Further preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. An example of a C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (II) 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 (E1) 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-phenylene diamine, 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-methyl- aniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -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- Acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8- Diaminobenzo-1,4-dioxane and their physiologically tolerable salts.

P-Phenylenediamine derivatives of the formula (E1) which are very particularly preferred according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

It can further be preferred according to the invention that the group Y is derived from a developer component containing at least two aromatic nuclei, the with Amino and / or hydroxyl groups are substituted.  

Among these binuclear developer components, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

in which:

• Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ to C ₄ alkyl radical, by a C ₁ to C ₄ hydroxyalkyl radical and / or by a bridging Y. is or is possibly part of a bridging ring system,
• - The bridge Y stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,
• - G ⁵ and G ⁶ independently of one another represent 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 aminoalkyl radical or a direct connection to the 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 bridging Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that
• - The compounds of formula (E2) contain only one bridge Y per molecule and  
• - The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

According to the invention, the substituents used in formula (E2) are analogous to the above Executions defined.

Preferred dinuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) - tetramethylene diamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylene diamine, N, N'-bis (4-methylaminophenyl) tetramethylene diamine, N, N'-diethyl-N, N'-bis- (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 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 its physiologically acceptable salts.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2- hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiological tolerable salts.

Furthermore, it can be preferred according to the invention that the group Y is derived from developer components which are a p-aminophenol derivative or one of its physiologically tolerable salts. P-Aminophenol derivatives of the formula (E3) are particularly preferred

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 ₁ - to C ₄ ) -alkylamino radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ hydroxyalkyl aminoalkyl (C ₁ to C _4), or (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄₎ alkyl, 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 ₁ to C ₄ ) alkyl, a C ₁ to C ₄ aminoalkyl or a C ₁ to C ₄ cyanoalkyl,
• G ¹⁵ represents 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 represents hydrogen or a halogen atom.

According to the invention, the substituents used in formula (E3) are analogous to the above Executions defined.

Preferred p-aminophenols of the formula (E3) 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-fluorophenol, 4-amino-2-chlorophenol, 4- Amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) phenol and their physiolo gisch compatible salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4- Amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2- (diethyl aminomethyl) phenol.  

Furthermore, the developer component can be selected from o-aminophenol and its Derivatives such as 2-amino-4-methylphenol, 2-amino-4-chlorophenol or 2- Amino-5-methylphenol.

Furthermore, group Y can be derived 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 patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'- Methoxyphenyl) amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2- (β-methoxy ethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 23 59 399, the Japanese patent application 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 the patents DE 38 43 892, DE 41 33 957 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- (β-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 pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole- [1,5-a] pyrimidine of the following formula (E4) and its tautomeric forms, provided there is a tautomeric equilibrium:

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently 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 radical is a (C ₁ - to C ₄ ) -alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical which is optionally protected by an acetyl-ureide or a sulfonyl radical can be a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) - aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) - aminoalkyl radical,
• - The X radicals 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 radical, a C ₁ to C ₄ aminoalkyl, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) - aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links, 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 radical, 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 not equal to 0,
• - if p + q is 2, n has the value 0, 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);

• - if p + q is 1, n has the value 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7);

According to the invention, the substituents used in formula (E4) are analogous to the above Executions defined.

If the pyrazole- [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is illustrated, for example, in the following scheme:

Among the pyrazole- [1,5-a] pyrimidines of the above formula (E4), one can mention in particular:

• - pyrazole [1,5-a] pyrimidine-3,7-diamine;
• - 2,5-dimethyl-pyrazol [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethyl-pyrazol [1,5-a] pyrimidine-3,5-diamine;
• - 3-aminopyrazole [1,5-a] -pyrimidin-7-ol;
• - 3-aminopyrazole [1,5-a] pyrimidin-5-ol;
• - 2- (3-aminopyrazole [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazole [1,5-a] pyrimidine-3-ylamino) ethanol;  
• - 2 - [(3-aminopyrazole [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-aminopyrazole [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 5,6-dimethylpyrazole [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazole [1,5-a] pyrimidine-3,7-diamine;
• - 3-amino-7-dimethylamino-2,5-dimethylpyrazole [1,5-a] -pyrimidine;

as well as their physiologically tolerable salts and their tautomeric forms, if one tautomeric equilibrium is present.

The pyrazole- [1,5-a] pyrimidines of the above formula (E4) can be as in the literature described by cyclization starting from an aminopyrazole or from hydrazine getting produced. According to a second, also preferred, embodiment of the In the present invention, group Y is derived from one Coupler type oxidation dye precursor. Suitable and preferred groups Y are derived in principle from the same connections, which are described in detail above under the Definition of group X are listed.

Although according to the invention within the defined group of hybrid dyes Structure (I) such compounds should not be excluded, in which the Groups X and Y are identical, so the compounds according to this Embodiment usually different groups X and Y on.

According to the invention, one of the two groups X or Y preferably contains one heterocyclic five or six ring.

According to a first embodiment of the invention, the group S is in the Structural formula (I) for a direct bond.

The spacer group S can have a direct single bond between the groups X and Y his.

In these cases, an interaction of the π-electron Systems of groups X and Y occur, so that usually The light absorption behavior of the hybrid dye differs from that of groups X and Y  clearly differentiates. This results in a significantly changed color tone on the hair achieved in comparison to discolorations with a mixture of appropriate dyes be performed that correspond to groups X and Y.

A key idea of the present invention, however, is that com plexer dye mixtures in many areas, e.g. B. in terms of winding capacity and Wash fastness to fix any problems that arise without losing the shade and nuance change.

It is therefore generally preferred according to the invention that in the coupler / developer and coupler / coupler hybrid dyes and hybrid dye precursors of structure (I),

XSY (I)

S represents at least one spacer group.

S is preferably a spacer group via which there is no interaction of the π electron systems of groups X and Y. S therefore preferably contains at least one carbon atom with sp ³ hybridization on the direct connecting line between the groups X and Y.

If there are several spacer groups, for example two spacer groups, these are preferably, independently of one another, an unsubstituted or substituted one Alkylene group, each of which attacks terminally on nitrogen atoms of groups X and Y.

Preferred spacer groups S are:

• - Alkylene groups of the general formula -C _n H _2n -, in particular - (CH ₂ ) _n -, in which n is an integer, in particular a number from 1 to 8 and very particularly preferably a number from 1 to 4;
  Alkylene groups preferred according to the invention are the methylene, 1,2-ethylene and 1,3-propylene group;
• - Cycloaliphatic groups such as cyclopentyl, cyclohexyl and cycloheptyl groups;  
• - Mono- and polyhydroxyalkylene groups of the general formula -C _n H _2n-x (OH) _x , in which n is an integer, in particular a number from 1 to 8 and very particularly preferably a number from 1 to 4, and x represents an integer, in particular a number from 1 to 3;
  Preferred hydroxyalkylene groups are the hydroxymethylene, the hydroxy-1,2-ethylene, the 2-hydroxy-1,3-propylene, the 2,3-dihydroxy-1,3-propylene and the 2,3-dihydroxy-1 , 4-butylene group;
• dialkylene amino groups optionally substituted on the alkyl chains, in particular those of the general formula - (CH ₂ ) _n -N (Z) - (CH ₂ ) _m -,
  in which n and m independently of one another can represent an integer from 1 to 8, in particular from 1 to 4, but preferably stand for the same number, and Z represents hydrogen, a C _1-8 -, in particular C _1-4 -, alkyl group, a C _1-8 -, especially C _1-4 -, monohydroxyalkyl group, a C _2-8 -, especially C _2-4 -dihydroxyalkyl group or a C _3-8 -, especially C _3-4 -trihydroxyalkyl group stands,
  as well as those of the general formula
  in which a and b independently of one another represent integers from 0 to 4 and c and d stand for 0 or 1 with the proviso that c = 0 if a = 0 and d = 0 if b = 0, n stands for an integer from 1 to 5 and m stands for an integer from 1 to 3, with the proviso that the sum n + m is 3 to 8. The 1,4-piper azo group is particularly preferred;
• - Trialkylenediamino groups optionally substituted on the alkyl chains, in particular those of the general formula - (CH ₂ ) _n -N (Z) - (CH ₂ ) _m -N (A) - (CH ₂ ) _p -, in which n, m and p can independently represent an integer from 1 to 8, in particular from 1 to 4, but n and m preferably represent the same number, and Z and A independently of one another represent hydrogen, a C _1-8 -, in particular C _1-4 alkyl group, a C _1-8 , especially C _1-4 monohydroxyalkyl group, a C _2-8 , especially C _2-4 dihydroxyalkyl group or a C _3-8 , especially C _3-4 trihydroxyalkyl stand group;
• ether groups optionally substituted on the alkyl chains, in particular those of the general formula - (CH ₂ ) _n -O- (CH ₂ ) _m -, in which n and m independently of one another for an integer from 1 to 8, in particular from 1 to 4 , can stand, but before stands for the same number;
• - Polyether groups optionally substituted on the alkyl chains, in particular those of the general formula - (CH ₂ ) _n -O- (CH ₂ ) _m -O- (CH ₂ ) _m -O- (CH ₂ ) _n -, in which n and m can independently represent an integer from 1 to 8, in particular from 1 to 4, but preferably stand for the same number;
• - Sulfur-containing groups, in particular groups of the general formula - (CH ₂ ) _n -S (O) _o - (CH ₂ ) _m -, in which n and m independently of one another for an integer from 1 to 8, in particular from 1 to 4 can stand, but preferably stand for the same number, and o stands for 0, 1 or 2.

The spacers S are free in the hybrid dyes according to the invention via their two Bonds linked to the groups X and Y so that they each as a substituent on the Replacing a hydrogen atom of the dye or dye precursor molecules, that underlie groups X and Y.

According to a first preferred embodiment, the spacer group S takes the place of a hydrogen atom as a substituent which is bonded directly to a ring system of the group X or Y. Examples of such ring systems are

• - aromatic and cycloaliphatic hydrocarbon ring systems, in particular Benzene, naphthalene, anthracene, naphthoquinone and anthraquinone systems;
• - Heterocyclic ring systems, especially pyridine, pyrazole, pyrimidine, indole and Indolinsysteme.

According to a second preferred embodiment, the spacer group S occurs as a substi does instead of a hydrogen atom of a primary or secondary amino group, which directly or via an aliphatic hydrocarbon group to an aromatic, cycloaliphatic or heterocyclic ring system is bound.

According to a third embodiment, the spacer group S takes the place of a substituent of the hydrogen atom of a hydroxyl group, directly or via an aliphatic  Hydrocarbon group to an aromatic, cycloaliphatic or heterocyclic Ring system is bound.

The hybrid dyes according to the invention are outstandingly suitable for coloring kerati fibers. Among the keratin fibers are furs, wool, feathers and in particular to understand their human hair. Use in other areas, too special in color photography, but nothing stands in the way.

A second object of the present invention are therefore agents for coloring kerati African fibers, especially human hair, which have a hybrid dye according to the structure tur (I) included. Of course, the teaching of the invention also includes such Agents containing combinations of more than one hybrid dye of structure (I).

The agents according to the invention contain the hybrid dyes of structure (I) usually in amounts of 0.01% by weight - 10% by weight, based on the total Colorants, amounts of 0.05% by weight - 5% by weight, in particular amounts of 0.1% by weight % -3% by weight are preferred.

The agents for dyeing human hair according to the invention can all be used for such agents contain common ingredients.

The colorants according to the invention preferably contain at least one further color substance, another dye precursor and / or an indole or indoline derivative as Me lanin precursor.

In a first embodiment, those colorants are particularly preferred which, in addition to a hybrid dye of structure (I) ent at least one oxidation dye intermediate hold. These oxidation dye precursors can be of the coupler type as well be of the developer type.

The developer type oxidation dye precursors include, for example, primary ones aromatic amines with another free one in the para or ortho position or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic  Hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its deri vate into consideration.

Preferred classes of developer types as dye / dye precursor according to the invention are:

• - 1,4-diaminobenzene and its derivatives;
  Preferred representatives are p-phenylenediamine, p-toluenediamine, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis- (2-hydroxy-ethyl) -p-phenylenediamine, bis- (4- aminophenyl) amine, 2- (2,5-diaminophenoxy) ethanol, 1,3-bis (N (2-hydroxyethyl) - N (4-aminophenylamino)) - 2-propanol, 1,10-bis- (2, 5-diaminophenyl) -1,4,7,10-tetraoxadecane and N, N'-bis- (4'-aminophenyl) -1,4-diazacycloheptane, and corresponding compounds with one or more halogen atoms, in particular chlorine and fluorine, on benzene ring;
• - 1,2-diaminobenzene and its derivatives;
• - 1,2,4-triaminobenzene and its derivatives;
• - 4-aminophenol and its derivatives;
  Preferred representatives are p-aminophenol, 2-chloro-4-aminophenol, 4-amino-3-methylphenol, 2-hydroxyethylamino-4-aminophenol, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2 Hydroxymethyl-4-aminophenol, 4-amino-2- ((diethylamino) methyl) phenol, bis (2-hydroxy-5-aminophenyl) methane, 4-amino-2- (2-hydroxyethoxy) phenol ;
• - 2-aminophenol and its derivatives;
  Preferred representatives are o-aminophenol and 2-amino-5-methylphenol;
• - diaminopyridine derivatives;
  Preferred representatives are 2,5-diaminopyridine, 2,5-diamino-4-methylpyridine, 2,5-diamino-3-methylenamino-4,6-dimethylpyridine;
• - triaminopyridine derivatives;
  a preferred representative is 2,3,5-triaminopyridine;
• - heterocyclic hydrazones;
• - 4-aminopyrazole derivatives;
  Preferred representatives are 4,5-diamino-1,3-dimethylpyrazole, 1-phenyl-3-carboxyamido-4-amino-pyrazolon-5 and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94/08970 such as z. B. 4,5-diamino-1- (2'-hydroxyethyl) pyrazole and 4,5-diamino-1- (4'-chlorobenzyl) pyrazole;
• - pyrimidine derivatives;
  Preferred representatives are 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triamino pyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diamino pyrimidine and 2-dimethylamino-4,5,6-triaminopyrimidine.

Particularly preferred developer types or substances are these aforementioned formulas E1, E2, E3 and E4 and in particular p-phenylenediamine, p-Toluy lendiamine, 1,2,4-phenylenetriamine, p-aminophenol, 1- (2'-hydroxyethyl) -2,5-dia minobenzene, N, N-bis- (2'-hydroxyethyl) -p-phenylenediamine, 2- (2 ', 5'-diaminophenyl) - ethanol, N, N'-bis- (2'-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, 2- (2 ', 5'-diaminophenoxy) ethanol, 4-amino-3-methylphenol, 4-amino-2 - ((diethylamino) - methyl) phenol, 2-aminomethyl-4-aminophenol, 2,5-diaminopyridine, 2,5-diamino-4- methylpyridine, 2,5-diamino-3-methylenamino-4,6-dimethylpyridine, 2,3,5-triaminopyridine 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6- diaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine and 4,5-diamino-1,3- dimethylpyrazole, 4,5-diamino-1- (2'-hydroxyethyl) pyrazole.

For example, m-phenylene comes as oxidation dye precursors of the coupler type diamond derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophe nol derivatives into consideration.

Preferred classes of coupler types according to the invention are:

• - 3-aminophenol and its derivatives;
  Preferred representatives are 5-amino-2-methylphenol, 5- (3-hydroxypropylamino) -2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 3-amino-6- methoxy-2-methylaminophenol, 2,6-dimethyl-3-aminophenol, 3-tri-fluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy- 2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3-dimethylamino-phenol, 3-diethylamino-phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol;
• - 2-aminophenol and its derivatives;
• - 1,3-diaminobenzene and its derivatives;
  Preferred representatives are 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 1,3-bis- (2nd , 4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, 1,2-bis (2,4 -diaminophenoxy) benzene and 1,3-bis (2,4-diaminophenoxy) benzene;
• - 1,2-diaminobenzene and its derivatives;
  Preferred representatives are 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene;
• - Di- and trihydroxybenzenes and their derivatives;
  Preferred representatives are resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chloro-resorcinol, 4-chloro-resorcinol, pyrogallol and 1,2,4-trihydroxybenzene as well as resorcinol dimethyl ether;
• - pyridine derivatives;
  Preferred representatives are 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-3,4-diaminopyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6 -dimethoxypyridin;
• - naphthalene derivatives;
  Preferred representatives are 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy naphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxy naphthalene and 2,3-dihydroxynaphthalene and also 1-aminonaphthalene;
• - morpholine derivatives;
  Preferred representatives are 6-hydroxybenzomorpholine and 6-aminobenzomorpholine;
• - quinoxaline derivatives;
  A preferred representative is 6-methyl-1,2,3,4-tetrahydroquinoxaline;
• - pyrazole derivatives;
  A preferred representative is 1-phenyl-3-methylpyrazol-5-one;
• - indole derivatives;
  Preferred representatives are 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole;
• - methylenedioxybenzene derivatives;
  Preferred representatives are 3,4-methylenedioxyphenol, 1-amino-3,4-methylenedioxy benzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene;
• - pyrimidine derivatives;
  Preferred representatives are 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;
• Heterocyclic compounds, as described in WO 97/35550, WO 97/35552, WO 97/35553, WO 98/08485 and WO 98/08486, to which expressly Reference is disclosed.

Particularly preferred coupler substances are 3-aminophenol, 5-amino-2- methylphenol, 2,4-dichloro-3-aminophenol, 2-chloro-6-methyl-3-aminophenol, 2-methyl-4- chloro-5-aminophenol, 1,3-phenylenediamine, 1,3-bis (2 ', 4'-diaminophenoxy) propane, Resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylre sorcinol, 2-chloro-resorcinol, 4-chloro-resorcinol, 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, 1-phenyl-3-methyl-pyrazol-5-one, 2-amino-3-hydroxypyridine and 2,6-dihydroxy-3,4-dimethylpyridine.

In the context of this embodiment, the following may be preferred:

• - Hybrid dye of structure (I) with a group X and / or Y, derived from one Oxidation dye intermediate of the coupler type, in combination with at least one another developer type oxidation dye precursor
• - Hybrid dye of structure (I) with a group Y, derived from an oxidation dye intermediate of the developer type, in combination with at least one white tere oxidation dye intermediate of the coupler type

In a second embodiment, those colorants are preferred which, in addition to a Hybrid dye of structure (I) contain at least one substantive dye.

Such substantive dyes to be used according to the invention are, for example Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones and indophenols.  Preferred direct dyes are those under the international designation HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 13, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 7, Basic Blue 26, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Basic Violet 2, Basic Violet 14, Acid Violet 43, Disperse Black 9, Acid Black 52, Basic Brown 16 and Basic Brown 17 known compounds and 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, 1- (2'- Hydroxyethyl) amino-4-methyl-2-nitrobenzene, picramic acid, 2-amino-6-chloro-4- nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4- nitrobenzene. The cationic direct dyes that are under the trademark Arianor® are particularly preferred direct dyes.

Furthermore, the agents according to the invention can also be naturally occurring colors contain substances such as those in henna red, henna neutral, henna black, Chamomile flower, sandalwood, black tea, sapwood, sage, blue wood, madder root, Catechu, Sedre and Alkanna root are included.

The inventive agents according to this embodiment contain the direct dyes preferably in an amount of 0.01 to 20 wt .-%, based on the entire colorant.

In a third embodiment, those colorants which, in addition to a hybrid dye of structure (I) at least one derivative of indole or indoline as Precursor of melanin included.

Those indoles and indolines which have at least one Hy droxy and / or amino group, preferably as a substituent on the six-membered ring. This Groups can carry further substituents, e.g. B. in the form of etherification or Ver esterification of the hydroxy group or an alkylation of the amino group. Connections with two of these groups, especially two hydroxy groups, one or both of which etherified or esterified are particularly preferred.  

Dye precursors which are particularly preferred according to the invention are derivatives of indoline, such as the 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxy indoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxy indoline-2-carboxylic acid, 5-hydroxyindoline, 6-hydroxyindoline, 5-aminoindoline, 6- Aminoindoline and 4-aminoindoline.

Derivatives of 5,6-dihydroxyindoline of the formula (Va) are very particularly preferred,

in the independently of each other
R ¹ represents hydrogen, a C1-C4-alkyl group, a C1-C4-hydroxyalkyl group, a C3-C6-cycloalkyl group, a vinyl group or an allyl group,
R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
R ³ represents hydrogen or a C1-C4 alkyl group,
R ⁴ stands for hydrogen, a C1-C4-alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C1-C4-alkyl group or an optionally substituted phenyl group, and
R ⁵ stands for one of the groups mentioned under R ⁴ , or a physiologically compatible salt of these compounds with an organic or inorganic acid.

Preferred representatives according to the invention are 5,6-dihydroxyindoline, N-methyl-5,6-dihy doxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6- dihydroxyindoline. The main body, the 5,6-dihydroxyindoline, is very special Trains t.  

Indoles preferred according to the invention are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxy indole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihy hydroxy indole, 5,6-dihydroxyindole-2-carboxylic acid, 5-hydroxyindole, 6-hydroxyindole, 5- Aminoindole, 6-aminoindole and 4-aminoindole.

Derivatives of 5,6-dihydroxyindole of the formula (Vb) are particularly preferred,

in the independently of each other
R ¹ represents hydrogen, a C1-C4-alkyl group, a C1-C4-hydroxyalkyl group, a C3-C6-cycloalkyl group, a vinyl group or an allyl group,
R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
R ³ represents hydrogen, a C1-C4-alkyl group or a group -CH ₂ -NR ⁷ R ⁸ , in which R ⁷ and R ⁸ independently of one another represent hydrogen or a C1-C4-alkyl group,
R ⁴ stands for hydrogen, a C1-C4-alkyl group or a group -CO-R ⁶ , in which R ⁶ stands for a C1-C4-alkyl group or an optionally substituted phenyl group, and
R ⁵ stands for one of the groups mentioned under R ⁴ , or a physiologically compatible salt of these compounds with an organic or inorganic acid.

Preferred representatives according to the invention are 5,6-dihydroxyindole, N-methyl-5,6-dihy hydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihy droxyindol. The main body, the 5,6-dihydroxyindole, is very particularly preferred.  

The indoline and indole derivatives contained in the agents according to the invention can both as free bases and in the form of their physiologically tolerable salts with anor ganic or organic acids, e.g. B. the hydrochloride, sulfate and hydrobro mide, can be used.

Of course, the present invention also includes agents which contain more than one indoline or indole derivative or mixtures of indoline and indole derivatives.

The indole or indoline derivatives in the agents according to the invention are usually in Contain amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In the context of this embodiment, the following may be preferred:

• - Hybrid dye of structure (I) with a group Y, derived from an oxidation dye intermediate of the coupler type, in combination with at least one derivative of indole or indoline as a precursor of melanin,
• - Hybrid dye of structure (I) with a group Y, derived from an oxidation dye-precursor of the developer type, in combination with at least one derivative of indole or indoline as a precursor of melanin.

In the context of the embodiments mentioned, it is not necessary for the oxides tion dye precursors, substantive dyes or melanin precursors represent uniform connections. Rather, in the hair dye according to the invention average, due to the manufacturing process for the individual dyes, in below orderly quantities, other components may be included, unless these Adversely affect the coloring result or for other reasons, e.g. B. toxicological, must be excluded.

Regarding the usable in the hair coloring and tinting agents according to the invention Dyes continue to be expressly referred 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 "Dermato logy "(Ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European inventory of cosmetic raw materials", published by the  European Community, available in disk form from the Federal Association of German Industrial and trading company for pharmaceuticals, health products and personal care tel e. V., Mannheim, referred to.

Agents according to the invention, comprising an additional hybrid dye of structure (I), in which group Y is derived from an indole or indoline type melanin precursor, contained according to a preferred variant of this embodiment in addition to those mentioned Hybrid dyes no other dyes or dye precursors.

According to a further preferred variant, in particular contain according to the invention Agent with an additional hybrid dye of structure (I), in which the group Y derived from an indole or indoline type melanin precursor, and / or with one Melanin precursors furthermore at least one amino acid or an oligopeptide.

Amino acids in the sense of the invention are those substances which have at least one amino group and at least one -COOH or -SO ₃ H group.

Preferred amino acids are amino carboxylic acids, especially α-amino carboxylic acids and ω-aminocarboxylic acids. Among the α-aminocarboxylic acids are arginine, Lysine, ornithine and histidine are particularly preferred.

The amino acids can preferably be added to the agents according to the invention in free form will give. It is also possible to use the amino acids in salt form. preferred Salts are then the compounds with hydrohalic acids, especially the hydro chloride and the hydrobromide.

Very particularly preferred amino acids are lysine and especially arginine, in particular used in free form, but also as hydrochloride.

Furthermore, the amino acids can also be in the form of oligopeptides and protein hydro lysates are used if it is ensured that the required amounts of ver contain bonds that correspond to the definition of amino acids according to the invention  are. In this context, the disclosure of DE-OS 22 15 303 referred to, to which express reference is made.

Of course, the invention also includes those agents that have two or more amino contain acids or oligopeptides. Combinations of arginine with are preferred another amino acid or an oligopeptide.

The agents according to the invention preferably contain the amino acid or the oligopeptide in amounts of 0.1 to 10% by weight, in particular 1 to 4% by weight, based on the total Medium.

Hair dye, especially if the coloration is oxidative, be it with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually slightly acidic to alkaline, d. H. adjusted to pH values in the range from about 5 to 11. For this purpose, the colorants contain alkalizing agents, usually alkali or alkaline earth metal hydroxides, ammonia or organic amines.

According to a special embodiment of the present invention, the ami serves nonic acid or the oligopeptide not only intensifying the coloration, but via also takes, at least in part, the function of the alkalizing agent. As part of the In this embodiment, such amino acids and oligopeptides are preferred used, whose 2.5 wt .-% solutions in water have a pH of 9 and greater exhibit. Such amino acids are the preferred arginine compounds and lysine. In the context of this embodiment, the further alkalizing agent preferably selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-pro Pandiol, 2-amino-2-methylbutanol and triethanolamine as well as alkali and alkaline earth metal hydroxides is formed. In particular monoethanolamine, triethanolamine and 2- Amino-2-methyl-propanol and 2-amino-2-methyl-1,3-propanediol are within the scope of these Group preferred. Also the use of ω-amino acids such as ω-aminocaproic acid is preferred as an alkalizing agent in this embodiment.  

Particularly advantageous properties have been found in agents in which the Ami no acid or the oligopeptide and the further alkalizing agent in a ratio of 1: 5 to 5: 1. Ratios of 1: 2 to 2: 1 have been found to be particularly suitable proved.

To produce the colorants according to the invention, the above-mentioned zwin ing and optional components in a suitable, preferably water-containing, Trä ger incorporated. Such carriers are e.g. B. creams, emulsions, gels or surfactant term foaming solutions, e.g. B. shampoos, aerosols or other preparations, which are suitable for use on the hair. These wording forms will with the above-mentioned alkalizing agents or suitable acids, such as esp special edible acids such as citric acid, tartaric acid, lactic acid and acetic acid before added to a pH of 5 to 11, in particular 7 to 10, adjusted.

Furthermore, the colorants according to the invention can all be in such preparations Known active ingredients, additives and auxiliaries. In many cases, the colorants contain at least one surfactant, in principle both anionic and zwitterionic, Ampholytic, nonionic and cationic surfactants are suitable. In many cases it has but proved to be advantageous, the surfactants from anionic, zwitterionic or select nonionic surfactants. Anionic surfactants can be very special be preferred.

Suitable anionic surfactants in preparations according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ether, amide and hydroxyl groups and generally also ester groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group,

• - linear and branched fatty acids with 8 to 22 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,
• Acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• Acyl taurides with 10 to 18 carbon atoms in the acyl group,
• Acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates with 12 to 18 carbon atoms,
• Linear alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (-CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group with 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bin solutions according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide Represent fatty alcohols with 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ethers carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups pen in the molecule and in particular salts of saturated and especially unsaturated C8-C22 carboxylic acids such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylamino-propyl-dimethyl-ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.

Ampholytic surfactants are those surface-active compounds which, in addition to a C8-C18-alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkylimino dipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with approximately 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-18 acylsarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a poly lyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles Propylene oxide on linear fatty alcohols with 8 to 22 carbon atoms, on fatty acids with 12 to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group,
• - C12-C22 fatty acid monoesters and diesters of adducts from 1 to 30 mol Ethylene oxide on glycerol,
• - C8-C22 alkyl mono- and oligoglycosides, their ethoxylated analogues and their Esters e.g. B. with tartaric acid and citric acid,
• - Adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,
• Addition products of ethylene oxide onto sorbitan fatty acid esters,
• - Addition products of ethylene oxide with fatty acid alkanolamides.

Examples of the katio which can be used in the hair treatment compositions according to the invention African surfactants are especially quaternary ammonium compounds. Are preferred Ammonium halides such as alkyltrimethylammonium chlorides, dialkyldi-methylammoni umchloride and trialkylmethylammoniumchloride, e.g. B. Cetyltrimethyl-ammonium chloro rid, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldi methylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylme methylammonium. Provide further cationic surfactants that can be used according to the invention the quaternized protein hydrolyzates.

Also suitable according to the invention are cationic silicone oils such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modified silicone, also called amodimethicone), SM-2059 (Her Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines like the one under the name Tego Amid®S 18 available stearylamidopropyldimethylamine, stand out next to one good conditioning effect especially due to its good biodegradability.

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as the Methyl-hy sold under the trademark Stepantex® droxyalkyl-dialkoyloxyalkyl-ammonium methosulfates and the corresponding products, which are commercially available under the trademark Dehyquart®.

An example of a quaternary sugar derivative that can be used as a cationic surfactant is provided represents the commercial product Glucquat®100, according to the CTFA nomenclature a "Lauryl Methyl Gluceth-10 hydroxypropyl dimonium chloride ".

The compounds with alkyl groups used as surfactants can in each case be act uniform substances. However, it is usually preferred in the manufacture these substances from natural vegetable or animal raw materials, so that one  Mixtures of substances with different alkyl kets depending on the respective raw material ten lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide Representing fatty alcohols or derivatives of these adducts, both Pro products with a "normal" homolog distribution as well as those with a narrowed Homolog distribution can be used. Under "normal" homolog distribution understood mixtures of homologues that are used in the implementation of fatty alcohols hol and alkylene oxide using alkali metals, alkali metal hydroxides or Alkali metal alcoholates obtained as catalysts. Narrow homolog distributions who on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts ver be applied. The use of products with a narrow homolog distribution can be preferred.

According to the invention, the use of anionic surfactants in combination with zwitterionic surfactants may be particularly preferred.

According to the invention, preference is also given to agents which additionally comprise a polymer, selected from the group consisting of anionic, zwitterionic, ampholytic, cationic and comprises nonionic polymers.

Particularly preferred according to the invention are those agents which additionally contain a cationic agent Polymer included.

The permanent cationic polymers are among the cationic polymers Trains t. According to the invention, such polymers are termed “permanently cationic” if which have a cationic group regardless of the pH of the agent. These are in usually polymers that have a quaternary nitrogen atom, for example in the form of a Ammonium group.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat® and Po lymer JR® are commercially available. The connections Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives,
• - Polysiloxanes with quaternary groups, such as those obtained commercially products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino modified silicone, also called amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• - Cationic guar derivatives, in particular those under the trade names Cos products sold by media®Guar and Jaguar®,
• - Polymer Dimethyldiallylammoniumsalze and their copolymers with esters and Amides of acrylic acid and methacrylic acid. The under the designations Mer quat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyl diallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers,
• - Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminoethyl methacrylate copolymers. Such connections are under the names Gafquat®734 and Gafquat®755 commercially available,
• - Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as described under the Be drawings Luviquat® FC 370, FC 550, FC 905 and HM 552 are available.
• - quaternized polyvinyl alcohol,
• - as well as under the names
• - polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Po lymerhauptkette.

Can also be used as cationic polymers under the designation Polyquaternium-24 (commercial product e.g. Quatrisoft® LM 200), Polyquaternium- 32, Polyquaternium-35 and Polyquaternium-37 (commercial products e.g. Salcare® SC 92 and Salcare®SC 95) known polymers. The can also be used according to the invention Copolymers of vinylpyrrolidone, as are commercially available as copolymer 845 (Her manufacturer: ISP), Gaffix® VC 713 (manufacturer: ISP), Gafquat®ASCP 1011, Gafquat®HS 110, Luviquat®8155 and Luviquat® MS 370 are available.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives, polymeric dimethyldiallylammonium salts, polyquaternium-27 and their copolymers as well as polymers of the type polyquaternium-2. Cationic cellulose derivatives, esp in particular the commercial product Polymer®JR 400, and polymers of the type Polyquaternium-2, especially the commercial product Mirapol®A-15 are very particularly preferred katio African polymers.

The cationic polymers are preferred in amounts in the agents according to the invention from 0.05 to 5 wt .-%, based on the entire preparation.

In many cases, amphopolymers can also be used as an alternative to the cationic polymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free - COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - COO ^- - or - SO ₃ ^- groups, and summarized such polymers that contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer which can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acid (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acid (e.g. acrylamidopropyltrimethylammonium chloride) and optionally other ionic or nonionic monomers, such as, for example, in German Laid-open specification 39 29 973 and the state of the art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat® 2001 N, and the commercial product Merquat®280 can also be used according to the invention.

The agents according to the invention likewise preferably contain at least one nonio nogeneic or anionic polymer with thickening properties. Are preferred optionally crosslinked, polyacrylic acids, cellulose derivatives, e.g. B. methyl cellulose, Hydroxyalkyl cellulose and carboxymethyl cellulose, and xanthan gum.

Other active ingredients, auxiliaries and additives are, for example

• - Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copoly mers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and poly siloxanes,
• Anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,
• Thickeners such as agar agar, guar gum, alginates, gum arabic, karaya Gum, locust bean gum, linseed gums, dextrans, starch fractions and Derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as B. polyvinyl alcohol,
• Structurants such as glucose, maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soy lecithin, Egg lecithin and cephaline, as well as silicone oils,
• - Protein hydrolyzates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids as well as quaternized protein hydrolyzates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,  
• - Solvents and intermediates such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol, ethoxybutanol and butoxyethanol and Ben zylalkohol,
• - anti-dandruff agents such as Piroctone Olamine and Zink Omadine,
• - other substances for adjusting the pH, such as α- and β- hydroxy,
• - Active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins,
• - cholesterol,
• - light stabilizers,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as walrus, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
• - fatty acid,
• Complexing agents such as EDTA, NTA and phosphonic acids,
• - Swelling and penetration substances such as glycerin, propylene glycol monoethyl ether, carbo nates, hydrogen carbonates, guanidines, ureas and primary, secondary and ter tertiary phosphates,
• Opacifiers such as latex,
• - pearlescent agents such as ethylene glycol mono- and distearate,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

The constituents of the water-containing carrier are used for the production of the invention moderate colorants used in amounts customary for this purpose; z. B. become Emul yaw in concentrations of 0.5 to 30% by weight and thickeners in concentrate tions of 0.1 to 25 wt .-% of the total colorant used.

Regarding the further constituents of the colorants according to the invention, expressly on the monographs known to those skilled in the art, e.g. B. Umbach, cosmetics, 2. Edition, Georg Thieme Verlag, Stuttgart New York, 1995, and Kh. Schrader, Fundamentals  and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, ver grasslands.

All known methods can be used to form the color on the keratin fiber be applied.

According to a preferred embodiment, the coloring is carried out with air oxygen as the only oxidizing agent. This embodiment is particularly then preferred if the group Y of the hybrid dye differs from an air-oxidizable Derives developer and coupler component, or the agent precursor of melanin and / or contains air-oxidable dye precursors of the coupler or developer type. As According to the invention, air-oxidizable compounds are such compounds or To understand dye precursors in which the oxidative formation of the final Coloring with the help of atmospheric oxygen alone without the use of conventional chemical Oxidizing agents can take place. Triaminobenzene derivatives are examples of such air-oxidizable compounds.

In certain cases where group Y of the hybrid dye is different from developer and derived coupler components, or the agent precursor of melanin and / or Contains dye precursors of the coupler or developer type, the co-use a chemical oxidizing agent. This also applies if in addition to the Coloring a lightening effect on human hair is desired. As an oxidizing agent then especially hydrogen peroxide or its addition products arrive Urea, melamine or sodium borate in question.

The preparation of the oxidizing agent is expediently immediately before Dyeing the hair mixed with the preparation with the dye precursors. That included The resulting ready-to-use hair dye preparation should preferably have a pH in the Range from 5 to 11. The use of hair is particularly preferred colorants in a weakly alkaline environment. The application temperatures can be in a range between 15 and 40 ° C, preferably at the temperature of the scalp. After an exposure time of approx. 5 to 45, in particular 15 to 30, minutes, this becomes Hair dye removed by rinsing from the hair to be dyed. The washing up  with a shampoo if a strong surfactant carrier, e.g. B. a coloring shampoo, was used.

Especially with hair that is difficult to dye, the preparation can be prepared with the dye prepro products applied to the hair without prior mixing with the oxidation component be brought. After an exposure time of 20 to 30 minutes, optionally after an intermediate rinse - the oxidation component applied. After a further exposure time of 10 to 20 minutes, rinsing and ge if necessary aftershampooed. In this embodiment, according to a first Variant in which the previous application of the dye precursors is better Penetration in the hair should cause the corresponding agent to have a pH of set about 4 to 7. According to a second variant, air oxidation is performed first sought, the applied agent preferably having a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidic adjusted peroxidisulfate solutions may be preferred as the oxidizing agent.

According to a special embodiment of this method, the final staining by applying the agent several times and then connecting air oxidation. The respective application of the agent is preferably carried out in Ab stands that are between about a day and about two weeks. This allows very specific nuances are obtained.

Regardless of which of the above-mentioned methods is chosen for the application of the agent according to the invention, the formation of the coloring can be supported and increased by adding certain metal ions to the agent. Such metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Ru ³⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ , Mn ²⁺ , Ru ³⁺ and Ca ²⁺ are particularly suitable. The metal ions can in principle be used in the form of any physiologically acceptable salt. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner.

It is also possible according to the invention to carry out the oxidation with the aid of enzymes respectively. The enzymes (enzyme class 1: oxidoreductases) can remove electrons  suitable developer components (reducing agents) transferred to atmospheric oxygen. Be oxidases such as tyrosinase and laccase are preferred, but also glucose oxidase and uricase or pyruvate oxidase. Furthermore, the enzymes can be lower to enhance the effect Amounts of existing oxidizing agents are used. An example of such an enzyme The table shows the procedure, the effect of small amounts (e.g. 1% and less, based on the total agent) hydrogen peroxide by veroxidase strengthen.

Another object of the invention is the use of a hybrid dye Structure (I) or a mixture of these hybrid dyes for dyeing keratin fibers, especially human hair.

Furthermore, it has been shown that the hybrid dyes according to the invention also stand out excellent for coloring, especially for tanning, the human skin. On Another object of the invention is therefore the use of a hybrid dye Structure (I) or a mixture of these hybrid dyes for coloring human Skin.

Claims (10)

1. coupler / developer and coupler / coupler hybrid dyes and hybrid dye precursors, in particular for dyeing keratin fibers, of structure (I),
XSY (I)
where X represents a group derived from a coupler type oxidation dye precursor;
Y stands for a group derived from
a developer type oxidation dye precursor, or
a coupler type oxidation dye precursor; and
S stands for a direct bond or at least one spacer group; with the proviso that X, Y and S are not chosen so that they correspond to one of the compounds of the general formulas (II), (III) or (IV) listed below:
where the compounds of the general formulas (II) and (III) R ¹ to R ¹⁰ independently of one another are H, (C ₁ -C ₄ ) -alkyl, hydroxy- (C ₂ -C ₃ ) -alkyl, (C ₁ - C ₄ ) -alkoxy- (C ₂ -C ₃ ) -alkyl, amino- (C ₂ -C ₃ ) -alkyl or 2,3-dihydroxypropyl and n represents an integer from 1-6 and the groups -NR ¹ R ² and -NR ⁷ R ^{8 are} either in positions 4 and 4 'or in positions 5 and 5';
where for the compounds of the general formula (IV) X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ are nitrogen or CR ⁶ , CR ⁷ , CR ⁸ , CR ⁹ , CR ¹⁰ , at least one and at most three of the Radicals X ⁶ to X ^{10 can} denote nitrogen and optionally the radicals R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ independently of one another hydrogen, a halogen atom, a cyano group, a hydroxyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ alkylthioether group, a mercapto group, a nitro group, an amino group, a C ₁ -C ₄ alkylamino group, a di (C ₁ - C ₄ ) alkylamino group, a trifluoromethane group , a -C (O) H group, a - C (O) CH ₃ group, a -C (O) CF ₃ group, a -Si (CH ₃ ) ₃ group, a -C (O) -NH ₂ group, a C ₁ -C ₄ hydroxyalkyl group, a C ₃ -C ₄ dihydroxyalkyl group, a - CH = CHR ¹¹ group, a - (CH ₂ ) _p -CO ₂ R ¹² group or one - (CH ₂ ) _p -R ¹³ group with p = 1, 2, 3 or 4, a -C (R ¹⁴ ) = NR ¹⁵ group or a C (R ¹⁷ ) Mean H-NR ¹⁸ R ¹⁹ group; R ¹ , R ² , R ³ and R ⁴ independently of one another are hydrogen, a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₂ -C ₄ dihydroxyalkyl group or a C ₁ -C ₄ alkoxy - (C ₁ -C ₄ ) alkyl group, or R ¹ and R ² or R ³ and R ^{4 form} a four-membered to eight-membered aliphatic ring, at least two of the radicals R ¹ to R ^{4 being} hydrogen; R ⁵ is hydrogen, a hydroxy group, a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group or a C ₁ -C ₄ alkoxy group; R ¹¹ is hydrogen, a hydroxy group, an amino group, a CO ₂ R ¹² group or a -C (O) CH ₃ group; R ¹² , R ¹⁴ and R ^{17 are} independently hydrogen or a C ₁ -C ₄ alkyl group; R ¹³ is an amino group or a nitrile group; R ¹⁵ , R ¹⁸ and R ¹⁹ independently of one another are equal to hydrogen, a hydroxy group, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ hydroxyalkyl group, a C ₃ - C ₄ dihydroxyalkyl group or a radical of the formula
is; R ¹⁶ is hydrogen, an amino group or a hydroxy group. 2. Coupler / developer and coupler / coupler hybrid dyes and -hybrid dye precursors according to claim 1, wherein one of the two groups X or Y contains a heterocyclic six-membered ring. 3. Agent for dyeing keratin fibers, characterized in that it contains at least one coupler / developer and / or coupler / coupler hybrid dye and / or hybrid dye precursor of structure (I),
XSY (I)
where X represents a group derived from a coupler type oxidation dye precursor;
Y stands for a group derived from

• - a developer type oxidation dye precursor, or
• - a coupler-type oxidation dye precursor; and

S stands for a direct bond or at least one spacer group. 4. Means according to claim 3, characterized in that it is still a Contains oxidation dye intermediate of the coupler and / or developer type. 5. Means according to claim 3 or 4, characterized in that it also has a contains direct dye. 6. Composition according to one of claims 3 to 5, characterized in that it further contains a derivative of indole or indoline as a precursor of melanin.   7. Composition according to one of claims 3 to 6, characterized in that it is a surfactant contains, selected from the group comprising anionic, zwitterionic, ampholytic, cationic and / or nonionic surfactants. 8. Composition according to one of claims 3 to 7, characterized in that it is a polymer contains selected from the group comprising cationic, anionic, nonionic and / or amphopolymer. 9. Use of a hybrid dye of structure (I) according to claim 1 or 2 or an agent according to any one of claims 3 to 8 for dyeing keratin fibers, especially human hair. 10. Use of a hybrid dye of structure (I) according to claim 1 or 2 or one Agent according to one of claims 3 to 8 for coloring human skin.