DE10116759A1 - Composition for dyeing keratinic fibers, especially for oxidation dyeing of human hair, comprises dye precursors, an oxidizing enzyme, a sugar surfactant and a reducing agent - Google Patents

Abstract

Composition for dyeing keratinic fibers comprises one or more dye precursors, an enzyme capable of catalyzing oxidation of the precursors, a sugar surfactant selected from alk(en)yl oligoglycosides and fatty acid N-alkyl polyhydroxyalkylamides, and a reducing agent.

Description

The present invention relates to agents for dyeing keratinic fibers, among others at least one enzyme that can catalyze the oxidation of the dye precursors, and an active ingredient combination of at least one sugar surfactant and a Reducing agent, the use of these agents for dyeing keratinic fibers and various methods for coloring keratinic fibers with this agent.

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 generally much more sensitive to shampooing than oxidative dyeing gene, so that much faster then a much undesirable nuance shift or even a visible "discoloration" occurs.  

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. For natural looking Dyeing must usually be a mixture of a larger number of oxida tion dye precursors are used; in many cases will continue to be direct drawing dyes used for shading.

The oxidative development of the dyeing can in principle be carried out with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used. As oxidizing agent come persulfates, chlorites and in particular hydrogen peroxide or its Anla products of urea, melamine and sodium borate. Usually will used an approximately 2-9% aqueous hydrogen peroxide solution. Under the influence such high oxidant concentrations, the keratinic fibers, in particular however, if they are already permed or bleached, they are damaged and rare Cases can also cause skin irritation due to these high concentrations.

An essential solution to this problem is the reduction of the Oxi dationsmittelkonzentration. It was therefore in the past on the one hand by color Due to their chemical structure already sought by low Amounts of hydrogen peroxide or can be oxidized by atmospheric oxygen. other The use of enzymes as biocatalysts has been proposed desired oxidation process with very little or no hydrogen peroxide only in can catalyze the presence of atmospheric oxygen.

In the German patent application DE-OS 21 55 390 an enzyme-activated, oxida tive hair dyeing method is described, are used in the small amounts of H ₂ O ₂ in combination with a peroxidase. Also in EP-A1-0 310 675 enzymatic hair treatment compositions are disclosed which contain at least a two-electron-reducing Oxi dase that uses oxygen as an acceptor. EP-B1-0 548 620 describes enzymatic hair dyes in which the oxidation of the dye precursors is catalyzed by the use of a peroxidase. Finally, EP-A2-0 795 313 describes enzymatic hair dyes which contain an oxygen-oxidoreductase / substrate system and a peroxidase and, as coupler components, an m-phenylenediamine derivative. However, all of these colorants can not completely convincing the achievable dyeing power (intensity, nuance, gloss, fastness properties).

The technique of easily oxidizable dye precursors as well as the previously be described enzymatic color development the disadvantage that in comparison to the her conventional methods, in particular with regard to the intensity, the gloss and the real properties of the dyeings worse results can be achieved. The enzyme The hair dyeing agents of the prior art also have the disadvantage that rela tively high amounts of enzyme are required to obtain conventional staining results.

The present invention is therefore based on the task of enzymatic colorants for To provide keratinic fibers that - even when in use minimum amounts of enzyme and / or dye - which are provided to colorants Meet requirements to a high degree. It is a further object of the present invention Invention to provide colorants that are gentle on the skin and hair.

A first object of the present invention are therefore agents for dyeing kerati African fibers, which are in a cosmetically acceptable carrier

• A) at least one dye precursor,
• B) at least one enzyme that catalyzes the oxidation of the dye precursors can
• C) at least one sugar surfactant selected from the group formed by
  • - alkyl and alkenyl oligoglycosides and
  • Fatty acid N-alkylpoly-hydroxyalkylamides and
  • - At least one reducing agent

contain.  

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

dye precursors

With regard to the dye preproducts (A) used in the colorants according to the invention, the present invention is not subject to any restrictions. The colorants according to the invention can be used as dye precursors

• - Developer and / or coupler type oxidation dye precursors, and
• Precursors of nature-analogous dyes, such as indole and indoline derivatives,

and mixtures of representatives of these groups.

In a first preferred embodiment, the colorant contains at least one Developer component. As developer components are usually primary aro matic amines with another, in 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.

It may be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerated salts as the developer component. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

in which
G ¹ represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ - monohydroxyalkyl, a C ₂ - to C ₄ -Polyhydroxyalkylradikal, 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'-amino phenyl radical;
G ² represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ - monohydroxyalkyl, a C ₂ - to C ₄ -Polyhydroxyalkylradikal, a (C ₁ - to C ₄₎ - alkoxy ( 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 -Carbamoylaminoalkaxyradikal;
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-alkylenedioxo group such as 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, a hydroxy methyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. Examples of halogen atoms according to the invention are 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 (E1) are especially the amino groups, C ₁ - to C ₄ monoalkylamino, C ₁ - to C ₄ - dialkylamino, C ₁ - to C ₄ -Trialkylammoniumgruppen, C ₁ - to C ₄ alkylamino groups -Monohydroxy , 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- 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-dihy droxypropyl) -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 (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

It may further be preferred according to the invention, as a developer component verbin use at least two aromatic nuclei containing amino acids and / or hydroxyl groups are substituted.

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made, in particular, of the compounds corresponding 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 bridge Y. or which is optionally part of a bridging ring system,
the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring 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, 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 -hydro-hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,
G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that
the compounds of the formula (E2) contain only one bridge Y per molecule and
the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred binuclear 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) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N ' bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) -N, N'-bis (4 'amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,4-bis (4'-aminophenyl) -diazacycloheptane, N, N'-bis (2-hydroxy-5-aminophenyl) methane hydroxy-5-aminobenzyl) piperazine, N- (4-aminophenyl) -p-phenylenediamine and 1,10-bis (2 ', 5'-diamino-phenyl) -1,4,7,10-tetraoxadecane and their 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 physiologically ver suitable salts.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particularly preferred are p-aminophenol derivatives of the formula (E3)

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₎ -alkylaminoradikal, a C ₁ - to C ₄ -Hydroxyalkoxyradikal, a C ₁ - to C ₄ hydroxyalkyl (C ₁ -C ₄ ) -aminoalkyl radical or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl radical, and
G ¹⁴ represents a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy - (C 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 mono hydroxyalkyl 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 (E3) are analogous to the above according to the invention Executions defined.  

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N- Methyl p-aminophenol, 4-amino-3-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxy methylamino-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 physio logically compatible salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, Amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2 - ((diethyl amino) 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 Ent 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-dimethyl amino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino pyrimidine.  

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'-chloro benzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopy razole, 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-methylpy razole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) - pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1 methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl 1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5- Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole and 3,5-diamino-4 (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazolo [1,5-a] -pyrimidine of the following formula (E4) and their tautomeric forms, provided that a tautomeric equilibrium exists:

in which:
G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkykadical, 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 radicals, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) -amino alkyl radical,
the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -Hydroxyalkyladikal, a C ₂ - to C ₄ - Polyhydroxyalkylradikal, 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 radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ - hydroxyalkyl) -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,
when p + q is 2, n is 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 (E4) are according to the invention analogous to the above Executions defined.

If the pyrazolo [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 represented, for example, in the following scheme:

Among the pyrazolo [1,5-a] -pyrimidines of the above formula (E4) can be called in particular special:
Pyrazol [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-dimethyl pyrazolo [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 (E4) can be used as in the literature described by cyclization starting from an aminopyrazole or hydrazine getting produced.

Furthermore, the compositions of the invention cationic dye precursors of Coupler and / or developer type included, as for example in the Publication WO-A1-99 / 03 819, WO-A2-99 / 03 834, WO-A1-99 / 03 836, WO-A1-99 / 48 856, WO-A1-99 / 48 874, WO-A1-99 / 48 875, WO-A2-00 / 42 971, WO-A1-00 / 42 979, WO-A1-00 / 42 980, WO-A1-00 / 43 356, WO-A1-00 / 43 367, WO-A1-00 / 43 368, WO-A1-00 / 43 386, WO-A1-00 / 43 388, WO-A1-00 / 43 389, WO-A1-00 / 43 396, EP-A1-0 984 006, EP-A1-0 984 007 and EP-A1-0 989 128 are described.

Particularly preferred cationic dye precursors are
[2- (2 ', 5'-diamino-phenoxy) -ethyl] -diethyl-methyl-ammonium chloride,
[2- (4'-amino-phenylamino) propyl] trimethylammonium chloride,
[4- (4'-Amino-phenylamino) pentyl] diethyl (2-hydroxyethyl) ammonium chloride,
1 - {[5'-amino-2 '- (2 "-hydroxyethylamino) -phenylcarbamoyl] -methyl} -1,4-dimethyl-piperazine-1-ium chloride,
1,4-bis-1- {3- [3 '- (2 ", 5" diamino-phenoxy) -propyl] -3H-imidazol-1-ium} butane dichloride,
1,3-bis [3 '- (2 ", 5" diamino-phenoxy) -propyl] -3H-imidazol-1-ium chloride,
N, N'-bis [3-N-methyl-4-N- (4'-aminoaniline) -ethyl] -1,1,4,4-tetramethyl-diammonium-1,3-propane-dibromide,
1,3-Bis-1- {3- {3 '- [(4 "-aminomethyl-aniline) -N-propyl]} - 3H-imidazol-1-ium} -propane dichloride
1,3-bis-1- {3- {3 '- [(4 "-amino-aniline) -N-propyl]} - 3H-imidazol-1-ium} -propandichlorid
1,3-Bis-1- {3- {3 '- [(4 "-amino-2" -methyl-aniline) -N-propyl]} - 3H-imidazol-1-ium} -propane dichloride
3- [3- (4'-Amino-phenylamino) propyl] -1-methyl-3H-imidazol-1-ium chloride
[3- (2 ', 5'-diamino-phenoxy) -propyl] -3-methyl-3H-imidazol-1-ium chloride
3- [3- (4'-amino-3'-methyl-phenylamino) propyl] -1-methyl-3H-imidazol-1-ium chloride
3- [3- (4'-Amino-2'-methyl-phenylamino) propyl] -1-methyl-3H-imidazol-1-ium chloride
1- [2- (4'-amino-2'-methoxy-phenylamino) -ethyl] -3-methyl-3H-imidazol-1-ium chloride
3- [3- (4'-Amino-2'-fluoro-phenylamino) propyl] -1-methyl-3H-imidazol-1-ium chloride
3- [3- (4'-amino-2'-cyano-phenylamino) propyl] -1-methyl-3H-imidazol-1-ium chloride
3- [2- (2 ', 5'-diamino-phenyl) -ethyl] -1-methyl-3H-imidazol-1-ium chloride
1- {2 - [(4'-amino-phenyl) -ethyl-amino] -ethyl} -3-methyl-3H-imidazol-1-ium chloride
N, N-bis [2- (3'-methyl-3H-imidazol-1-ium) ethyl] -4-amino-aniline hydrochloride
3- [2- (4'-amino-phenylamino) -butyl] -1-methyl-3H-imidazol-1-ium chloride
[2- (2 ', 4'-diamino-phenoxy) -ethyl] -diethyl-methyl-ammonium chloride
1- [3- (2 ', 4'-diamino-phenoxy) -propyl] -3-methyl-3H-imidazol-1-ium chloride
1 - [(3'-hydroxy-4'-methyl-phenylcarbamoyl) -methyl] -3-methyl-3H-imidazol-1-ium chloride
1,4-bis-1- {3- [3- (2 ', 4'-diamino-phenoxy) -propyl] -3H-imidazol-1-ium} butane dichloride
3 - [(3'-Hydroxy-4'-methanesulphonylamino-phenylcarbamoyl) -methyl] -1-methyl-3H-imidazol-1-ium chloride
3 - [(3 ', 5'-dichloro-2'-hydroxy-4'-methyl-phenylcarbamoyl) -methyl] -1-methyl-3H-imidazol-1-ium chloride
1 - [(3 ', 5'-dichloro-2'-hydroxy-4'-methyl-phenylcarbamoyl) -methyl] -1,4-dimethyl-piperazine-1-ium chloride
3 - [(4'-Acetylamino-2'-hydroxy-phenylcarbamoyl) -methyl-1-methyl-3H-imidazol-1-ium chloride
4- {3 - [(3'-Hydroxy-naphthalene-2'-carbonyl) -amino] -propyl} -4-methyl-morpholine-4-iodo-iodide
3 - [(1'-hydroxy-naphthalene-2'-ylcarbamoyl) -methyl] -1-methyl-3H-imidazol-1-ium chloride
3 - [(5'-Acetylamino-1'-hydroxy-naphthalene-2'-ylcarbamoyl) -methyl] -1-methyl-3H-imidazol-1-ium chloride
3 - [(1'-Hydroxy-5'-methanesulfonylamino-naphthalen-2'-ylcarbamoyl) -methyl] -1-methyl-3H-imidazol-1-ium chloride
[3- (4'-Amino-2 ', 5'-dimethyl-2H-pyrazol-3'-ylamino) -propyl] - (2-hydroxyethyl) -dimethylammonium chloride
1,3-bis - [(2'-hydroxy-4'-methyl-phenylcarbamoyl) -methyl] -3H-imidazol-1-ium chloride
1- [2- (6'-amino-benzo [1,3] dioxol-5-ylamino) -ethyl] -3-methyl-3H-imidazol-1-ium chloride
3- [2- (6'-amino-benzo [1,3] dioxol-5'-ylamino) ethyl] -1- (4- {3- [2- (6 "-amino) benzo [1,3] dioxol-5 "-ylamino) -ethyl] -3H-imidazol-1-ium} -butyl) -3H-imidazol-1-ium dichloride
3- [3- (3'-Amino-5'-methyl-pyrazolo [1,5-a] pyrimidin-7'-ylamino) -propyl] -1- (2-hydroxyethyl) -3H-imidazol-1-ium -chloride
1,3-bis-1- {3- {3 - [(2'-amino-aniline) -N-propyl]} - 3H-imidazol-1-ium} propane dibromide
N, N'-bis [3-N- (2'-amino-aniline) -N-propyl] -1,1,3,3-tetramethyl-diammonium-1,3-propane-dibromide
3- [3- (2'-aminophenylamino) propyl] -1-methyl-3H-imidazol-1-ium chloride
[2- (2'-Aminophenylamino) ethyl] trimethylammonium chloride and
3- (4'-hydroxy-1'-methyl-1H-indol-5-ylmethyl) -1-methyl-pyridinium methosulfate.

Furthermore, colorants are preferred according to the invention, the at least one Kupplerkom component included. As coupler components are usually m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives used. Suitable coupler substances are in particular 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 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-diaminophenoxy ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethyl amino) -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-3,4 dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxy-methyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-Dihy droxynaphthalin, 1,7-dihydroxynaphthalene , 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxy pyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylene dioxybenzene.

Particularly preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihy droxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

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 staining result or for other reasons, z. As 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.  

If the dye precursors are amino compounds, leave from these produce in a conventional manner, the known acid addition salts. All Statements of this document and accordingly the claimed scope of protection relate there both on the compounds present in free form and on their water soluble, physiologically acceptable salts. Examples of such salts are the hydro chlorides, hydrobromides, sulphates, phosphates, acetates, propionates, Citrates and the lactates.

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. In a second preferred embodiment, the colorants contain min at least one indole and / or indoline derivative.

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

in the independently of each other
R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl 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 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 (Ib)

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-dihy droxyindole, 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 a further embodiment, it may be preferred according to the invention, the indoline or indole derivative in hair dyes in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-Ami nosäure; most preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, especially arginine.

In addition to the dye precursors, the inventive compositions for achieving the desired dyeing effects continue to at least one substantive dye contain. Direct dyes are usually nitrophenylenediamines, nitro aminophenols, azo dyes, anthraquinones or indophenols. Preferred directly Drawing dyes are those under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 known compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) - amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-  Hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2- nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-ol nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'- carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, Hy droxyethyl-2-nitro-toluidine, picramic acid and its salts, 2-amino-6-chloro-4- nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4- nitrobenzene.

Furthermore, the agents according to the invention may contain a cationic substantive dye. Particularly preferred are

• a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well
• c) direct dyes containing a heterocycle containing at least one having quaternary nitrogen atom, as for example in EP-A2-998 908, on which is explicitly referred to at this point, in the claims 6 to 11 ge be called.

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

The compounds of formulas (DZ1), (DZ3) and (DZ5) are most preferred cationic substantive dyes of group (iii).

The agents according to the invention according to this embodiment contain the direct draw the dyes preferably in an amount of 0.01 to 20 wt .-%, based on the ge whole 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.

enzymes

Furthermore, the agents according to the invention contain, as second compelling component, at least one enzyme which can catalyze the oxidation of the dye precursors. Although in principle all enzymes which can catalyze this process are suitable according to the invention, the enzymes which have proved to be particularly suitable are those which have been described

• a) generate in situ small amounts of hydrogen peroxide,
• b) directly oxidize the dye precursors using atmospheric oxygen or
• c) accelerate the oxidation of the dye precursors by hydrogen peroxide.

The behavior described under (i) typically have oxidases associated with their respective substrate react to form hydrogen peroxide. examples for such enzymes are glucose oxidase (EC No. 1.1.3.4), alcohol oxidase (EC no. 1.1.3.13), oxidase for secondary alcohols (EC No. 1.1.3.18), oxidase for long-chain Alcohols (EC No. 1.1.3.20), glycerol-3-phosphate oxidase (EC No. 1.1.3.21), glycolate Oxidase (EC No. 1.1.3.15), methanol oxidase (EC No. 1.1.3.31), vanillyl alcohol oxidase (EC No. 1.1.3.38), pyruvate oxidase (EC No. 1.2.3.3), oxalate oxidase (EC No. 1.2.3.4), Cholesterol oxidase (EC No. 1.1.3.6), uricase (EC No. 1.7.3.3), lactate oxidase (EC no. 1.13.12.4), xanthine oxidase (EC No. 1.1.3.22), pyranose oxidase (EC No. 1.1.3.10), Amino acid oxidases (EC No. 1.4.3.2, EC No. 1.4.3.3), acyl-CoA oxidase (EC no. 1.3.3.6), glutamate oxidases (EC No. 1.4.3.7, EC No. 1.4.3.11), protein lysine 6-oxidase (EC No. 1.4.3.14), lysine oxidase (EC No. 1.4.3.14), sulfite oxidase (EC No. 1.8.3.1), Catechol oxidase (EC No. 1.10.3.1), L-ascorbate oxidase (EC No. 1.10.3.3), choline Oxidase (EC No. 1.1.3.17), monoamine oxidase (EC No. 1.4.3.4), diamine oxidase (EC no. 1.4.3.6), sarcosine oxidase (EC No. 1.5.3.1) and galactose oxidase (EC No. 1.1.3.9). Particularly preferred examples of such oxidases are uricase, glucose oxidase as well as the choline oxidase. Uricase is a particularly preferred enzyme of the Class (i). For these enzymes to catalyze the dyeing process, the Means according to the invention always the corresponding substrates in a sufficient Quantity included.

Enzymes that directly oxidize dye precursors using atmospheric oxygen, (ii) are, for example, the laccases (EC No. 1.10.3.2), the tyrosinases (EC No. 1.10.3.1), Ascorbate oxidase (EC No. 1.10.3.3), the bilirubin oxidases (EC No. 1.3.3.5) and Phenol oxidases of the type Acremonia, Stachybotrys or Pleurotus. The laccases are Very particularly preferred according to the invention enzymes of class (ii).

Category (iii) of the enzymes preferred according to the invention includes the peroxidases (EC No. 1.11.1.7). These allow dyeings even at low levels Hydrogen peroxide. It is immaterial whether small amounts of hydrogen peroxide in the formulation is incorporated or whether it is listed by (i) Enzyme is formed in situ. Particularly preferred according to the invention is the peroxidase, which can be obtained from horseradish.  

The enzymes can be incorporated into the colorant itself; they are preferred but made up separately from the dye precursors and only immediately before Application mixed with the actual colorant. Should the enzymes be 1- Component system incorporated in the colorant, it is according to the invention preferred to assemble the system under exclusion of air.

Furthermore, it has been found that it may be preferred according to the invention, the colorant free of blowing agents, that is not to make up as foam formulation.

The enzyme is preferably in an amount of 0.0001-1 wt .-%, based on the Pro teinmenge of the enzyme and the entire colorant used.

sugar surfactants

The agents according to the invention contain at least the third obligatory component (C) a sugar surfactant.

According to a first embodiment (C1), the sugar surfactant is an alkyl or alkenyl oligoglycoside. These sugar surfactants are known nonionic surfactants according to formula (II),

R ¹ O- [G] _p (II)

in which R ^{1 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representative of the extensive literature is here on the review by Biermann et al. in Starch / Stärke 45, 281 (1993), B. Salka in Cosm. Toil. 108, 89 (1993) and J. Kahre et al. in SÖFW Journal Heft 8, 598 (1995).

The alkyl and alkenyl oligoglycosides may be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred ones Alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.  

The index number p in the general formula (II) indicates the degree of oligomerization (DP), d. H. the distribution of mono- and oligoglycosides and stands for a number between 1 and 10. While p in the single molecule must always be integer and here especially the Values p = 1 to 6 is the value p for a particular alkyl oligoglycoside an analytically determined arithmetical variable, which is usually a fractional number. Preferably, alkyl and / or Alkenyloligoglykoside with a middle oligo merisierungsgrad p used from 1.1 to 3.0. From an application point of view such alkyl and / or Alkenyloligoglykoside preferred, their degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis. Preference is given to alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3), which are obtained as a feed in the distillative separation of technical C ₈ -C ₁₈ coconut fat alcohol and with a content of less than 6 wt .-% C _12th Alcohol can be contaminated as well as alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Preference is given to alkyloligo glucosides based on hydrogenated C _12/14 cocoalcohol having a DP of 1 to 3.

According to a second embodiment (C2) of the invention, the zuc kertensid is a fatty acid-N-alkylpolyhydroxyalkylamide, a nonionic surfactant of the formula (III),

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{3 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.

The fatty acid N-alkylpolyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their preparation, reference may be made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984. An overview of this topic by H. Kelkenberg can be found in Tens. Surf. Det. 25, 8 (1988). Preferably, the fatty acid N-alkylpolyhy droxyalkylamide derived from reducing sugars with 5 or 6 carbon atoms, in particular from the special glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides, as represented by the formula (IV):

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (IV) in which R ^{3 is} hydrogen or an alkyl group and R ² CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petro selinsäure, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or those technical mixtures. Particular preference is given to fatty acid N-alkylglucamides of the formula (IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C _12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The sugar surfactant is preferred in amounts in the agents used in the invention from 0.1 to 20% by weight, based on the total agent. Quantities of 0.5-5 Wt .-% are particularly preferred.  

reducing agent

Furthermore, the agents according to the invention preferably contain a reducing agent. Examples of reducing agents which are preferred according to the invention are sodium sulfite, Ascorbic acid, thioglycolic acid and its derivatives, sodium thionite, Alkali metal citrate salts and N-acetyl-L-cysteine. Very particularly preferred Reducing agents are alkali metal citrate salts, especially sodium citrate, and N-acetyl L-cysteine. N-acetyl-L-cysteine is a most preferred alkalizing agent.

fatty acid partial

As a further component, the agents according to the invention may contain fatty acid partial glycerides. These fatty acid partial glycerides are monoglycerides, diglycerides and their technical mixtures. With the use of technical products can still be small amounts of triglycerides in terms of production. The partial glycerides preferably follow the formula (V),

in which R ⁴ , R ⁵ and R ⁶ independently of one another are hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents a Acyl radical and at least one of these groups is hydrogen. The sum (m + n + q) is 0 or numbers from 1 to 100, preferably 0 or 5 to 25. Preferably, R ^{4 is} an acyl radical and R ⁵ and R ^{6 are} hydrogen and the sum (m + n + q) is 0. Typical examples are mono- and / or diglycerides based on caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic , Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Preferably, oleic acid monoglycerides are used.

The fatty acid partial glyceride is preferred in the agents used in the invention Amounts of 0.1-20 wt .-%, in particular 0.5-2 wt .-%, based on the total Contain funds.

The teaching of the invention also includes embodiments in which the Invention according to the mean of several sugar surfactants and / or more fatty acid partial glycerides ent hold.

thickener

As a further optional component, the agents according to the invention can also be used contain at least one thickener. Regarding these thickeners exist no restrictions in principle. Although in principle both organic and pure inorganic thickening agents can be used are the organic Thickening agent according to the invention preferably.

According to a first preferred embodiment, the thickening to an anionic, synthetic polymer. Preferred anionic groups are Carboxylate and the sulfonate group.

Examples of anionic monomers making up the polymeric anionic thickening may consist of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The can acidic groups in whole or in part as sodium, potassium, ammonium, mono- or Triethanolammonium salt present. Preferred monomers are maleic anhydride and in particular 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred Be networking agents. Such compounds are, for example, under the goods Draw Carbopol® commercially available. Also preferred is the homopolymer of the 2- Acrylamido-2-methylpropanesulfonic acid, for example, under the name Rheothik® 11-80 is commercially available.  

Within this first embodiment, it may further be preferred to use copolymers from at least one anionic monomer and at least one nonionic Use monomer. With respect to the anionic monomers is referred to above passed substances directed. Preferred nonionic monomers are acrylamide, Methacrylamide, acrylic esters, methacrylic acid esters, itaconic acid mono- and diesters, Vinyl pyrrolidone, vinyl ethers and vinyl esters.

Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ - to C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn® 33 from Rohm & Haas. But also preferred are copolymers of acrylic acid, methacrylic acid or their C ₁ - to C ₆ -alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol. Suitable ethylenically unsaturated acids are in particular acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are in particular steareth-20 or ceteth-20. Such copolymers are sold by Rohm & Haas under the trade name Aculyn® 22 and by National Starch under the trade names Structure® 2001 and Structure® 3001.

Preferred anionic copolymers are also acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers having sulfonic acid-containing mono mers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer may also be present in crosslinked form, with polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide preferably being used as crosslinking agents. Such a polymer is contained in the commercial products Sepigel® 305 and Simul gel® 600 from SEPPIC. The use of these compounds, in addition to the Polyierkomponente a hydrocarbon mixture (C ₁₃ -C ₁₄ -Isoparaffin relationship isohexadecane) and a non-ionic emulsifier (Laureth-7 or polysorbate-80), has proved in the context of the teaching of the invention as FITS advantageous ,

Also polymers of maleic anhydride and methyl vinyl ether, especially those with Crosslinks are preferred thickeners. A time crosslinked with 1,9-decadiene Methylacrylate acid copolymer is marketed under the name Stabileze® QM Trade available.

In a second embodiment, the thickener is a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group are bonded via a C _1-4 hydrocarbon group to a built-up of acrylic acid, methacrylic acid or their derivatives polymer backbone, have proved to be FITS suitable.

Homopolymers of the general formula (VI),

wherein R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from C _1-4 alkyl, alkenyl or hydroxyalkyl groups, m = 1, 2, 3 or 4 , n is a natural number and X ^{- is} a physiologically acceptable organic or inorganic anion, as well as copolymers consisting essentially of the monomer units listed in formula (I) and nonionic monomer units, are particularly preferred cationic polymeric thickeners. In the context of these polymers, preference is given to those according to the invention for which at least one of the following conditions applies:
R ¹ is a methyl group,
R ² , R ³ and R ⁴ are methyl groups,
m has the value 2.

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

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

The homopolymer is preferably in the form of a nonaqueous polymer dispersion which should have a polymer content not less than 30 wt .-%, used. Such polymer Dispersions are known under the names Salcare © SC 95 (about 50% polymer content, white tere component: mineral oil (INCI name: mineral oil) and tridecyl polyoxy propylene-polyoxyethylene ether (INCI name: PPG-1-Trideceth-6)) and Salcare® SC 96 (about 50% polymer content, other components: mixture of diesters of Propy lenglykols with a mixture of caprylic and capric acid (INCI name: Propylene glycol dicaprylates / dicaprate) and tridecyl polyoxypropylene polyoxyethylene ether (INCI name: PPG-1-Trideceth-6) commercially available.

Also suitable according to the invention are nonionic thickeners of the type polymeric fatty acid amides, as described for example in EP-A1-632083 or the EP-A2-959066.

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

In a third preferred embodiment naturally occurring thickening agents are used. Preferred thickening agents of this embodiment are, for example, nonionic guar gums. According to the invention, both modified and unmodified guar gums can be used. Unmodified guar gums are sold, for example, under the trade name Jaguar® C by Rhone Poulenc. Modified guar gums preferred according to the invention contain C ₁ - to C ₆ -hydroxyalkyl groups. Preferably, the groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. Such modified guar gums are known in the art and can be prepared for example by reaction of the guar gums with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed in relation to the number of guar gum free hydroxy groups, is preferably between 0.4 and 1.2. Such modified guar gums are commercially available under the trade names Jaguar® HP8, Jaguar® HP60, Jaguar® HP120, Jaguar® DC293 and Jaguar® HP105 from Rhone Poulenc.

Further suitable natural thickening agents are also already known from the prior Technique known. It is therefore explicitly referred to the work of Robert L. Davidson with the Title "Handbook of Water soluble gums and resins", published by Mc Graw Hill Book Company (1980).

According to this embodiment, biosaccharide gums are further preferred microbial Origin, such as the scleroglucangum or xanthangum, gums from plant exsu data such as gum arabic, ghatti gum, karaya gum, gum tragacanth Gum, carrageenan gum, agar-agar, locust bean gum, pectins, alginates, starch Fractions and derivatives such as amylose, amylopectin and dextrins.

But also nonionic, fully synthetic polymers, such as polyvinyl alcohol or polyvinylpyrrolidone, can be used as thickening agents according to the invention. Preferred nonionic, fully synthetic polymers are, for example, from the company BASF sold under the trade name Luviskol®.  

According to the invention, preference is given to anionic and nonionic thickening polymers.

In a most preferred embodiment of the present invention as a thickener cellulose and / or cellulose derivatives, such as methyl cellulose, carboxyalkylcelluloses and hydroxyalkylcelluloses used.

Preferred hydroxyalkylcelluloses are in particular the hydroxyethylcelluloses, which under the names Cellosize the company Amerchol, Natrosol® the company Hercules or Culminal® and Benecel® from Aqualon. Likewise The hydroxypropylcelluloses are suitable according to the invention, as they are, for example, under the name Klucel® be sold by the company Hercules. suitable Carboxyalkylcelluloses are in particular the carboxymethylcelluloses, as they are among the Designations Blanose® from the company Aqualon, Aquasorb® and Ambergum® from the Hercules and Cellgon® are sold by Montello.

Nursing polymers

In a further preferred embodiment, the agents according to the invention contain furthermore at least one nourishing polymer. Among caring polymers are both natural as well as synthetic polymers which are anionic, cationic, amphoteric or non-ionic, to understand.

Cationic polymers are polymers which have groups in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group are bonded via a C _1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

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® H100, Celquat® L200 and Polymer JR®400 are preferred quaternized cellulose derivatives,
• Cationic alkyl polyglycosides according to DE-PS 44 13 686,
• Cationised honey, for example the commercial product Honeyquat® 50,
• - cationic guar derivatives, such as those under the trade name Cos media®Guar and Jaguar® distributed products,
• - Polysiloxanes with quaternary groups, such as those commercially available Products Q2-7224 (Manufacturer: Dow Corning; a stabilized trimethylsilylamodi methicon), Dow Corning® 929 emulsion (containing a hydroxylamino-modified Silicone, also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (Her steller: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80),
• Polymeric dimethyldiallylammonium salts and their copolymers with esters and amines that of acrylic acid and methacrylic acid. The under the names Merquat® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat® 550 (dimethyldiallyl-ammo ammonium chloride-acrylamide copolymer). Commercially available products are examples of such cationic polymers,
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino alkyl acrylate and methacrylate, such as quaternized with diethyl sulfate Vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are commercially available under the names Gafquat® 734 and Gafquat® 755,
• - Vinylpyrrolidone-Vinylimidazoliummethochlorid copolymers, as described in the Be drawings Luviquat® FC 370, FC 550, FC 905 and HM 552,
• - 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 poly merhauptkette.

Likewise, as cationic polymers can be used under the name Polyquaternium-24 (commercial product eg Quatrisoft® LM 200), known poly mers. Also usable according to the invention are the copolymers of vinylpyrrolidone, as available as commercial products Copolymer 845 (manufacturer: ISP), Gaffix® VC 713 (manufacturer: ISP), Gafquat® ASCP 1011, Gafquat® HS 110, Luviquat® 8155 and Luviquat® MS 370 are available.

Further cationic polymers according to the invention are the so-called "temporary cationi These polymers usually contain an amino group which is found in be agreed pH values as quaternary ammonium group and thus present cationic. before zugt are, for example, chitosan and its derivatives, such as those under the Tradenames Hydagen® CMF, Hydagen® HCMF, Kytamer® PC and Chitolam® NB / 101 are freely available on the market. Chitosans are deacetylated chitins that are in under different degrees of deacetylation and different degrees of degradation (Molekularge weights) are commercially available. Their preparation is z. B. in DE 44 40 625 A1 and in DE 195 03 465 A1.

Particularly suitable chitosans have a degree of deacetylation of at least 80% and a molecular weight of 5.10 ⁵ to 5.10 ⁶ (g / mol).

For the production of preparations according to the invention, the chitosan must be converted into the salt form be led. This can be done by dissolving in dilute aqueous acids. When Acids are both mineral acids such. Hydrochloric acid, sulfuric acid and phosphoric acid as well as organic acids, eg. As low molecular weight carboxylic acids, polycarboxylic acids and Hydroxycarboxylic acids suitable. Furthermore, higher molecular weight alkyl sulfone acids or alkyl sulfuric acids or organophosphoric acids are used so far these have the required physiological compatibility. Suitable acids for Transfer of chitosan in the salt form are z. Acetic acid, glycolic acid, tartaric acid, Malic acid, citric acid, lactic acid, 2-pyrrolidinone-5-carboxylic acid, benzoic acid or Salicylic acid. Preference is given to low molecular weight hydroxycarboxylic acids such as. B. glycol acid or lactic acid.  

Furthermore, amphoteric polymers can be used as constituents as polymers to increase the action of the active substance according to the invention. The term amphoteric polymers includes both those polymers which contain in the molecule both free amino groups and free -COOH or SO ₃ H groups and are capable of forming internal salts, as well as zwitterionic polymers which contain quaternary ammonium groups in the molecule and COO ^- - or -SO ₃ ^- groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups.

An example of an amphopolymer which can be used according to the invention is that disclosed by Be Drawing Amphomer® available acrylic resin, which is a copolymer of tert-butyl aminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more Monomers from the group of acrylic acid, methacrylic acid and their simple esters represents.

Another example of a polymer which can be used according to the invention is the example under the name Merquat® 280 available Polyquaternium-22, which is a copolymer from dimethyldiallylammonium chloride and acrylic acid.

Further inventively usable amphoteric polymers are those in the British Laid-open publication 2 104 091, the European patent application 47 714, the euro European Patent Laid-Open Publication No. 217,274, European Patent Laid-Open Nos. 283,817 and the German Offenlegungsschrift 28 17 369 compounds.

Preferably used amphoteric polymers are those polymers which are composed in wesent union from

• a) monomers having quaternary ammonium groups of the general formula (VII),
  R ²² -CH = CR ²³ -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ²⁴ R ²⁵ R ²⁶ A ^(-) (VII)
  in the R ²² and R ²³ independently of one another are hydrogen or a methyl group and R ²⁴ , R ²⁵ and R ²⁶ independently of one another are alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A ^{(-) is} the anion of an organic or inorganic acid and
• b) monomeric carboxylic acids of the general formula (VIII),
  R ²⁷ -CH = CR ²⁸ -COOH (VIII)
  in which R ²⁷ and R ^{28 are} independently hydrogen or methyl groups.

These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention. With regard to the details of the preparation of these polymers is expressly made to the content of German Patent Application 39 29 973 reference. Very particular preference is given to those polymers in which monomers of the type (a) are used in which R ²⁴ , R ²⁵ and R ^{26 are} methyl groups, Z is an NH group and A ^{(-) is} a halide, methoxysulfate or ethoxysulfate Ion is; Acrylamide amidopropyl trimethyl ammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the stated polymers.

A preferred such polymer is, for example, that under the name Merquat® 2001 Polyquaternium-47 sold by Calgon.

The agents according to the invention can also be nonionic in a third variant containing nourishing polymers.

Suitable nonionic polymers are, for example:

• - Gramophone
• - siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, although not as Volatile siloxanes are understood as compounds whose boiling point at Normal pressure above 200 ° C is. Preferred siloxanes are polydialkyl siloxanes such as polydimethylsiloxane, polyalkylarylsiloxanes as in For example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and poly dialkylsiloxanes containing amine and / or hydroxy groups.
• - Glycosidically substituted silicones according to EP 0612759 B1.

It is according to the invention also possible that the preparations used several, esp in particular two different nourishing polymers of the same charge and / or one each ionic and an amphoteric and / or nonionic polymer included.

According to the invention, the term "care polymer" also means special preparations of polymers such as spherical polymer powders. There are various methods known to produce such microspheres of different monomers, for. Example, by special polymerization or by dissolving the polymer in a solvent and spraying in a medium in which the solvent can evaporate ver or herausdiffundieren from the particles. Such a method is z. B. from EP 466 986 B1. Suitable polymers are z. As polycarbonates, polyurethanes, polyacrylates, polyolefins, polyesters or polyamides. Particularly suitable are those spherical polymer powders whose primary particle diameter is less than 1 micron. Such products based on a polymethacrylate copolymer are, for. B. under the trademark Polytrap® Q5-6603 (Dow Corning) in the trade. Other polymer powders, e.g. Based on polyamides (nylon 6, nylon 12) are having a particle size of 2-10 microns (90%) and a specific surface area of about 10 m ² / g under the trade name Orgasol® 2002 DU Nat Cos (Atochem SA , Paris) available. Other spherical polymer powders which are suitable for the purpose according to the invention are, for. The polymethacrylates (Micro pearl M) from SEPPIC or (Plastic Powder A) from NIKKOL, the styrene-divinylbenzene copolymers (Plastic Powder FP) from NIKKOL, the polyethylene and polypropylene powders (ACCUREL EP 400) from AKZO, or silicone polymers (Silicone Powder X2-1605) from Dow Corning or even spherical cellulose powders.

The nourishing polymers are preferred in the agents used in the invention Amounts of 0.01 to 10 wt .-%, based on the total agent included. Quantities of 0.1 to 5, especially from 0.1 to 2 wt .-%, are particularly preferred.

Other ingredients

For the preparation of the colorants of the invention, the dye precursors in a suitable water-containing carrier can be incorporated. For the purpose of hair coloring advertising are such carrier z. As creams, emulsions, gels or surfactant-containing  mende solutions, eg. As shampoos, foam aerosols or other preparations for the Application on the hair are suitable.

The colorants of the invention may further be all for such preparations be knew active ingredients, additives and excipients included. In many cases, the colorants contain at least one other surfactant, in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. The A person skilled in the art can determine the possible influence of the various surfactants on the activity of the optionally enzyme system according to the invention by simple preliminary experiments check.

In a preferred embodiment of the present invention is in the means for Coloring keratinous fibers a combination of anionic and nonionic Ten siden or a combination of anionic and amphoteric surfactants used.

However, it has proved in individual cases to be advantageous, the surfactants from amphoteric or Select nonionic surfactants, as these are usually the inventive Less influence on dyeing process.

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. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or poly glycol ether groups, ester, ether and amide groups and hydroxyl 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 as well as the mono-, di- and trialkanolammonium salts with 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,
• - Sulfobernsteinsäuremono- 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,
• - Protein concentrates acid,
• - Cocosmonoglyceridsulfate,
• - Amidethersulfate.

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.

Furthermore, especially as co-surfactants, zwitterionic surfactants who used the. As zwitterionic surfactants are those surface-active compounds designated net, 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-dimethylammoniumglycinate, for example, the cocoalkyl dimethylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethyl ammoniumglycinate, for example Kokosacylaminopropyl-dimethylammonium glycinate, and 2-alkyl 3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethyl carboxymethylglycinat. 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-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C-Ato men in the alkyl group. Particularly preferred ampholytic surfactants are N-coco alkylaminopropionate, Kokosacylaminoethylaminopropionat and C _12-18 -Acylsarco sin.

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. B. cetyltrimethylammo 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 are included 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. An inventor According to the invention, particularly suitable compound from this group of substances provides that the name Tegoamid® S18 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 Coming 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 particular raw material alkyl chain lengths receives.

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 when, for example, hydrotalcites, alkaline earth metal salts of ethercar bonsäuren, alkaline earth metal oxides, hydroxides or alcoholates used as catalysts become. The use of products with restricted homolog distribution can be be preferred.

Furthermore, the agents according to the invention preferably contain at least one alkali metal insurance agent. Preferred alkalizing agents are ammonia, monoethanolamine, Isopropylamine, isopropanolamine, 2-amino-2-methylpropan-1-ol, an alkali metal hydroxide, in particular sodium hydroxide or potassium hydroxide, and in particular arginine, Lysine and histidine. Particularly preferred according to the invention are colorants which Monoethanolamine, 2-amino-2-methylpropan-1-ol, an alkali metal hydroxide, especially sodium hydroxide or potassium hydroxide, and in particular arginine, lysine and histidine.

Furthermore, the colorants of the invention can preferably still a konditio active ingredient selected from the group consisting of cationic surfactants, alkyl  amidoamines, paraffin oils, vegetable oils and synthetic oils is formed, ent hold. With regard to the cationic surfactants, reference is made to the above statements.

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 Corning® 929 emulsion (Containing a hydroxyl-amino-modified silicone, which is also called Amodimethicone be characterized), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil® Quat 3270 and 3272 (manufactured by Th. Goldschmidt; diquaternary Polydi methylsiloxanes, quaternium-80).

Also usable as conditioning agents are paraffin oils, synthetically herge introduced oligomeric alkenes as well as vegetable oils such as jojoba oil, 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.

Furthermore, the preparations used according to the invention preferably contain min at least one oil component.

Oil components which are suitable according to the invention are in principle all water-insoluble oils and fatty substances and their mixtures with solid paraffins and waxes. When According to the invention, those substances whose solubility in water is insoluble in water are defined Water at 20 ° C is less than 0.1 wt .-%. The melting point of the individual oil or fat components is preferably below about 40 ° C. Oil and fat comp at room temperature, d. H. are liquid below 25 ° C, can invent According to the invention, be particularly preferred. When using multiple oil and grease compo However, as well as solid paraffins and waxes, it is generally sufficient  when the mixture of oil and fat components and possibly paraffins and waxes these conditions are sufficient.

A preferred group of oil components are vegetable oils. Examples of such Oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, Wheat germ oil, peach kernel oil and the liquid portions of coconut oil.

However, other triglyceride oils are also suitable, such as the liquid components of beef tallow as well as synthetic triglyceride oils.

Another, particularly preferred group according to the invention as an oil component Barer compounds are liquid paraffin oils and synthetic hydrocarbons as well Di-n-alkyl ethers having a total of between 12 and 36 carbon atoms, in particular 12 to 24 carbon atoms Atoms, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n- undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl-n-decyl ether, n-decyl-n- undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether, and di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso-pentyl-n- octyl ether and 2-methylpentyl-n-octyl ether. The available as commercial products Verbin 1,3-di (2-ethylhexyl) cyclohexane (Cetiol® S) and di-n-octyl ether (Cetiol® OE). may be preferred.

Also usable according to the invention oil components are fatty acid and fatty alcohol ester. The monoesters of the fatty acids with alcohols having 3 to 24 C atoms are preferred. This substance group is the product of the esterification of fatty acids with 6 to 24 C atoms, such as, for example, caproic acid, caprylic acid, 2-ethylhexanoic acid, Capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitolein acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, Linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid as well as their technical mixtures, the z. B. in the pressure splitting of natural Fats and oils, in the oxidation of aldehydes from Roelen's oxosynthesis or the dimerization of unsaturated fatty acids incurred with alcohols such as Isopropyl alcohol, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, Lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol,  Stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, Li nolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol, erucyl alcohol and un 21391 00070 552 001000280000000200012000285912128000040 0002010116759 00004 21272d Brassidyl alcohol and technical mixtures thereof, the z. As in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction incurred in the dimerization of unsaturated fatty alcohols. According to the invention preferred are isopropyl myristate, C16-18 alkyl isononanoate (Cetiol® SN), Stearic acid 2-ethylhexyl ester (Cetiol® 868), cetyl oleate, glycerol tricaprylate, coconut fat alcohol caprinate / caprylate and n-butyl stearate.

Furthermore, dicarboxylic acid esters such as di-n-butyl adipate, di (2-ethylhexyl) adipate, Di (2-ethylhexyl) succinate and di-isotridecyl acelate, and diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2-ethylhexanoate), Propy glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate and Neopentyl glycol di-capylate is oil component usable in the invention, as well complex esters such. B. the diacetyl-glycerol monostearate.

Finally, fatty alcohols containing 8 to 22 carbon atoms may also be used according to the invention kende oil components are used. The fatty alcohols can be saturated or unge saturates and be linear or branched. Applicable in the context of the invention are, for example Decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, Decadienol, oleyl alcohol, eruca alcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, Cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, capryl alcohol, caprin alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols, and these listings are given by way of example and not by way of limitation should. However, the fatty alcohols are derived from preferably natural fatty acids, wherein usually characterized by recovery from the esters of fatty acids by reduction can be done. Also usable according to the invention are those fatty alcohols cuts caused by the reduction of naturally occurring triglycerides such as beef tallow, Palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or from their transesterification products with corresponding alcohols resulting fatty acid esters produced, and thus represent a mixture of different fatty alcohols.  

The oil components are preferably used in amounts of 0.05 to 10 wt .-%, in particular from 0.1 to 2 wt .-% used in the colorants of the invention.

Other active ingredients, auxiliaries and additives are, for example

• - structurants such as maleic acid and lactic acid,
• - 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, Glycerine 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, Oranges, Grapefruit, Sage, Ros male, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, 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,
• Stabilizing agent for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - Antioxidants and
• - preservatives.

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.

Conveniently, the enzyme preparation with just before dyeing the hair the preparation of the dye precursors mixed. The resulting Ready-to-use hair dye preparation should preferably have a pH in the range of 4 to 10, in particular from 6 to 9, especially from 7 to 8.5. Further, have yourself low-viscosity application preparations proved to be particularly advantageous, the Viscosity of less than 3000 mPa.s (Brookfield, spindle 4, 20 rev / min, 20 ° C) have. The application temperatures can range between 10 and 50 ° C, preferably between 20 and 35 ° C, lie. After an exposure time of approx. 30 minutes th the hair dye is removed by rinsing of the hair to be dyed. The Washing with a shampoo is eliminated if a strong surfactant-containing carrier, eg. B. a Dyeing shampoo, was used.

In order to further increase the dyeing power of the agents according to the invention, it can According to the invention be preferred, the fibers after treatment with the inventive agent of a post-treatment with a solution containing small amounts  Hydrogen peroxide containing undergo. The solution can be in the form of a Shampoos or a conditioner be prepared. Usually included such aftertreatment agent hydrogen peroxide in concentrations between 0.01 and 0.5% by weight.

In a further embodiment of the present invention, it may be preferred that Agent, in particular the separately prepared enzyme preparation, free of antioxidants dantien and / or complexing agents to formulate, as these the effect of the enzymes bloc can kieren.

A second object of the present invention is a method for dyeing kerati nischer fibers, in which an agent according to the invention is applied to the fibers and rinsed again after a contact time.

A third object of the present invention is a method for dyeing kerati nischer fibers, wherein in a first step, a preparation containing the compo Nenten (A), (C) and (D) is applied to the fibers, the fibers after a contact time optionally rinsed and in a second step, a preparation containing the component (B) to which fibers are applied. Also as inventive a method has proved suitable in which in a first step, the fibers with a preparation containing the component (B) are treated, the fibers after a Exposure time are optionally rinsed and then a preparation, containing components (A), (C) and (D) is applied.

A fourth object of the present invention is the use of the erfindungsge suitable means for oxidative coloring keratinischer fibers.

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

Examples

The quantities given in the following examples are, unless otherwise stated, Weight.

I) Composition of the staining gels

AL = L <coloring gel 1: Natrosol® 250 HR ¹ 2:00 Eumulgin® B2 ² 12:50 Plantacare® 1200 UP ³ 12:50 Lamesoft® PO65 ⁴ 12:20 Tri-sodium citrate dihydrate 12:50 2,4,5,6-tetra-sulfate 12:10 p-toluenediamine sulphate 12:10 4-amino-3-methylphenol 12:25 m-aminophenol 12:10 4-chlororesorcinol 12:12 2-amino-3-hydroxypyridine 12:13 Monoethanolamine ad pH 7 water ad 100.00 ¹ Hydroxyethylcellulose (INCI name: Hydroxyethylcellulose) (Hercules) @ ² cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) @ ³ C _12-16 -alkyl-1,4-glucoside (about 50 to 53% active ingredient), INCI name: lauryl glucoside) (Cognis) @ ⁴ Alkyl polyglucoside-oleic acid monoglyceride mixture (about 32 to 35% water content, INCI name: Glucoside, Glyceryl Oleate, Aqua (Water)) (Cognis)

AL = L <staining gel 2: Natrosol® 250 HR 2:00 Plantacare® 1200 UP 12:50 Lamesoft® PO65 12:20 Polymer W 37194 ⁵ 12:10 Tri-sodium citrate dihydrate 12:50 2,4,5,6-tetra-sulfate 12:10 1- (β-hydroxyethyl) -p-phenylenediamine sulfate 12:10 4-amino-3-methylphenol 12:20 m-aminophenol 12:10 4-chlororesorcinol 12:10 2-amino-3-hydroxypyridine 12:13 Rodol 9R Base ⁶ 12:10 Monoethanolamine ad pH 7 water ad 100.00 ⁵ Acrylic acid-sodium-salt-acrylamidopropyltrimethylammonium chloride copolymer preserved with Phenonip (about 19-21% active ingredient, INCI name: Acrylamidopropyl-Trimonium Chloride / Acrylates Copolymer) (Stockhausen) @ ⁶ 2-amino-6-chloro-4-nitrophenol

AL = L <staining gel 3: Natrosol® 250 HR 2:00 Eumulgin® B2 12:50 Plantacare® 1200 UP 1:00 Lamesoft® PO65 12:50 N-acetyl-L-cysteine 12:15 2,4,5,6-tetra-sulfate 1:50 p-phenylenediamine sulfate 12:20 4-amino-2-aminomethylphenol dihydrochloride 12:05 2-methyl 1:00 methyl yellow 12:10 L-arginine 1:00 Monoethanolamine ad pH 7 water ad 100.00

AL = L <coloring gel 4: Natrosol® 250 HR 2:00 Eumulgin® B2 12:50 Plantacare® 1200 UP 12:50 Lamesoft® PO65 12:20 Tri-sodium citrate dihydrate 12:50 2,4,5,6-tetra-sulfate 12:20 4,5-diamino-1- (β-hydroxyethyl) pyrazole 0.80 4-amino-3-methylphenol 12:40 2-methyl 12:20 2,7-dihydroxynaphthalene 0.60 4-chlororesorcinol 12:20 lysine 12:20 isopropanolamine ad pH 7 water ad 100.00

AL = L <coloring gel 5: Natrosol® 250 HR 2:00 Eumulgin® B2 12:50 Plantacare® 1200 UP 12:50 Lamesoft® PO65 12:20 N-acetyl-L-cysteine 12:20 p-toluenediamine sulphate 1.10 p-aminophenol 12:10 2-methyl 12:10 2,7-dihydroxynaphthalene 12:30 5,6-Dihydroxyindolin hydrobromide 12:20 m-aminophenol 12:06 2-methylamino-3-amino-6-methoxypyridine 12:02 2-amino-3-hydroxypyridine 12:01 resorcinol 12:20 Monoethanolamine ad pH 7 water ad 100.00

AL = L <coloring gel 6: Natrosol® 250 HR 2:00 Eumulgin® B2 12:50 Plantacare® 1200 UP 1:50 Tri-sodium citrate dihydrate 12:20 N-acetyl-L-cysteine 12:20 p-toluenediamine sulphate 0.60 Bis- (2-hydroxy-5-aminophenyl) -methane 12:03 2-methyl 12:07 m-aminophenol 12:03 4-chlororesorcinol 12:18 resorcinol 12:10 histidine 12:50 Monoethanolamine ad pH 7 water ad 100.00

AL = L <coloring gel 7: Carbopol® 934 ⁷ 1:50 Eumulgin® B2 12:50 Plantacare® 1200 UP 1:50 Polymer JR® 400 ⁸ 12:50 Tri-sodium citrate dihydrate 12:50 2,4,5,6-tetra-sulfate 12:20 p-toluenediamine sulphate 0.90 4-amino-2-aminomethylphenol dihydrochloride 12:40 2-methyl 12:25 2,7-dihydroxynaphthalene 0.60 4-chlororesorcinol 12:24 5,6-Dihydroxyindolin hydrobromide 12:20 L-arginine 1:00 isopropanolamine ad pH 7 water ad 100.00 ⁷ Carboxyvinyl polymer (INCI name: Carbomer) (Goodrich) @ ⁸ quaternized hydroxyethylcellulose (INCI name: Polyquaternium-10) (Amerchol)

AL = L <coloring gel 8: Carbopol® 934 1:00 Eumulgin® B2 12:20 Eumulgin® B1 ⁹ 12:20 Plantacare® 1200 UP 12:50 Lamesoft® PO65 12:20 Tri-Kaliumcitratdihydrat 12:50 2,4,5,6-tetra-sulfate 0.70 p-toluenediamine sulphate 12:40 2- (β-hydroxyethyl) -p-phenylenediamine sulfate 12:10 3-methyl-4-aminophenol 12:50 2-methyl 12:50 2,7-dihydroxynaphthalene 12:16 4-chlororesorcinol 12:10 2-amino-3-hydroxypyridine 12:50 Rodol 9R Base 12:10 histidine 12:20 Monoethanolamine ad pH 7 water ad 100.00 ⁹ Cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis)

AL = L <coloring gel 9: Natrosol® 250 HR 2:00 Eumulgin® B2 12:20 Eumulgin® B1 12:20 Plantacare® 1200 UP 1:50 Lamesoft® PO65 12:20 Merquat® 280 ¹⁰ 0.80 Tri-sodium citrate dihydrate 1:00 2,4,5,6-tetra-sulfate 0.60 p-toluenediamine sulphate 12:02 3-methyl-4-aminophenol 0.60 4-chlororesorcinol 12:03 2-amino-3-hydroxypyridine 12:50 1- (β-hydroxyethylamino) -4-methyl-2-nitrobenzene 12:10 isopropanolamine ad pH 7 water ad 100.00 ¹⁰ dimethyldiallylammonium chloride-acrylic acid copolymer (about 35% active ingredient, INCI name: Polyquaternium-22) (Chemviron)

AL = L <coloring gel 10: Aculyn® 22 ¹¹ 2:00 Eumulgin® B2 12:50 Plantacare® 1200 UP 12:50 Lamesoft® PO65 12:20 Tri-sodium citrate dihydrate 12:50 Tri-potassium citrate dihydrate 12:50 2,4,5,6-tetra-sulfate 0.60 p-toluenediamine sulphate 12:27 2,6-di- (β-hydroxyethylamino) toluene 12:40 3,5-Diamino-2,6-dimethoxy 12:50 caustic soda ad pH 7 water ad 100.00 ¹¹ Methacrylic acid (stearyl alcohol + 20 EO ester) acrylic acid copolymer (about 30% active ingredient, INCI name: Acrylates / Steareth-20 Methacrylate Copolymer) (Rohm & Haas)

AL = L <staining gel 11: Natrosol® 250 HR 3:00 Eumulgin® B2 12:50 Plantacare® 1200 UP 1:50 Lamesoft® PO65 12:20 Tri-sodium citrate dihydrate 12:50 p-toluenediamine sulphate 1.10 1,3-bis (2 ', 4'-diaminophenoxy) propane hydrochloride 12:40 m-aminophenol 12:10 2-methylamino-3-amino-6-methoxypyridine 12:20 2-amino-4- (β-hydroxyethylamino) -anisole sulfate 12:20 Monoethanolamine ad pH 7 water ad 100.00

II) enzymes a) laccase

A laccase from Rhus vernificera from Sigma was used. The activity of the laccase is defined according to the manufacturer's instructions such that one unit [1U] corresponds to the amount of laccase which has a ΔA ₅₃₀ of 0.001 per minute at a pH of 6.5 and 30 ° C in 3 ml of a reaction solution with syringaldazine as a substrate.

The laccase was used in each case in such an amount that among the above mentioned conditions has an activity of 280000 U.

b) ascorbate oxidase

An ascorbate oxidase from Cucurbita species from Roche-Diagnostics was used. The activity of the ascorbate oxidase is defined such that one unit [1U] corresponds to the amount of ascorbate oxidase present in a phosphate buffer solution (KH ₂ PO ₄ , 0.1 mol / l; Na ₂ HPO ₄ , 4 mmol / l). 1 EDTA, 0.5 mmol / l) catalyzes the oxidation of 1 μmol L-ascorbic acid within one minute at pH 5.6 and 25 ° C (as defined by the commercial products of Roche Diagnostics). Detection is spectroscopically based on the decrease in absorbance at 245 nm.

The ascorbate oxidase was used in each case in an amount which is among the above-mentioned conditions has an activity of 100,000 U.

c) bilirubin oxidase

A bilirubin oxidase from Myrothecium verrucaria from Sigma was used. The activity of bilirubin oxidase is defined such that one unit [1U] of the amount corresponds to bilirubin oxidase, which inhibits the oxidation of 1 μmol bilirubin within a Minute catalysed at pH 8.4 and 37 ° C.

The bilirubin oxidase was used in each case in such an amount that among the above conditions has an activity of 1000 U.

d) Uricase

A uricase from Arthrobacter globiformis from Sigma was used. The Activity of uricase is defined such that one unit [1U] of the amount of uricase corresponds to the conversion of 1 μmol of uric acid to allantoin within one Minute catalysed at pH 8.5 and 25 ° C.

The uricase was used in each case in such an amount that among the above mentioned conditions has an activity of 25,000 U.

III) coloration Enzymes a to c

60 g of the respective Färbegels 1 to 11 were mixed with 10 ml of a (buffered by KHPO ₄ / KH ₂ PO ₄ ) to pH 7 solution containing the enzymes ac in the activities mentioned under point II). The mixture was applied to human hair (Kerling, natural white, 4 g of colorant per 0.5 g of hair), incorporated and for 30 min. left at room temperature. The hair was then rinsed and dried.

Enzyme d

60 g of the staining gels 1-11 were mixed with 0.35 g of uric acid and those defined under point II Amount of uricase added. It was made up to 70 g with bidistilled water. The  subsequent coloration was carried out analogously to that described for the enzymes a to c Method.

The respective staining results are shown in the following table:

Claims (21)

1. A composition for dyeing keratinic fibers containing in a cosmetically acceptable carrier

• A) at least one dye precursor,
• B) at least one enzyme which can catalyze the oxidation of the dye precursors,
• C) at least one sugar surfactant selected from the group formed by
  Alkyl and alkenyl oligoglycosides and
  Fatty acid N-alkylpoly-hydroxyalkylamides and
• D) at least one reducing agent.

2. Composition according to one of claims 1, characterized in that it is used as Farbstoffvor product (A) contains at least one developer component. 3. Composition according to one of claims 1 or 2, characterized in that it as a color fabric precursor (A) contains at least one indole and / or indoline derivative. 4. Composition according to one of claims 1 to 3, characterized in that it at least contains a coupler component. 5. Composition according to one of claims 1 to 4, characterized in that it continues contains at least one substantive dye. 6. Composition according to one of claims 1 to 5, characterized in that it as Reducing agent is an alkali metal citrate salt, in particular sodium citrate, and / or N- Contains acetyl-L-cysteine. 7. Composition according to claim 6, characterized in that it is used as a reducing agent N- Contains acetyl-L-cysteine. 8. Composition according to one of claims 1 to 7, characterized in that it continues contains at least one fatty acid partial glyceride. 9. Composition according to one of claims 1 to 8, characterized in that it continues contains at least one thickener.   10. A composition according to claim 9, characterized in that the thickening agent anionic or nonionic polymer. 11. Composition according to one of claims 9 or 10, characterized in that it as Thickener contains at least one cellulose and / or a cellulose derivative. 12. Composition according to one of claims 1 to 11, characterized in that it continues contains a nourishing polymer. 13. Composition according to one of claims 1 to 12, characterized in that it at least contains another surfactant. 14. Composition according to claim 13, characterized in that it is a nonionic or a contains amphoteric surfactant. 15. Composition according to one of claims 1 to 14, characterized in that it at least contains an alkalizing agent. 16. A composition according to claim 15, characterized in that it is used as alkalizing agent Monoethanolamine, isopropylamine, isopropanolamine, 2-amino-2-methylpropan-1-ol, Arginine, histidine or an alkali metal hydroxide, in particular sodium hydroxide or Potassium hydroxide. 17. Composition according to one of claims 1 to 16, characterized in that it has a pH Value of 4 to 10, in particular from 6 to 9, very particularly preferably from 7 to 8.5 having. 18. Composition according to one of claims 1 to 17, characterized in that it has a low-viscosity preparation with a viscosity of less than 3000 mPa.s (Brookfield, spindle 4, 20 rpm, 20 ° C). 19. A process for dyeing keratinic fibers, wherein a preparation according to one of Claims 1 to 18 is applied to the fibers and after an exposure time is rinsed off again. 20. A method for dyeing keratinic fibers, wherein in a first step an acce preparation, comprising the components (A), (C) and (D) being applied to the fibers,  the fibers are optionally rinsed after a contact time and in a second step comprises a preparation containing component (B) on the fibers is applied. 21. Use of one of the agents of claims 1 to 18 for the dyeing of keratinous fibers.