DE10030910A1 - Color for keratinous fibers, especially human hair, contains 5-(hydroxy)alkyl-2-hydroxypyridine as dye precursor and developer component with at least 2 aromatic rings - Google Patents

Abstract

Color for keratinous fibers contains 5-(hydroxy)alkyl-2-hydroxypyridine(s) (I) as dye precursor and developer component(s) (II) with at least 2 rings in a cosmetically acceptable medium. Color for keratinous fibers contains 5-(hydroxy)alkyl-2-hydroxypyridine(s) of formula (I) as dye precursor and developer component(s) (II) with at least 2 rings in a cosmetically acceptable medium. R = 1-4 carbon (C) (hydroxy)alkyl; X, Y = OH or 1-4 C alkyl. Independent claims are also included for: (1) a process for coloring keratinous fibers, in which the color is applied and rinsed off after an action time; (2) use of a dye combination of (I) and (II) for coloring keratinous fibers.

Description

The present invention relates to agents for dyeing keratinic fibers, the special Pyridine derivatives as coupler components in combination with 2-ringed Developer components containing a method of dyeing keratinic fibers with this agent and the use of this dye combination for staining keratinic fibers.

Human hair is used today in a variety of ways with hair cosmetic preparations treated. These include cleaning the hair with shampoos, taking care and re generation with rinses and cures, as well as the bleaching, dyeing and shaping of the Hair with coloring, tinting, waving and styling preparations. Play it Means for changing or nuancing the color of the hair of the head an outstanding Role.

For temporary dyeings usually dyeing or tinting agents are used, the as a coloring component so-called Direktzieher included. This is Dye molecules that grow directly on the hair and no oxidative process for Need training of the paint. For example, these dyes already belong Henna known from ancient times for coloring body and hair. These dyes are sensitive to shampooing in general, so that a often undesirable Shade shift or even a visible "discoloration" may occur.

For permanent, intense colorations with corresponding fastness properties so-called oxidation colorants used. Such colorants usually contain Oxidation dye precursors, so-called developer components and Kupplerkom  components. The developer components form under the influence of oxidants or of atmospheric oxygen with each other or under coupling with one or more Coupler components from the actual dyes. Draw the oxidation colorants characterized by excellent, long lasting staining results.

Good oxidation dye precursors are primarily the following prerequisites You must: In the oxidative coupling you have the desired color shades in form sufficient intensity and authenticity. You also need a good one Ownership of the fiber, especially in human hair no noticeable differences between strained and newly regrown hair may exist (leveling ability). They should be resistant to light, heat, Friction and the influence of chemical reducing agents, e.g. B. permanent wave fluids. Finally, they should - if used as a hair dye used - the scalp Do not stain too much, and above all, they should be toxicological and dermatological Regard safe. Furthermore, the coloring obtained by bleaching should be easy can be removed from the hair if they are not the individual Wishes of the individual person corresponds and should be reversed.

Alone with a developer component or a special coupler / developer combination usually does not succeed, a naturally acting on the hair To get color nuance. In practice, therefore, usually combinations various developer and / or coupler components used. It therefore exists Constant need for new, improved dye components.

It has now surprisingly been found that particularly intense dyeings with excellent fastness properties and exceptionally good toxicological Properties can be obtained when using colorants that are special Pyridine derivatives as coupler components and binuclear developer components contain.

A first subject of the present invention is therefore an agent for coloring keratinous fibers, contained in a cosmetically acceptable medium

• A) at least one compound of the formula (I)
  wherein R represents a C _1-4 alkyl group or a C _1-4 hydroxyalkyl group, and X and Y independently represent a hydroxy group or a C _1-4 alkyl group, and
• B) at least one binuclear developer component.

According to the invention, keratinic fibers include furs, wool, feathers and, in particular, furs understood human hair.

Examples of the C _1-4 -alkyl groups 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 groups. Preferred C _1-4 -hydroxyalkyl groups are the groups hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-hydroxyethyl is a particularly preferred hydroxyalkyl group.

Be particularly advantageous, the compounds of formula (I) have been found in which at least one of X or Y is a hydroxy group.

Preferred compounds of the formula (I) are 2,6-dihydroxy-3,4-dimethylpyridine, 2,4- Dihydroxy-5,6-dimethylpyridine, 2,6-dihydroxy-3-ethyl-4-methylpyridine and 2,6- Dihydroxy-3- (β-hydroxyethyl) -4-methylpyridine. 2,6-dihydroxy-3,4-dimethylpyridine a very particularly preferred compound of formula (I).

Among binuclear developer components according to the invention compounds which contain at least two aromatic nuclei containing at least two optionally substituted amino and / or hydroxyl groups which are present in para and / or ortho position to each other.  

Dinuclear developer components of the formula (II) are preferred according to the invention.

in which:

• - Z ¹ and Z ² are each independently a hydroxyl or NH ₂ radical optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ - hydroxyalkyl radical and / or by a bridge Y substituted is
• - 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 interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals,
• R ² and R ³ independently of one another represent a hydrogen or halogen atom, a C ₁ to C ₄ alkylkadical, 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 compound for bridging Y,
• R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ 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 proviso that the compounds of formula (II) only one bridge Y per Contain molecule.

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 -C ₄ -alkoxy radicals which are 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. 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 formula (II) are especially the amino groups, C ₁ - to C ₄ - monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ - to C ₄ - trialkylammonium groups, C ₁ - to C ₄ -Monohydroxyalkylaminogruppen, Imidazolinium and ammonium.

It may be preferred according to the invention if the compound of the formula (II) is selected from N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-amino phenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis (4'-amino, 3'-methylphenyl) -ethylenediamine, 1,8-bis- (2,5-) Diaminophenoxy) -3,5-dioxoctane, bis (2-hydroxy-5-aminophenyl) -methane, 1,4-bis (4-bis) aminophenyl) diaza-cycloheptane and 1,10-bis- (2,5-diaminophenyl) -1,4,7,10- tetraoxadecane and its physiologically acceptable salts.

The compounds N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, 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 a their physiologically acceptable salts are particularly preferred according to the invention.

In a preferred embodiment, the color-modifying invention contain Means at least one additional dye precursor.

With regard to the dye precursors which can be used in the agents according to the invention, the present invention is not subject to any restrictions. The agents according to the invention can be used as dye precursors

• - Developer and coupler type oxidation dye precursors, and
• Precursors of nature-analogous dyes, such as indole and indoline derivatives,  and mixtures of representatives of these groups.

As developer components are usually primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4- Aminopyrazolderivate 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 (III)

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 radical (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 radical (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical substituted with 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 ₁ to C ₄ -Hydroxyalkoxyradikal, a C ₁ - to C ₄ -Acetylaminoalkoxyradikal, a C ₁ - to C ₄ -Mesylaminoalkoxyradikal or a C ₁ - to C ₄ -Carbamoylaminoalkoxyradikal;
• 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 -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 which are 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. 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 (III) are especially the amino groups, C ₁ - to C ₄ - monoalkylamino, C ₁ - to C ₄ dialkylamino, C ₁ - to C ₄ - trialkylammonium groups, C ₁ - to C ₄ -Monohydroxyalkylaminogruppen, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (III) 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-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 acceptable salts.  

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

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. Particularly preferred are p-aminophenol derivatives of the formula (IV)

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 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 -Hydroxyalkoxyradikal, a C ₁ - to C ₄ - hydroxyalkyl, (C ₁ to C ₄₎ -aminoalkyl radical, or a (di-C ₁ - to C ₄ - alkylamino) - (C ₁ - to C ₄₎ alkyl radical, and
• G ¹⁴ is 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 radical, a C ₁ to C ₄ aminoalkyl radical 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 (IV) are according to the invention analogous to the above Executions defined.  

Preferred p-aminophenols of the formula (IV) are in particular p-aminophenol, N- Methyl-p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluorophenol, 2- Hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2- (2- 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, 2,6-dichloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (IV) are p-aminophenol, 4-amino 3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2- ((Diethylamino) methyl) phenol.

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

Furthermore, 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 the German Patent DE 23 59 399, Japanese Patent Laid-Open JP 02019576 A2 or in the Offenlegungsschrift 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 740931 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'-dihydroxy) 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- hydrazino pyrazole, 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'-methyl) 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 the pyrazolo [1,5-a] pyrimidine of the following formula (V) and their tautomeric forms, provided that a tautomeric equilibrium exists:

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 a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl radical, a C ₁ to C ₄ aminoalkyl radical optionally protected by an acetyl-ureide or sulfonyl radical may 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 having 5 or 6 chain members, 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 radical, 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 radicals, 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) 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 equals 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);
• 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 (V) are analogous to the above according to the invention Executions defined.

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

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

• - pyrazole [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazole [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] -pyrimidine-3,5-diamine;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-7-ol;
• 3-amino-pyrazolo [1,5-a] -pyrimidin-5-ol;
• - 2- (3-amino-pyrazolo [1,5-a] -pyrimidin-7-ylamino) -ethanol;
• - 2- (7-amino-pyrazolo [1,5-a] -pyrimidin-3-ylamino) -ethanol;
• - 2 - [(3-amino-pyrazolo [1,5-a] -pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;
• - 2 - [(7-amino-pyrazolo [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;
• 2,5, N7, N7-tetramethylpyrazolo [1,5-a] -pyrimidine-3,7-diamine;

and their physiologically acceptable salts and their tautomeric forms, when tautomeric equilibrium is present.

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

As coupler components usually m-phenylenediamine derivatives, naphthols, Re sorcin and resorcinol derivatives, pyrazolones and m-aminophenol derivatives. When Coupler substances are particularly suitable 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resor cinomonomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-  aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-Chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5- Methyl resorcinol and 2-methyl-4-chloro-5-aminophenol.

Coupler components preferred according to the invention are:

• M-aminophenol and its derivatives such as, for example, 5-amino-2-methylphenol, 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 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-bis) hydroxyethylamino) -1-methylbenzene 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-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-Diamino-2,6-dimethoxy,
• Naphthalene derivatives such as, for example, 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-amino benzomorpholine,  
• 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 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
• Methylene dioxybenzene derivatives such as 1-hydroxy-3,4- methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) - amino-3,4-methylenedioxybenzene.

Particularly preferred coupler components 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 and 2,5-dimethylresorcinol.

It is not necessary that the oxidation dye precursors or the substantive Dyes each represent uniform compounds. Rather, in the inventions Hair colorants according to the invention, due to the production process for the individual NEN dyes, in minor amounts still contain other components, as far as these do not adversely affect the dyeing result or for other reasons, eg. B. toxicological, must be excluded.

With regard to the hair dyeing and tinting compositions according to the invention can be used Dyes is still 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 series "Dermato logy "(ed .: Ch., Culnan and H. Maibach), published by 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 Bundesverband Deutscher Industrial and commercial enterprise for pharmaceuticals, health products and personal care tel e.V., Mannheim.  

The oxidation dye precursors are preferred in the agents according to the invention Amounts from 0.01 to 20 wt .-%, preferably 0.5 to 5 wt .-%, each based on the entire medium, included.

As precursors of naturally-analogous dyes such indoles and indolines are preferred set, the at least one hydroxy or amino group, preferably as a substituent on Six-ring, exhibit. These groups may carry further substituents, e.g. B. in shape an etherification or esterification of the hydroxy group or an alkylation of the amino group.

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

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 is a C ₁ -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 indoline are the 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 the 6-hydroxy indoline, 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-dihydroxy indoline and in particular 5,6-dihydroxyindoline.

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

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 is a C ₁ -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-dihy droxyindole, 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.  

Within this group, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6- dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and especially in particular the 5,6-dihydroxyindole.

The indoline and indole derivatives can in the Ver used as both free bases and in the form of their physiolo gically compatible salts with inorganic or organic acids, eg. B. the hydrochlo ride, the sulfates and hydrobromides used. The indole or indoline derivatives are in these usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-% contain.

In particular when using dye precursors of the indoline or indole type it has proved to be advantageous as alkalizing an amino acid and / or a Use oligopeptide.

In addition to the dye precursors, the agents according to the invention can be used for further Nuancierung substantive dyes included. These are usually selected from Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophe nole. Preferred substantive dyes are those under the international name trade names 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, hydroxyethyl-2- nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3- nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The Means according to this embodiment according to the invention contain the substantive ones Dyes preferred in an amount of 0.01 to 20 wt .-%, based on the total Colorant.  

Furthermore, the preparations according to the invention can also occur in nature Dyes such as henna red, henna neutral, henna black, chamomile flower, Sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alcano root included.

The inventive compositions contain dye precursors preferably in one suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of Hair coloring are such carriers, for example creams, emulsions, gels or else surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations suitable for use on the hair. It is also conceivable, the dye precursors in a powdered or tablet-shaped To integrate formulation.

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

The actual oxidative dyeing of the fibers can in principle be successful with atmospheric oxygen However, preference is given to using a chemical oxidizing agent, in particular if, in addition to the coloring, a lightening effect on human hair is desired. When Oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate in question. Furthermore, it is possible to carry out the oxidation by means of enzymes, wherein the Enzymes are used both for the production of oxidizing per-compounds as also to enhance the effect of a small amount of existing oxidizing agent. Thus, the enzymes (enzyme class 1: oxidoreductases) can make electrons from suitable Developer components (reducing agent) transferred to atmospheric oxygen. Preferred are while oxidases such as tyrosinase, ascorbate oxidase and laccase but also glucose oxidase, Uricase or pyruvate oxidase. Furthermore, the procedure is called, the effect less  Amounts (eg, 1% and less, based on total agent) of hydrogen peroxide to amplify by peroxidases.

The actual hair dye is expediently immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the Dye precursors, prepared. The resulting ready to use Haarfärbeprä It should preferably have a pH in the range from 6 to 12. Especially the use of the hair dye is preferred in a weakly alkaline medium. The application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye is turned off Rinse away from the hair to be dyed. The washing with a shampoo deleted if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

The agents according to the invention can furthermore all be known for such preparations Active substances, additives and auxiliary substances. In many cases, these remedies contain at least a surfactant, whereby in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be proved to be advantageous, the surfactants from anionic, zwitterionic or nonionic Select surfactants.

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

• - linear fatty acids with 10 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 having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,  
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• - Sulfobemsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 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 having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• - Sulfated Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether according to DE-A-37 23 354,
• - Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 doublebin 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 with fatty alcohols having 8 to 22 Represent C atoms.

Preferred anionic surfactants are alkyl sulfates, Alkylpolyglykolethersulfate and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 Glykolethergrup groups in the molecule and in particular salts of saturated and especially unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Nonionic surfactants contain as hydrophilic group z. As a polyol group, a Po lyalkylenglykolethergruppe or a combination of polyol and polyglycol ether group. Such compounds are, for example

• - Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols containing 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms Atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated Ri zinusöl.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched ver. Preference is given to primary linear and methyl-branched in the 2-position aliphati cal radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When so-called "oxo-alcohols" are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are made starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

Particular preference is given to those alkylpolyglycosides in which R ¹

• consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• essentially of C ₁₂ and C ₁₄ alkyl groups,
• - Essentially from C ₈ - to C ₁₆ alkyl groups or
• - Consists essentially of C ₁₂ - to C ₁₆ -alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding Used oligosaccharides. Such sugars are, for example, glucose, fructose, galac tose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.  

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 Sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. All particularly preferred are alkyl glycosides in which x is 1.1 to 1.4.

The alkyl glycosides can also serve, in addition to their surfactant effect, the fixation to improve fragrance components on the hair. The person skilled in the art will therefore be that on the duration of the hair treatment beyond the effect of the perfume oil on the hair is desired, preferably to this class of substance as further ingredient resort to the preparations of the invention.

The alkoxylated homologs of said alkylpolyglycosides can also be invented be used according to. These homologs can average up to 10 ethylene contain oxide and / or propylene oxide per alkyl glycoside unit.

Furthermore, especially as co-surfactants, zwitterionic surfactants who used the. As zwitterionic surfactants are those surface-active compounds be distinguished, which carry in the molecule at least one quaternary ammonium group and at least one -COO ^(-) - or -SO ₃ ^(-) group. 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 dimethylammoniumglycinate, for example Kokosacylaminopropyl-dime thylammoniumglycinat, and 2 Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylamino ethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Under on pholytic surfactants are those surface-active compounds understood that in addition to a C ₈ -C ₁₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO ₃ H group and capable of forming inner salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodiopropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

According to the invention as cationic surfactants in particular those of the type of quar ammonium compounds, esterquats and amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, in particular These are chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylam ammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetyl methylammonium chloride, as well as those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants mentioned preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain at least one ester radio tion and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized esters salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products will be for example under the trademarks Stepantex®, Dehyquart® and Armocare® distributed. The products Armocare® VGH-70, an N, N-bis (2-palmitoyloxy ethyl) dimethyl ammonium chloride, and Dehyquart® F-75 and Dehyquart® AU-35 Examples of such esterquats.

The Alkylamidoamine are usually by amidation natural or synthetic fatty acids and fatty acid sections prepared with dialkylaminoamines. A compound according to the invention particularly suitable from this group of substances provides that the name Tegoamid® S 18 commercially available Stearamidopropyl-dimethylamine represents.  

Further cationic surfactants which can be used according to the invention are the quaternized Protein hydrolysates.

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

An example of a cationic surfactant employable quaternary sugar derivative the commercial product Glucquat® 100, according to INCI nomenclature a "Lauryl Methyl Glu ceth-10 hydroxypropyl dimonium chlorides ".

The compounds used as surfactant with alkyl groups may be in each case act uniform substances. However, it is usually preferred in the production These substances are based on native plant or animal raw materials, so that one Substance mixtures with different, depending on the respective raw material Alkyl chain lengths.

For the surfactants, the adducts of ethylene and / or propylene oxide to fat Alcohols or derivatives of these addition products may represent both products with a "normal" homolog distribution as well as those with a narrow homologue genverteilung be used. Under "normal" homolog distribution are thereby Mixtures of homologues understood in the reaction of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali obtained metal alkoxides as catalysts. Narrow homolog distributions become obtained, however, if, for example, hydrotalcites, alkaline earth metal salts of Ethercarbonsäuren, alkaline earth metal oxides, hydroxides or alkoxides as catalysts be used. The use of products with narrow homolog distribution may be preferred.  

Furthermore, the agents according to the invention can preferably also have a conditioning Active ingredient selected from the group consisting of cationic surfactants, cationic Polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils is formed.

Cationic polymers may be preferred as conditioning agents. These are in usually polymers containing a quaternary nitrogen atom, for example in the form of an Am monium group.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as they are known under the names Celquat® and Po lymer JR® are commercially available. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
• - Dimethyldiallylammoniumsalze polymeric and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The under the Designations Merquat®100 (poly (dimethyldiallylammonium chloride)), Mer quat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylates and methacrylates such as vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are under the names Gafquat®734 and Gafquat®755 commercially available.
• - Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, as described under the name Luviquat®.
• - Quaternized polyvinyl alcohol

as well as those under the designations

• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Po lymerhauptkette.

Particularly preferred are cationic polymers of the first four groups, completely Polyquaternium-2, polyquaternium-10 and polyquaternium-22 are particularly preferred.

Further suitable conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes such as dimethylpolysiloxane and methylphenylpolysi loxan, as well as their alkoxylated and quaternized analogs. Examples of such silicones are those of Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 distributed products as well as the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Coming® 929 emulsion (containing a hydroxylamino-modified silicone, which may also be described as amodimethicones characterized), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternäre Polydimethylsiloxanes, quaternium-80).

Also usable as conditioning agents are paraffin oils, synthetic prepared oligomeric alkenes and vegetable oils such as 3ojobaöl, sunflower oil, Orange oil, almond oil, wheat germ oil and peach kernel oil.

Likewise suitable hair conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephaline.

Other active ingredients, auxiliaries and additives are, for example

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Zwitterionic and amphoteric polymers such as acrylamidopropyl tri methylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate lat / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers,
• Anionic polymers such as, for example, 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 acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers  
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum ara bicum, karaya gum, locust bean gum, linseed gums, dextran, cellu loose derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethylcel cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair conditioning compounds such as phospholipids, for example soya lecithin, Egg lecithin and cephalins,
• - Protein hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• - Fiber structure improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - Sunscreens, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• - Substances for adjusting the pH, such as conventional acids, in particular special edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as extracts of green tea, oak bark, stinging nettle, Witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, Almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, Mango, Apricot, Lime, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Rosmann, Birch, Mallow, Meadowfoam, Quendel, Yarrow, Thyme, Melissa, hominy, coltsfoot, marshmallow, meristem, ginseng and ginger root,  
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• - fatty acid,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, Hydrogencarbonates, guanidines, ureas as well as primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants.

Regarding further optional components as well as the amounts of this com components is expressly referred to the relevant manuals known to those skilled in the art, z. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced.

The following examples are intended to be the subject of the present application clarify without, however, restricting to it.  

embodiments 1. Preparation of the coloring cream

Partial mixture A Hydrenol® D ¹ 8.50 g Lorol® techn ² 2,00 g Eumulgin® B2 ³ 0.75 g Texapon NSO ⁴ 20.00 g Dehyton K ⁵ 12.50 g water 30.00 g ¹ C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis) ² C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis) ³ Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) @ ³ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) @ ⁴ lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis) @ ⁵ N, N-dimethyl-N- (C _8-18 -cocoamidopropyl) ammonium acetobetaine (about 30% active, LNCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

The substances Hydrenol® D, Lorol® and Eumulgin® B2 were at 80 ° C melted with the 80 ° C hot water containing Texapon® NSO and Dehyton® K, mixed and emulsified with vigorous stirring. Thereafter, the emulsion was under cooled gently.

Partial mixture B sodium 1.00 g ammonium sulfate 1.00 g dye precursors in each case 7.5 mmol Ammonia (25% solution) ad pH = 10.0 water 10.00 g

The dye precursors were in the 50 ° C hot water with the addition of Dissolved sodium sulfite, ammonium sulfate and ammonia.

The dye precursor solution (sub-mixture B) became the emulsion (sub-mixture A) adjusted with ammonia to pH = 10 and made up to 100 g with water. It was stirred until reaching room temperature.

2. Coloring of the keratinic fibers

The coloring cream thus obtained was in the ratio 2: 1 with a 1% H ₂ O 2 solution or a β% H ₂ O ₂ solution and mixed on standardized Scm long tresses of 80%, but not especially pretreated human hair (Kerling) applied. After 30 min exposure time at 32 ° C, the hair was rinsed, washed with a conventional shampoo and then dried. Furthermore, a series of experiments on air oxidation was carried out. In these cases, the resulting coloring cream was mixed with water in a ratio of 1: 1 and also applied to Scm long strands of standardized, 80% gray, but not specially pretreated human hair (Kerling). After 30 min exposure time at 32 ° C, the hair was rinsed, washed with a conventional shampoo and then dried.

The following abbreviations were used:
OFV oxidation dye precursor
E1 N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propanol hydrochloride
E2 1,4-bis (4-aminophenyl) diaza-cycloheptane
E3 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane
E4 bis (2-hydroxy-5-aminophenyl) methane
E5 2,4,5,6-tetraaminopyrimidine sulfate
E6 4-amino-3-methylphenol
E7 4-hydroxy-2,5,6-triaminopyrimidine sulfate
K1 is 2,6-dihydroxy-3,4-dimethylpyridine
K2 1-naphthol
K3 2,4-diaminophenoxyethanol dihydrochloride
K4 1,3-bis (2,4-diaminophenoxy) propane tetrahydrochloride

The result of the dyeing tests is shown in Table I.

Table I

Claims (12)

1. Agent for coloring keratinic fibers, containing in a cosmetically acceptable medium as a dye precursor

• A) at least one compound of the formula (I)
  wherein R represents a C _1-4 alkyl group or a C _1-4 hydroxyalkyl group and
  X and Y independently represent a hydroxy group or a C _1-4 alkyl group, and
• B) at least one binuclear developer component.

2. Composition according to claim 1, characterized in that the radical R of the formula (I) for a methyl group, an ethyl group or a β-hydroxyethyl group. 3. Composition according to claim 1 or 2, characterized in that at least one of Radicals X or Y represents a hydroxy group. 4. Composition according to one of claims 1 to 3, characterized in that the Compound of formula (I) is 2,6-dihydroxy-3,4-dimethylpyridine. 5. Composition according to one of claims 1 to 4, characterized in that the binuclear developer components is a compound of formula (II)
in which:

• - Z ¹ and Z ² are each independently a hydroxyl or NH ₂ radical optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ - hydroxyalkyl radical and / or by a bridge Y substituted is
• - 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 interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms may be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals,
• R ² and R ³ are each independently hydrogen or halogen, C ₁ to C ₄ alkyl, C ₁ to C ₄ monohydroxyalkyl, C ₂ to C ₄ polyhydroxyalkyl, C ₁ to C ₄ -aminoalkyl radical or a direct compound for bridging Y,
• R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ 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 proviso that the compounds of formula (II) contain only one bridge Y per molecule.

6. Composition according to one of claims 1 to S. characterized in that the Compound of the formula (II) is selected from N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-Aminophenyl) -1,3-diamino-propanol, N, N'-bis (β-hydroxyethyl) -N, N'-bis- (4'-) aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'- bis- (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -tetramethylenediamine, N, N'-bis (4-aminophenyl) -tetramethylenediamine; Methyl-aminophenyl) -tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis (4'-amino, 3'- methylphenyl) ethylenediamine, 1,8-bis (2,5-diaminophenoxy) -3,5-dioxoctane, bis (2-bis) hydroxy-5-aminophenyl) methane, 1,4-bis (4-aminophenyl) diaza-cycloheptane and 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane and its physiological compatible salts. 7. Composition according to claim 6, characterized in that the compound of the formula (II) is selected from N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, 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 physiologically acceptable salts. 8. Composition according to one of claims 1 to 7, characterized in that it at least contains another developer or coupler type oxidation dye precursor. 9. Composition according to one of claims 1 to 8, characterized in that it continues contains at least one dye precursor of the indole or indoline type. 10. Composition according to one of claims 1 to 9, characterized in that it continues contains at least one substantive dye. 11. A process for coloring keratinic fibers, characterized in that an agent according to any one of claims 1 to 10 is applied to the fibers and after a Exposure time is rinsed off again. 12. Use of a dye combination

• A) at least one compound of the formula (I)
  wherein R represents a C _1-4 alkyl group or a C _1-4 hydroxyalkyl group, and X and Y independently represent a hydroxy group or a C _1-4 alkyl group, and
• B) at least one binuclear developer component

for coloring keratinous fibers.