RU2311898C2 - Enzymatic coloring agent - Google Patents

Abstract

FIELD: method and kit for coloring of keratin fibers.

SUBSTANCE: claimed agent contains at least one enzyme capable of catalyzing coloring agent intermediate oxidation and combination of active substances selected from at least one surfactant, such as sugar, reducing agent, and partial glyceride of fatty acid.

EFFECT: coloring agent of high effectiveness and safety for human hair.

17 cl, 12 ex, 6 tbl

Description

The present invention relates to a means for dyeing keratin fibers, which, among other things, contains at least one enzyme that can catalyze the oxidation of dye intermediates and a combination of active substances from at least one surfactant - sugar and a reducing agent, the use of this agent for dyeing keratin fibers, as well as various methods of dyeing keratin fibers with these agents.

Human hair is currently being treated with hair cosmetics in a variety of ways. These include: shampooing hair, rinsing and rinsing and treatment, as well as lightening, dyeing and changing the shape of dyeing products, tonic agents, hair curlers and stylizing preparations. At the same time, means for changing the color of the hair and tone the hair of the head play a special role.

For temporary coloring, a coloring or tonic agent is usually used containing the so-called direct dye as a coloring component. This is a dye molecule that is directly (directly) selected by the fiber and does not require any oxidative process to form a color. Such dyes include, for example, henna, which has long been known for dyeing the body and hair. These stains, as a rule, are clearly more sensitive to shampoo treatment than oxidative dye stains, as a result of which a varied undesirable change in the color shade or even its visible discoloration is much faster.

For sustainable intense staining with the corresponding properties of the strength of the color, so-called oxidizable coloring agents are used. Such a dyeing agent typically contains an intermediate of an oxidizable dye, the so-called developer components and color-forming components. The components of the developer, under the action of oxidizing agents or under the action of atmospheric oxygen, form a dye between itself or when combined with one or more color-forming components. Oxidizable dyes are characterized by excellent lasting staining results. To obtain natural colors, it is usually necessary to use a mixture of a larger number of oxidizable dyes intermediates. In many cases, direct dyes are also used to tone.

The oxidative manifestation of color can be carried out, in principle, by atmospheric oxygen. However, a chemical oxidizing agent is preferably used. Persulfates, chlorates and, especially, hydrogen peroxide or products of its addition to urea, melamine, and also sodium borate are considered as an oxidizing agent. Usually use about 2-9% aqueous solution of hydrogen peroxide. Upon manifestation, such a high concentration of an oxidizing agent can damage keratin fibers, especially if they have already been subjected to permanent wave and lightening repeatedly. In some cases, skin irritation may occur due to such high concentrations.

The main solution to this problem is to reduce the concentration of the oxidizing agent. Therefore, in the past, on the one hand, they tried to find dye intermediates that in their chemical structure could already be oxidized with a small amount of hydrogen peroxide or atmospheric oxygen. On the other hand, it was proposed to use enzymes as biocatalysts that could catalyze the desired oxidation process with very little hydrogen peroxide or without it only in the presence of atmospheric oxygen.

German Patent Application Laid-Open DE-OS-2155390 describes an enzyme-activated oxidative dyeing process in which a small amount of hydrogen peroxide is used in combination with peroxidase. In the European patent application EP-A1-0310675, an enzymatic agent for treating hair is also published, comprising at least one oxidation reducible by two electrons using oxygen as an acceptor. European patent application EP-B1-0548620 describes an enzymatic hair dye in which the oxidation of a dye intermediate is catalyzed by the use of peroxidase.

Finally, European patent application EP-A2-0795313 describes an enzymatic hair dye containing an oxygen-oxidoreductase / substrate system and peroxidase, and also a m-phenylene-diamine derivative as color-forming components. However, all these coloring agents cannot fully satisfy with respect to the achieved staining efficiency (color intensity, shade, gloss, color fastness).

The technique of easily oxidizable dye intermediates, as well as the long-described enzymatic manifestation of dyeing, has the disadvantage that in comparison with traditional methods, worse results are achieved, especially in terms of color intensity, gloss and color fastness. Enzymatic hair dyeing agents according to the prior art also have the disadvantage that a relatively large amount of enzyme is required to achieve conventional dyeing results.

Therefore, it is an object of the present invention to provide an enzymatic agent for dyeing keratin fibers that substantially satisfies the dye requirements even when using minimal amounts of an enzyme and / or dye. In addition, an object of the present invention is to provide a dyeing agent that is gentle on skin and hair.

Therefore, one object of the present invention is a means for dyeing keratin fibers, containing in a cosmetically acceptable carrier

(A) at least one dye intermediate,

(B) at least one enzyme capable of catalyzing the oxidation of a dye intermediate,

(C) at least one surfactant is a sugar selected from the group formed

- alkyl and alkenyl oligoglycosides and

- N-alkyl polyhydroxyalkylamides of a fatty acid, and

(D) at least one reducing agent.

Keratin fibers according to the invention are understood to mean furs, wool, feathers and, especially, human hair.

Intermediates of dye

From the point of view of the dye intermediates (A) used in the dyeing agents of the invention, the present invention does not have any limitations. The dyeing agent according to the invention may contain, as an intermediate, a dye:

- oxidizable intermediates of the dye type developer and / or color-forming component and

- intermediates of similar in nature dyes, such as derivatives of indole and indoline, as well as mixtures of representatives of these groups.

In a first preferred embodiment, the dyeing agent comprises at least one developer component. Primary aromatic amines with another para or ortho free or substituted hydroxyl group or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives, and 2,4,5,6-tetraaminopyrimidine are usually used as a developer component and its derivatives.

According to the invention, it may be preferable to use a p-phenylenediamine derivative or physiologically acceptable salts thereof as a developer component. Particularly preferred derivatives of p-phenylenediamine of the formula (E1):

moreover

G ¹ means a hydrogen atom, an alkyl radical with 1-4 carbon atoms, a monohydroxyalkyl radical with 1-4 carbon atoms, a polyhydroxyalkyl radical with 2-4 carbon atoms, an alkoxy alkyl radical with 1-4 carbon atoms in the alkyl group and 1-4 carbon atoms in an alkoxyl group, a 4'-aminophenyl radical or an alkyl radical with 1-4 carbon atoms substituted with a nitrogen-containing group, a phenyl or 4'-aminophenyl radical;

G ² means a hydrogen atom, an alkyl radical with 1-4 carbon atoms, a monohydroxyalkyl radical with 1-4 carbon atoms, a polyhydroxyalkyl radical with 2-4 carbon atoms, an alkoxy alkyl radical with 1-4 carbon atoms in the alkyl group and 1-4 carbon atoms in an alkoxyl group or an alkyl radical with 1-4 carbon atoms substituted with a nitrogen-containing group;

G ³ means a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, an alkyl radical with 1-4 carbon atoms, a monohydroxyalkyl radical with 1-4 carbon atoms, a hydroxy-alkoxy radical with 1-4 carbon atoms, C ₁ -C ₄ -acetylamino-alkoxyl radical, mesylaminoalkoxyl radical with 1-4 carbon atoms in the alkoxyl group or carbamoylaminoalkoxyl radical with 1-4 carbon atoms in the alkoxyl group;

G ⁴ means a hydrogen atom, a halogen atom or an alkyl radical with 1-4 carbon atoms, or if G ³ and G ⁴ are in the ortho position with respect to each other, then together they form an α, ω-alkylene dioxo group attached via a bridge, for example, such as ethylenedioxy.

Examples of alkyl radicals having from 1 to 4 carbon atoms named as substituents in the compounds of the invention are methyl, ethyl, propyl, isopropyl and butyl groups. Preferred alkyl radicals are ethyl and methyl. Preferred alkoxy radicals having 1 to 4 carbon atoms according to the invention are, for example, methoxy or ethoxy groups. In addition, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl groups may be mentioned as preferred examples of hydroxyalkyl groups with 1-4 carbon atoms. Particularly preferred is a 2-hydroxyethyl group. Examples of halogen atoms according to the invention are fluorine, chlorine or bromine atoms. Most preferred is a chlorine atom. Other designations used are obtained according to the invention from the definition given here. Examples of nitrogen-containing groups of the formula (E1) are, in particular, amino groups, monoalkylamino groups containing from 1 to 4 carbon atoms in the alkyl, dialkylamino groups with 1-4 carbon atoms in the alkyls, trialkylammonium groups with 1-4 carbon atoms in the alkyls, monohydroxyalkylamino groups with 1 -4 carbon atoms, imidazolinium groups and ammonium groups.

Particularly preferred are p-phenylenediamines of formula (E1) selected from p-phenylenediamine, p-toluene diamine, 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-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-phen of ylendiamine, 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, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- ( β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane, as well as their physiologically acceptable salts.

The most preferred derivatives of p-phenylenediamine of formula (E1) according to the invention are p-phenylenediamine, p-toluylene diamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

According to the invention, it may be preferable, in addition, to use as a developer component compounds containing at least two aromatic nuclei substituted by amino groups and / or hydroxyl groups.

As two-core developer components that can be used in the dyeing composition of the invention, in particular, compounds corresponding to the following formula (E2), as well as their physiologically acceptable salts, can be named:

moreover

Z ¹ and Z ² , independently of one another, mean a hydroxyl radical or an NH ₂ radical, optionally substituted with an alkyl radical with 1-4 carbon atoms, a hydroxyl radical with 1-4 carbon atoms and / or a Y bridge, or which, when necessary, part of a ring system connected via a bridge,

bridge Y means an alkylene group with 1-14 carbon atoms, such as, for example, a straight-chain or branched alkylene chain or alkylene ring, which may be interrupted or may end with one or more nitrogen-containing groups and / or one or more heteroatoms, such as oxygen atoms , sulfur or nitrogen and, if necessary, can be substituted by one or more hydroxyl radicals or alkoxyl radicals with 1-8 carbon atoms, or a direct bond,

G ⁵ and G ⁶ mean, independently of one another, a hydrogen or halogen atom, an alkyl radical with 1-4 carbon atoms, a monohydroxyalkyl radical with 1-4 carbon atoms, a polyhydroxyalkyl radical with 2-4 carbon atoms, an aminoalkyl radical with 1-4 carbon atoms or a direct bond to bridge Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² mean, independently of each other, a hydrogen atom, a direct bond to the Y bridge or an alkyl radical with 1-4 carbon atoms,

provided that:

- the compounds of formula (E2) contain in the molecule only one bridge Y and

- compounds of formula (E2) contain at least one amino group containing at least one hydrogen atom.

The substituents contained in formula (E2) according to the invention are characterized similarly to the above types.

Particularly preferred binuclear developer components of formula (E2) are: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropan-2-ol, N, N 'bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetra-methylenediamine, 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-aminobenzyl) piperazine , N- (4'-aminophenyl) -p-f enylenediamine and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

The most preferred binuclear developer components of formula (E2) are: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diaminopropan-2-ol, bis (2 -hydroxy-5-amino-phenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7 , 10-tetraoxadecane and their physiologically acceptable salts.

In addition, according to the invention, it may be preferable to use a derivative of p-aminophenol or its physiologically acceptable salts as a developer component. Particularly preferred derivatives of p-aminophenol of the formula (E3):

moreover:

G ¹³ means a hydrogen atom, a halogen atom, an alkyl radical with 1-4 carbon atoms, a monohydroxyalkyl radical with 1-4 carbon atoms, an alkoxyalkyl radical with 1-4 carbon atoms in an alkyl radical and an alkoxy group, an aminoalkyl radical with 1-4 carbon atoms a hydroxyalkylamino radical with 1-4 carbon atoms, a hydroxyalkoxy radical with 1-4 carbon atoms, a 4-hydroxyalkylaminoalkyl radical with 1-4 carbon atoms in the alkyl parts or a (dialkylamino) alkyl radical with 1-4 carbon atoms in the alkyl parts, and

G ¹⁴ means a hydrogen or halogen atom, an alkyl radical with 1-4 carbon atoms, a monohydroxyalkyl radical with 1-4 carbon atoms, a polyhydroxyalkyl radical with 2-4 carbon atoms, an alkoxy-alkyl radical with 1-4 carbon atoms in the alkyl and alkoxy parts an aminoalkyl radical with 1-4 carbon atoms or a cyanoalkyl radical with 1-4 carbon atoms,

G ¹⁵ means hydrogen, an alkyl radical with 1-4 carbon atoms, a monohydroxyalkyl radical with 1-4 carbon atoms, a polyhydroxyalkyl radical with 2-4 carbon atoms, a phenyl radical or a benzyl radical and

G ¹⁶ means hydrogen or a halogen atom.

The substituents in the formula (E3) according to the invention are similar to the above types.

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-hydroxymethylamino-4-aminophenol 4-amino-3-hydroxymethylphenol, 4-amino-2- (2-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxy-methylphenol, 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, as well as their physiologically acceptable salts.

Particularly preferred compounds of formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2 - [(diethylamino) methyl] phenol.

In addition, the developer component may be selected from o-aminophenol and its derivatives, for example, such as 2-amino-4-methylphenol or 2-amino-4-chlorophenol.

In addition, the developer component may be selected from heterocyclic developing components, for example, such as derivatives of pyridine, pyrimidine, pyrazole, pyrazolpyrimidine and their physiologically acceptable salts.

Preferred pyridine derivatives are, in particular, the compounds described in GB patent applications GB 1026978 and GB 1153196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino-3-aminopyridine, 2,3-diamino-6 -methoxypyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent Application DE 2359399, Japanese Patent Application Laid-Open JP 02019576 A2 or International Patent Application Laid-Open WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2, 5,6-triaminopyrimidine.

Preferred pyrazole derivatives are, in particular, the compounds described in German patent applications DE 3843892, DE 4133957, in international patent applications WO 94/08969, WO 94/08970, in European patent applications EP 740931 and in German patent application DE 195 43988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3- dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5 -diamino-3-tert.butyl-1-methylpyrazole, 4,5-diamino-1-tert.butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxy-ethyl) -3-methylpyrazole, 4 5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl-pyrazole, 4, 5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropyl-pyrazole, 4-amino-5- (2 '-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-tri-aminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3, 5-diamino-4- (β-hydroxyethyl) amino-1-methyl-pyrazole.

Preferred pyrazole derivatives are, in particular, pyrazole- [1,5-a] pyrimidine derivatives of the following formula (E4) and their tautomeric forms, since there is a tautomeric equilibrium:

moreover:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ mean, independently of each other, a hydrogen atom, an alkyl radical with 1-4 carbon atoms, an aryl radical, a hydroxyalkyl radical with 1-4 carbon atoms, a polyhydroxy-alkyl radical with 2-4 atoms, an alkoxy-alkyl radical with 1-4 carbon atoms in the alkyl and alkoxyl parts, an aminoalkyl radical with 1-4 carbon atoms, which may be optionally protected by an acetylureido radical or sulfonyl radical, an alkylamino-alkyl radical with 1-4 atoms carbon in alkyl parts, dialkylamino-alkyl radical feces with 1-4 carbon atoms in the alkyl parts, and dialkyl radicals, if necessary, form a hydrocarbon ring or heterocycle with 5-6 members in the chain, a hydroxyalkyl radical with 1-4 carbon atoms or a di [hydroxyalkyl] aminoalkyl radical with 1- 4 carbon atoms in the alkyl parts.

X-radicals mean, independently of each other, a hydrogen atom, an alkyl radical with 1-4 carbon atoms, an aryl radical, a hydroxyalkyl radical with 1-4 carbon atoms, a polyhydroxyalkyl radical with 2-4 carbon atoms, an aminoalkyl radical with 1-4 atoms carbon, an alkylamino-alkyl radical with 1-4 carbon atoms in the alkyl parts, a dialkylamino-alkyl radical with 1-4 carbon atoms in the alkyl parts, and dialkyl radicals, if necessary, form a hydrocarbon ring or heterocycle with 5-6 members in the chain, hydroxyalkyl p a radical with 1-4 carbon atoms or a di [hydroxyalkyl] aminoalkyl radical with 1-4 carbon atoms in the alkyl parts, an amino radical, alkyl with 1-4 carbon atoms or a di [hydroxyalkyl] amino radical with 1-4 carbon atoms in the alkyl part halogen, carboxylic acid group or sulfonic acid group,

i has the value 0, 1, 2 or 3,

p has a value of 0 or 1,

q is 0 or 1 and

n is 0 or 1,

provided that

- the sum p + q is not equal to 0,

- if p + q is 2, then n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy positions (2,3); (5.6); (6.7); (3.5) or (3.7);

- if p + q is 1, then n has the value 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the OH group occupy positions (2,3); (5.6); (6.7); (3.5) or (3.7).

The substituents used in the formula (E4) according to the invention are defined similarly to the above types.

If the pyrazole- [1,5-a] -pyrimidine of the above formula (E4) contains a hydroxyl group at positions 2, 5 or 7 of the ring system, then there is a tautomeric equilibrium, which, for example, can be represented by the following scheme:

Among the pyrazole [1,5-a] pyrimidines of the above formula (E4), it is preferable to name:

- pyrazole- [1,5-a] pyrimidin-3,7-diamine;

- 2,5-dimethylpyrazole- [1,5-a] pyrimidin-3,7-diamine;

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

- 2,7-dimethylpyrazole- [1,5-a] pyrimidin-3,5-diamine;

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

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

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

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

- 2 - [(3-aminopyrazol- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;

- 2 - [(7-aminopyrazol- [1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol;

5,6-dimethylpyrazole- [1,5-a] pyrimidin-3,7-diamine;

- 2,6-dimethylpyrazole- [1,5-a] pyrimidin-3,7-diamine;

- 2,5, N7, N7-tetramethylpyrazole- [1,5-a] pyrimidine-3,7-diamine;

as well as their physiologically acceptable salts and their tautomeric forms, if tautomeric equilibrium exists.

Pyrazole- [1,5-a] pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization starting from aminopyrazole or hydrazine.

In addition, the agent according to the invention contains cationic intermediates of a dye such as a color-forming component and / or a color developer component. For example, as described in the internationally laid out applications WO-A1-99 / 03819, WO-A2-99 / 03834, WO-A1-99 / 03836, WO-A1-99 / 48856, WO-A1-99 / 48874, WO- A1-99 / 48875, WO-A2-00 / 42971, WO-A1-00 / 42979, WO-A1-00 / 42980, WO-A1-00 / 43356, WO-A1-00 / 43367, WO-A1- 00/43368, WO-A1-00 / 43386, WO-A1-00 / 43388, WO-A1-00 / 43389, WO-A1-00 / 43396, in European patent applications EP-A1-0984006, EP-A1 -0984007 and EP-A1-0989128.

Particularly preferred cationic dye intermediates are:

[2- (2 ', 5'-diaminophenoxy) ethyl] diethylmethylammonium chloride;

[2- (4'-aminophenylamino) propyl] trimethylammonium chloride;

[4- (4'-aminophenylamino) pentyl] diethyl- (2-hydroxyethyl) ammonium chloride;

1 - {[5'-amino-2 '- (2' '- hydroxyethylamino) phenylcarbamoyl] methyl} -1,4-dimethylpiperazin-1-chloride;

1,4-bis-1- {3- [3 '- (2' ', 5' '- diaminophenoxy) propyl] -3H-imidazol-1} -butane-dichloride;

1,3-bis- [3 '- (2``, 5' '- diaminophenoxy) propyl] -3H-imidazol-1-yl} chloride;

N, N'-bis [3-N-methyl-4N- (4'-aminoaniline) ethyl] -1,1,4,4-tetramethyldiammonium-1,3-propanedibromide;

1,3-bis-1- {3- {3 '- [(4' '- amino-3' '- methylaniline) -N-propyl]} - 3H-imidazol-1-yl} -propanedichloride;

1,3-bis-1- {3- {3 '- [(4' '- aminoaniline) -N-propyl]} - 3H-imidazol-1} propanedichloride;

1,3-bis-1- {3- {3 '- [(4' '- amino-2' '- methylaniline) -N-propyl]} - 3H-imidazol-1-yl} -propanedichloride;

3- [3- (4'-aminophenylamino) propyl] -1-methyl-3H-imidazol-1-yl chloride;

[3- (2 ', 5'-diaminophenoxy) propyl] -3-methyl-3H-imidazol-1-yl chloride;

3- [3- (4'-amino-3'-methylphenylamino) propyl] -1-methyl-3H-imidazol-1-yl chloride;

3- [3- (4'-amino-2'-methylphenylamino) propyl] -1-methyl-3H-imidazol-1-yl chloride;

1- [2- (4'-amino-2'-methoxyphenylamino) ethyl] -3-methyl-3H-imidazol-1-th chloride;

3- [3- (4'-amino-2'-fluorophenylamino) propyl] -1-methyl-3H-imidazol-1-yl chloride;

3- [3- (4'-amino-2'-cyanophenylamino) propyl] -1-methyl-3H-imidazol-1-yl chloride;

3- [2- (2 ', 5'-diaminophenyl) ethyl] -1-methyl-3H-imidazol-1-yl chloride;

1- {2 - [(4'-aminophenyl) ethylamino] ethyl} -3-methyl-3H-imidazol-1-yl chloride;

N, N-bis [2- (3'-methyl-3H-imidazol-1-th) ethyl] -4-aminoaniline chloride;

3- [2- (4'-aminophenylamino) butyl] -1-methyl-3H-imidazol-1-yl chloride;

[2- (2 ', 4'-diaminophenoxy) ethyl] diethylmethyl ammonium chloride;

1- [3- (2 ', 4'-diaminophenoxy) propyl] -3-methyl-3H-imidazol-1-yl chloride;

1 - [(3'-hydroxy-4'-methylphenylcarbamoyl) methyl] -3-methyl-3H-imidazol-1-yl chloride;

1,4-bis-1- {3- [3- (2 ', 4'-diaminophenoxy) propyl] -3H-imidazol-1} butane-dichloride;

3 - [(3'-hydroxy-4'-methanesulfonylaminophenylcarbamoyl) methyl] -1-methyl-3H-imidazol-1-yl chloride;

3 - [(3 ', 5'-dichloro-2'-hydroxy-4'-methylphenylcarbamoyl) methyl] -1-methyl-3H-imidazol-1-yl chloride;

1 - [(3 ', 5'-dichloro-2'-hydroxy-4'-methylphenylcarbamoyl) methyl] -1,4-dimethyl-piperazin-1-yl chloride;

3 - [(4'-acetylamino-2'-hydroxyphenylcarbamoyl) methyl] -1-methyl-3H-imidazol-1-yl chloride;

4- {3- [3'-hydroxynaphthalen-2'-carbonyl) amino] propyl} -4-methylmorpholin-4-yl-iodide;

3- [1'-hydroxynaphthalen-2'-ylcarbamoyl) methyl] -1-methyl-3H-imidazol-1-yl chloride;

3 - [(5'-acetylamino-1'-hydroxynaphthalen-2'-ylcarbamoyl) methyl] -1-methyl-3H-imidazol-1-yl chloride;

3 - [(1'-hydroxy-5'-methanesulfonylaminonaphthalen-2'-ylcarbamoyl) methyl] -1-methyl-3H-imidazol-1-yl chloride;

[3- (4'-amino-2 ', 5'-dimethyl-2H-pyrazol-3'-ylamino) propyl] - (2-hydroxy-ethyl) dimethylammonium chloride;

1,3-bis - [(2'-hydroxy-4'-methylphenylcarbamoyl) methyl] -3H-imidazol-1-yl chloride;

1- [2- (6'-aminobenzo [1,3] dioxol-5'-ylamino) ethyl] -3-methyl-3H-imidazol-1-yl chloride;

3- [2- (6'-aminobenzo [1,3] dioxol-5'-ylamino) ethyl] -1- (4- {3- [2- (6 '' - amino-benzo [1,3] dioxol -5 '' - amylamino) ethyl] -3H-imidazol-1-yl-butyl) -3H-imidazol-1-yl-dichloride;

3- [3- (3'-amino-5'-methyl-pyrazolo [1,5-a] pyrimidin-7'-ylamino) propyl] -1- (2-hydroxyethyl) -3H-imidazol-1-y- chloride;

1,3-bis-1- {3- {3 - [(2'-aminoaniline) -N-propyl]} - 3H-imidazol-1} propanedibromide;

N, N'-bis [3N- (2'-aminoaniline) -N-propyl] -1,1,3,3-tetramethyldiammonium-1,3-propanedibromide;

3- [3- (2'-aminophenylamino) propyl] -1-methyl-3H-imidazol-1-yl chloride;

[2- (2'-aminophenylamino) ethyl] trimethylammonium chloride and

3- (4'-hydroxy-1'-methyl-1H-indol-5'-ylmethyl) -1-methylpyridinium methosulfate.

In addition, according to the invention, a dyeing agent containing at least one color-forming component is preferred. As a color-forming component, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable substances for the color-forming component are, in particular: 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxy-naphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl 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-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Preferred color-forming components according to the invention are:

- m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophen-hydroxyethanol, 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-aminopheno and its derivatives;

- m-diaminobenzene and its derivatives, such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene 1,3-bis (2,4-diaminophenyl) propane, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene;

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

- derivatives of di- or trihydroxybenzene, such as, for example, 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, for example, 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2.6 -dihydroxy-3,4-dimethyl-pyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine;

naphthalene derivatives, for example, such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene and 2, 3-dihydroxynaphthalene;

- morpholine derivatives, such as, for example, 6-hydroxybenzomorpholine and 6-aminobenzomorpholine;

quinoxaline derivatives, such as, for example, 6-methyl-1,2,3,4-tetrahydroquinoxaline,

pyrazole derivatives, such as, for example, 1-phenyl-3-methyl-pyrazol-5-one;

derivatives of indole, such as, for example, 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole;

pyrimidine derivatives, such as, for example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine , 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine or

derivatives of methylenedioxybenzene, such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

Particularly preferred color-forming components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methyl-resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

It is not required that the intermediates of oxidizable dyes or direct dyes be individual compounds in each case. On the contrary, other components in small amounts may also be contained in the hair dyeing agents, which is due to the production methods of individual dyes, unless they adversely affect the dyeing result or should not be excluded for other reasons, for example, toxicological.

As for the dyes used in the means for coloring and tinting hair according to the invention, they are described in monographs: Ch. Zviak, The Science of Hair Care, Kapitel 7, Seiten 248-250 (direct dyes), sowie Kapitel 8, Seiten 264-267 (intermediates of oxidizable dyes), Band 7 der Reihe “Dermatology” (Hrg .: Ch., Culnan und H. Maibach), Verlag Marcel Dekker Inc., New York, Basel, 1986, sowie das "Europäische Inventar der Kosmetik-Rohstoffe", herausgegeben von der Europaischen Gemeinschaft, produced in the form of disks of the state industrial and commercial business of Germany (Bundesverband Deutscher Industrie - und Handelsunternehmen) for pharmaceuticals, reforming products and body care products, Mannheim.

Since amino compounds are involved with dyes intermediates, known acid addition salts can be prepared from them in the usual manner. Therefore, all the arguments in this text and, accordingly, the declared scope of protection relate both to the free form of the present compounds and to their water-soluble physiologically acceptable salts. Examples of such salts are hydrochlorides, hydrobromides, sulfates, phosphates, acetates, propionates, citrates and lactates.

Intermediates of oxidizable dyes are contained in the agent according to the invention in an amount of preferably from 0.01 to 20% by weight, preferably from 0.5 to 5% by weight, based on the total agent.

As intermediates of dyes similar to natural ones, indoles and indolines are preferably used which have at least one hydroxyl group or an amino group, preferably in the form of a six-membered ring substituent. These groups may have other substituents, for example, in the form of a simple or complex ester of a hydroxyl group or an alkylated amino group. In a second preferred embodiment, the dyeing agent comprises at least one derivative of indole and / or indoline.

Derivatives of 5,6-dihydroxyindoline of the formula (Ia) are particularly suitable as intermediates for hair dyes similar to natural ones:

in which, independently of each other,

R ¹ means a hydrogen atom, an alkyl group with 1-4 carbon atoms or an alkyl group with 1-4 carbon atoms;

R ² means a hydrogen atom or a —COOH group, wherein the —COOH group may also be in the form of a salt with a physiologically acceptable cation;

R ³ means a hydrogen atom or an alkyl group with 1-4 carbon atoms;

R ⁴ means a hydrogen atom or an alkyl group with 1-4 carbon atoms or a group -CO-R ⁶ in which R ⁶ means an alkyl group with 1-4 carbon atoms; and

R ⁵ means one of the groups named for R ⁴ ,

and physiologically acceptable salts of these compounds with organic or inorganic acids.

Particularly preferred indoline derivatives are 5,6-di-hydroxyindoline, 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, as well as 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5 , 6-dihydroxyindoline.

In addition, derivatives of 5,6-dihydroxyindoles of the formula (1b) are excellently suitable as intermediates for hair dyes similar to natural ones:

in which, independently of each other,

R ¹ means a hydrogen atom, an alkyl group with 1-4 carbon atoms or a hydroxyalkyl group with 1-4 carbon atoms;

R ² means a hydrogen atom or a group - COOH, and - COOH group may also be in the form of a salt with a physiologically acceptable cation;

R ³ means a hydrogen atom or an alkyl group with 1-4 carbon atoms;

R ⁴ means a hydrogen atom or an alkyl group with 1-4 carbon atoms or a group —CO-R ⁶ , in which R ⁶ means an alkyl group with 1-4 carbon atoms; and

R ⁵ means one of the groups named for R ⁴ ,

and physiologically acceptable salts of these compounds with organic or inorganic acids.

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

N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5 6-dihydroxyindole.

Derivatives of indoline and indole can be used within the framework of the dyeing agents used in the method according to the invention, both in the form of free bases and in the form of their physiologically acceptable salts with organic and inorganic acids, for example in the form of hydrochlorides, sulfates and hydrobromides. Derivatives of indole or indoline are usually contained in an amount of 0.05-10 wt.%, Preferably 0.2-5 wt.%.

In one of the other variants according to the invention, it may be preferable to use derivatives of indoline or indole in means for dyeing hair in combination with at least one amino acid or oligopeptide. The amino acid is predominantly an α-amino acid. The most preferred α-amino acid is arginine, ornithine, lysine, serine and histidine, especially arginine.

In addition, to achieve the desired staining effect, the agent according to the invention may contain, in addition to dyes intermediates, at least one direct dye. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are compounds known by international names or trade names: HC yellow 2, HC yellow 4, HC yellow 5, HC yellow 6, HC yellow 12, HC orange 1, dispersed 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, dispersed blue 3, HC purple 1, dispersed purple 1, dispersed purple 4, acid purple 43, dispersed black 9 and acid black 52, such as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-gy Droxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) amino-phenol, 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-nitrophenol, 1- (2'-ureidoethyl) amino-4- nitrobenzene, 4-amino-2-nitrodiphenylamino-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, hydroxyethyl-2-nitrotoluidine, picraminic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

In addition, the agent of the invention may contain cationic direct dyes. Particularly preferred are:

(i) cationic triphenylmethane dyes, for example, such as basic blue 7, basic blue 26, basic violet 2 and basic violet 14;

(ii) aromatic systems substituted by quaternary nitrogen-containing groups, such as, for example, base yellow 57, base red 76, base blue 99, base brown 16 and base brown 17, and

(iii) direct dyes containing heterocycles with at least one quaternary nitrogen atom, such as, for example, those referred to in European patent application EP-A2-998908 (referred to herein) in claims 6 to 11.

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

Compounds of formulas (DZ1), (DZ3) and (DZ5) are the most preferred cationic direct dyes of group (iii).

The agent of the invention according to this embodiment contains direct dyes, preferably in an amount of 0.01 to 20% by weight, based on the weight of the coloring agent.

In addition, the compositions of the invention may also contain dyes of natural origin, for example, such as red henna, neutral henna, black henna, chamomile flowers, santalacea, black tea, bark of buckthorn buckwheat, sage, blue sandalwood, crustacean root, catechu, Sedre and alcann root.

Enzymes

In addition, the agent according to the invention contains, as a second mandatory component, at least one enzyme capable of catalyzing the oxidation of the dye intermediate. Although according to the invention, in principle, all enzymes capable of catalyzing this process are suitable, however, enzymes which are

(i) form a small amount of hydrogen peroxide in situ;

(ii) directly oxidize the dye intermediates with atmospheric oxygen;

(iii) accelerate the oxidation of dye intermediates with hydrogen peroxide.

The properties described in (i) are usually possessed by oxidases that react with their given specific substrate to form hydrogen peroxide. Examples of enzymes of this kind 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 -№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), vanillin 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 oxidase (EC-No1.4 .3 .2, EC-No 1.4.3.3), acyl-CoA oxidase (EC-No 1.1.3.6), glutamate oxidase (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), sulfate oxidase (EC-No 1.8.3.1), catechinooxidase (EC-No 1.10.3.1), L-ascorbate oxidase (EC-No. 110.3.3), 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), as well as galactose oxidase (EC-No. 1.1.3.9). Particularly preferred examples of such oxidases are uricase, glucose oxidase, and choline oxidase. Uricase is the most preferred class (i) enzyme. In order for the enzymes to catalyze the dyeing process, the agent according to the invention must always contain sufficient substrates.

Enzymes (ii) that oxidize the dye intermediates with atmospheric oxygen are, for example, laccases (EC-No. 1.10.3.2), tyrosinase (EC-No. 1.10.3.1), ascorbate oxidase (EC-No. 1.10.3.3), bilirubin -oxidases (EC-No. 1.3.3.5), as well as phenol oxidases such as Acremonia, Stachybotrys or Pleurotus. Laccases according to the invention are the most preferred class (ii) enzyme.

Peroxidases (EC-No. 11.11.1.7) fall under category (iii) as the enzyme according to the invention. They make dyeing possible even with small amounts of hydrogen peroxide. It does not matter if a small amount of hydrogen peroxide is introduced into the composition or if it is formed in situ by the enzymes listed in (i). Most preferred according to the invention is peroxidase, which can be obtained from horseradish.

Enzymes can be introduced into the dyeing agent itself. However, it is preferable that they are prepared separately from the dyes intermediates and mixed with the actual dyeing agent only immediately before use. If the enzyme is to be introduced into the dyeing agent as a one-component system, it is preferable according to the invention to prepare the system in the absence of air.

In addition, it turns out that according to the invention it may be preferable to prepare a dyeing agent without a blowing agent, that is, not in the form of a foamy composition.

The enzyme is used preferably in an amount of 0.0001-1 wt.% Based on the amount of protein of the enzyme and the dyeing agent as a whole.

Sugar Surfactants

The agent according to the invention contains, as a third mandatory component (C), at least one surfactant-sugar.

According to the first embodiment (C1) with respect to the surfactant sugar, it is an alkyl or alkenyl oligoglycoside. These sugar surfactants are known non-ionic surfactants of the formula (II):

in which R ¹ means the residue of alkyl or alkenyl with 4-22 carbon atoms, G means the sugar residue with 5-6 carbon atoms and p means numbers from 1 to 10. They can be obtained by the appropriate method of preparative organic chemistry. As extensive publications, reference may be made to the review by Biermann et al., Starch / Stärke 45, 281 (1993); B. Salka, Cosm. Toil. 108, 89 (1993), as well as J. Kahre et al., SÖFW-Joumal Heft 8, 598 (1995).

Alkyl and alkenyl oligoglycosides can be obtained from aldoses or ketoses with 5-6 carbon atoms, mainly from glucose. Thus, preferred alkyl and / or alkenyl oligoglycosides are alkyl and / or alkenyl oligoglucosides. The numerical index p in the general formula (II) characterizes the degree of oligomerization (DP), that is, the distribution of mono- and oligoglycosides, and means a number between 1 and 10. While in a separate molecule p should mean an integer and, above all, p can take a value equal to from 1 to 6, then for a certain alkyl oligoglycoside, the value of p is an analytically averaged mathematical value, which in most cases is a fractional number. Preferably, the alkyl and / or alkenyl oligoglycosides have an average oligomerization degree p of from 1.1 to 3.0. From the point of view of technical use, such alkyl and / or alkenyl oligoglycosides are preferred whose oligomerization degree is less than 1.7 and, in particular, between 1.2 and 1.4.

The alkyl or alkenyl radical R ¹ may be a primary alcohol residue with 4 to 11 carbon atoms, preferably with 8 to 10 carbon atoms. Typical examples are butanol, capron alcohol, capric alcohol and undecyl alcohol, as well as their technical mixtures, such as, for example, those obtained by hydrogenation of methyl esters of fatty acids or during the hydrogenation of aldehydes, Rehlen oxysynthesis. Preferred are alkyl oligoglucosides with a chain length of C ₈ -C ₁₀ (the average degree of oligomerization is from 1 to 3), obtained as a head cut in the distillation separation of industrial coconut fatty alcohols with 8-18 carbon atoms, which may contain less than ₈ 6 wt.% Alcohol with 12 carbon atoms, as well as alkyl oligoglucosides based on industrial oxo alcohols with 9-11 carbon atoms (average degree of oligomerization from 1 to 3). The alkyl or alkenyl radical R ¹ may also, in addition, be the residue of primary alcohols with 12-22 carbon atoms, preferably with 12-14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petrozelinyl alcohol, arachyl alcohol, technical gadoleyl alcohol, behenyl alcohol and their adenyl alcohol which can be obtained as described above. Cured coconut alcohol alkyl oligoglucosides with 12-14 carbon atoms and an average degree of oligomerization of 1 to 3 are preferred.

According to a second embodiment of the invention (C2), a sugar surfactant is a fatty acid N-alkyl polyhydroxylamide, a nonionic surfactant of the formula (III):

in which R ² CO means an aliphatic acyl residue with 6-22 carbon atoms, R ³ means hydrogen, an alkyl or hydroxyalkyl residue with 1-4 carbon atoms, and [Z] means a straight-chain or branched polyhydroxyalkyl residue with 3-12 carbon atoms and 3 -10 hydroxyl groups.

As for N-alkyl polyhydroxyalkylamides of fatty acids, we are talking about known substances obtained in the usual way by reductive amination of reducing sugars with ammonia, alkylamine or alkanolamine and subsequent acylation with fatty acid, fatty acid alkyl ester or fatty acid chloride. Regarding the method of their preparation, reference can be made to US patents US 1985424, US 2016962 and US 2703798, as well as to international application WO 92/06984. A review of this topic is published in N. Kelkenberg, Tens. Surf Det. 25, 8 (1988). Preferably, the fatty acid N-alkyl-polyhydroxyalkylamides are derived from reducing sugars with 5 or 6 carbon atoms, especially glucose. In this case, the preferred N-alkyl polyhydroxyalkylamides of the fatty acid are compounds of the formula (IV):

Preferably, glucamides of the formula (IV) are used as N-alkyl polyhydroxyalkylamides, in which R ³ is hydrogen or an alkyl group and R ² CO is the acyl residue of caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petrozelinic (isooleic) acid, linoleic acid, linolenic acid, arachinic acid, gadoleic acid, behenic acid or erucovo th acid or their technical mixtures. Particularly preferred are the N-alkyl glucomides of a fatty acid of formula (IV) obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or coconut fatty acids with 12-14 carbon atoms or the corresponding derivative. In addition, polyhydroxyalkylamides can be obtained from maltose and palatinose.

Surfactant-sugar is contained in the tool according to the invention, preferably in an amount of 0.1-20% of the mass. calculated on the whole tool as a whole. Most preferably, in an amount of 0.5-5% of the mass ..

Reducing agent

In addition, the agent according to the invention advantageously comprises a reducing agent. Examples of preferred reducing agents of the invention are sodium sulfite, ascorbic acid, thioglycolic acid and its derivatives, sodium thionite, alkali metal and citric acid salts and N-acetyl-L-cysteine. Most preferred reducing agents are alkali metal salts of citric acid, in particular sodium citrate and N-acetyl-L-cysteine. The most preferred alkalizing agent is N-acetyl-L-cysteine.

Incomplete Fatty Acid Glyceride

As another component, the agent of the invention may contain partial fatty acid glycerides. Such partial fatty acid glycerides are monoglycerides, diglycerides and their technical mixtures. When using a technical product, a small amount of triglycerides may be contained, which depends on the conditions of preparation. Incomplete glycerides correspond to the formula (V):

in which R ⁴ , R ⁵ and R ⁶ , independently of one another, mean hydrogen or a straight-chain or branched unsaturated and / or unsaturated acyl residue with 6-22 carbon atoms, preferably with 12-18 carbon atoms, provided that, according to at least one of these groups means an acyl residue and at least one of these groups means hydrogen. The sum (m + n + q) means 0 or from 1 to 100, preferably 0 or a number from 5 to 25. Preferably R ⁴ means an acyl residue, and R ⁵ and R ⁶ mean hydrogen, and the sum (m + n + q) equal to 0. Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oligosaccharide acid, elaidic acid, petrozelinic acid, linole oh acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Oleic acid monoglyceride is preferably used.

The incomplete fatty acid glyceride is preferably contained in the agent used according to the invention in an amount of 0.1-20 wt.%, In particular 0.5-2 wt.%, Based on the agent as a whole.

The idea of the invention also encompasses variants in which the agent according to the invention contains several sugar surfactants and / or several partial fatty acid glycerides.

Thickener

As another possible component, the agent according to the invention may further comprise at least one thickener. Regarding such a thickener, there are no fundamental restrictions. Although, in principle, both organic and purely inorganic thickeners can be used, however, organic thickeners are preferred according to the invention.

According to a first preferred embodiment, the thickener is an anionic synthetic polymer. Preferred anionic groups are carboxylate and sulfate groups.

Examples of anionic monomers that the polymer anionic thickener can consist of are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, and 2-acrylamido-2-methylpropanesulfonic acid. In this case, the acid groups may be present, in whole or in part, in the form of sodium, potassium, ammonium, mono- or triethanolammonium salts. Preferred monomers are maleic anhydride, 2-acrylamido-2-methyl-propanesulfonic acid.

Preferred anionic homopolymers are crosslinked and crosslinked polyacrylic acids. In this case, allyl ester of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds, for example, are marketed under the trade name Carbopol ^® . Likewise preferred is the homopolymer of 2-acrylamido-2-methylpropane sulfonic acid, for example, is marketed under the tradename Rheothik ^® 11-80.

In the framework of this first embodiment, it may also be preferable to use copolymers of at least one anionic monomer and at least one non-anionic monomer. As for anionic monomers, it is possible to refer to the above substances. Preferred nonionic monomers are acrylamide, methacrylamide, acrylate, methacrylate, itaconic acid mono- and diester, vinylpyrrolidone, vinyl alcohol ether and ester.

Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid and their alkyl esters containing 1-6 carbon atoms in the alkyl, such as those implemented according to the INCI declaration of acrylate copolymers. A preferred commercial product is, for example, Aculyn ^® 33 company Rohm & Haas. In addition, copolymers of acrylic acid, methacrylic acid and their alkyl esters containing 1-6 carbon atoms and ethylenically unsaturated acid esters of hydroxyalkylated fatty alcohol are also preferred. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid. Suitable oxyalkylated fatty alcohols are, in particular, Steareth-20 or Geteth-20. This type of copolymer is marketed by Rohm & Haas under the trade name Aculyn ^® 33, and also by National Starch under the trade names Structure ^® 2001 and Structure ^® 3001.

Preferred anionic copolymers are, in addition, copolymers of acrylic acid and acrylamide, as well as, in particular, copolymers of acrylamide with monomers containing sulfonic acid groups. The most preferred anionic copolymer consists of 55-70 mol% of acrylamide and 30-45 mol% of 2-acrylamido-2-methyl-propanesulfonic acid, wherein the sulfonic acid group can be a complete or incomplete sodium, potassium, ammonium mono- or triethanolammonium salt. This copolymer may also be crosslinked, and polyolefin unsaturated compounds such as tetraallyloxytane, allyl sucrose, allyl pentaerythritol and methylene bisacrylamide are preferably used as the crosslinking agent. One such polymer is contained in commercial Sepigel ^® 305 and 600 Simulgel ^® company SEPPIC. In the framework of the idea of the invention, it is particularly preferable to use these compounds, which in addition to polymer components contain a mixture of hydrocarbons (isoparaffins with 13-14 carbon atoms or isohexadecane) and a nonionic emulsifier (Laureth-7 or Polysorbate-80).

Preferred thickeners are also polymers of maleic anhydride and methyl ester of vinyl alcohol, in particular polymers with molecular crosslinking. A copolymer of maleic acid and vinyl alcohol methyl ester crosslinked with 1,9-decadiene is marketed under the trade name Stabileze ^® QM.

In the second embodiment, in relation to the thickener, we are talking about a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. The most suitable polymers were those in which the quaternary ammonium groups are linked to the main polymer chain, consisting of acrylic acid, methacrylic acid and their derivatives, through a hydrocarbon group with 1-4 carbon atoms.

The most preferred cationic polymer thickeners are homopolymers of the general formula (VI):

in which R ¹ means a hydrogen atom or methyl, R ² , R ³ and R ⁴ , independently from each other, are selected from an alkyl group with 1-4 carbon atoms, an alkenyl group with 1-4 carbon atoms or a hydroxyalkyl group with 1- 4 carbon atoms, m = 1, 2, 3 or 4, n means a natural number, and X ^- is a physiologically acceptable organic or inorganic anion, as well as copolymers consisting mainly of monomer units represented by the formula (VI), as well as from nonionic monomer units. Preferred according to the invention are those of these polymers that satisfy at least one of the following conditions:

- R ¹ means a methyl group;

- R ² , R ³ and R ⁴ means a methyl group;

- m has a value of 2.

By physiologically acceptable counterions X are meant, for example, halide ions, sulfate ions, phosphate ions, metho-sulfate ions, as well as organic ions such as lactate, citrate, tartrate and acetate ions. Halide ions, in particular chloride, are preferred.

A particularly suitable homopolymer is, preferably crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the code name according to the INCI nomenclature of Polyguaternium-37. Crosslinking can be carried out using compounds containing several olefinically unsaturated bonds, for example, divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallyl polyglycerol ether or allyl sugar ethers or sugar derivatives such as erythritol, erythritol, penta, erythritol, penta . A preferred crosslinking agent is methylene bisacrylamide.

The homopolymer is preferably used in the form of a non-aqueous polymer dispersion, which should contain at least 30 wt.% Polymer. Such polymer dispersions, polymer dispersions are placed on the market under the name Salcare ^® SC 95 (about 50% of polymer, the other components: a mineral oil (INCI-name: mineral oil) and tridetsilpolioksipropilenpoli-oxyethylenated ether (INCI-name: PPG-1- Trideceth-6)) and Salcare ^® SC 96 (about 50% of polymer, the other components: a mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI-name: propylene glycol / dicaprylate) and tridetsilpolioksipropilenpolioksietilenovy ether (INCI-Description Type e: PPG-1-Trideceth-6).

In addition, according to the invention, a nonionic thickener such as polymeric fatty acid amides is suitable, such as, for example, those published in European patent applications EP-A1-632083 and EP-A2-959066.

The copolymers with monomer units according to formula (VI) preferably contain acrylamide, methacrylamide, an alkyl ester of acrylic acid with 1-4 carbon atoms and an alkyl ester of methacrylic acid with 1-4 carbon atoms as nonionic monomer units. Among these nonionic monomers, acrylamide is particularly preferred. As with the homopolymers described above, these copolymers can also be crosslinked. A preferred copolymer according to the invention is a crosslinked copolymer of acrylamide and methacryloyloxyethyltrimethylammonium chloride. Such copolymers, in which the mass ratio of monomer units is about 20:80, enter the market in the form of about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92.

According to a third embodiment, thickeners of natural origin are used. Preferred thickeners according to 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 from Rhone Poulenc. Preferred modified guar gums of the invention contain hydroxyalkyl groups of 1 to 6 carbon atoms. Preferred hydroxyl groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. Modified guar gums of this kind are known in the art and can, for example, be obtained by reacting guar gums with alkylene oxides. The degree of hydroxyalkylation corresponding to the number of consumed alkylene oxide molecules relative to the number of free hydroxyl groups of guar gums is preferably between 0.4 and 1.2. This type of modified guar gum is marketed under the trademarks Jaguar ^® HP8, Jaguar ^® HP60, Jaguar ^® HP120, Jaguar ^® DC293 and Jaguar ^® HP105 from Rhone Poulenc.

In addition, thickeners already known in the art are also suitable natural thickeners. In this case, reference can be made to the work of Robert L. Davidson, “Handbook of Water soluble gums and resins”, Mc Graw Hill Book Company (1980).

According to this variant, biosaccharide gums of microbiological origin are also preferred, such as scleroglucan gums and xanthan gums, plant exudates gums, such as gum arabic (gum arabic), gattigumi, karai-gum, tragum-gum, carragik-gum, carrag gummy, agar-agar, carob flour, pectins, alginates, starch fractions and derivatives such as amylose, amylopectin and dextrins.

Non-ionic purely synthetic polymers, for example, such as polyvinyl alcohol or polyvinylpyrrolidone, are also suitable as a thickener according to the invention. Preferred non-ionic purely synthetic polymers are commercially available, for example, from BASF under the brand name Luviskol ^® .

Preferred according to the invention are anionic or nonionic thickening polymers.

In a most preferred embodiment of the present invention, cellulose and / or cellulose derivatives, such as, for example, methyl cellulose, carboxyalkyl cellulose and hydroxyalkyl cellulose, are used as a thickening agent.

Preferred hydroxyalkylcelluloses are hydroxyethyl cellulose, is marketed under the code names: Cellosize ^® company Amerchol, Natrosol ^® company Hercules or Culminal ^® and Benecel ^® company Aqualon. According to the invention are also suitable hydroxypropyl cellulose, for example, placed on the market under the name of Klucel ^® company Hercules. Suitable carboxyalkyl celluloses are in E, especially carboxymethyl cellulose, such as coming to the market under the name of Blanose ^® company Aqualon, Aquasorb ^® and Ambergum ^® company Hercules and Cellgon ^® company Montello.

Care Polymers

In another preferred embodiment, the agent of the invention comprises at least one care polymer. By care polymers are meant both natural and synthetic polymers, which may be anionic, cationic, amphoteric or nonionic.

By cationic polymers are meant those polymers that contain groups in the main and / or side chain that can be cationic “temporarily” or “permanently”. "Constantly cationic" polymers according to the invention are those polymers that have cationic groups regardless of the pH of the agent. These are, as a rule, polymers containing a quaternary nitrogen atom, for example, in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. Particularly suitable are those polymers in which the quaternary ammonium group is linked to the main polymer chain, consisting of acrylic acid, methacrylic acid or their derivatives, through a hydrocarbon group with 1-4 carbon atoms.

Preferred cationic polymers are, for example:

- Quaternary cellulose derivatives marketed by the codenames Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternary cellulose derivatives;

- cationic alkyl polyglucosides according to German patent DE-PS 4413686;

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

- a cationic derivative of guars, in particular a product marketed under the trademarks Cosmedia ^® Guar and Jaguar ^® ;

- Quaternary polysiloxanes, for example, the marketed product Produkte Q2-7224 (manufactured by Dow Corning; stabilized trimethylsilylamodimethicone), Dow Corning ^® 929 Emulsion (containing hydroxylamino-modified silicone, also called amodimethicone, SM-2059 (manufactured by General Electric), SLM-55067 (manufactured by Wacker), as well as Abil ^® -Quat 3270 and 3272 (manufactured by Th. Goldschmidt; dicentric polydimethylsiloxane, Quaternium-80);

- polymers of dimethyldiallylammonium salt and its copolymers with esters and amides of acrylic and methacrylic acid. Examples of such cationic polymers are the products placed on the market under the name of Merquat ^® 100 (polydimethyldiallylammonium) and Merquat® 550 (copolymer diallilammoniyhlorida dimethyl-acrylamide);

copolymers of vinyl pyrrolidone with quaternary derivatives of dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates, such as, for example, copolymers of vinyl pyrrolidone with dimethylaminoethyl acrylate, quaternary diethyl sulfate. Such compounds are marketed under the symbols Gafquat ^® 734 and Gafquat ^® 755;

- copolymers of vinylpyrrolidone and vinylimidazolium methyl chloride, such as those offered under the symbols Luviquat ^® FC 370, FC 550, FC 905 and HM 552;

- Quaternary polyvinyl alcohol, as well as polymers with quaternary nitrogen atoms in the main polymer chain, known under the conventional names:

- Polyquaternium-2,

- Polyquaternium-17,

- Polyquaternium-18 and

- Polyquaternium-27.

Polymers known as Polyquaternium-24 (for example, the commercial product Quatrisoft ^® LM 200) can also be used as cationic polymers. Vinyl pyrrolidone copolymers such as the commercial products Copolymer 845 (ISP manufacturer), Caffioc ^® VC 713 (ISP manufacturer), Gafquat ^® ASCP 1011, Cafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 can also be used according to the invention.

Other cationic polymers of the invention are so-called “temporarily cationic” polymers. These polymers usually contain an amino group, which at certain pH values is a quaternary ammonium group, and therefore is a cationic group. Preferred are, for example, chitosan and its derivatives, such as, for example, those commercially available under the trademarks Hydagen ^® CMF, Hydagen ^® HCMF, Kytamer ^® PC and Chitolam ^® NB / 101. Chitosans are deacetylated chitins that enter the market with varying degrees of deacetylation and varying degrees of cleavage (with different molecular weights). Their preparation is described, for example, in German patent applications DE 4440652 A1 and DE 19503465 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.

To prepare the composition according to the invention, chitosan must be converted to its salt form, which can be accomplished by dissolving it in dilute aqueous solutions of acids. Suitable acids are both mineral acids, such as, for example, hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids, such as, for example, low molecular weight carboxylic acids, polycarboxylic acids and hydroxycarboxylic acids. In addition, high molecular weight alkyl sulfonic acids or alkyl sulfonic acids or organic phosphoric acids can also be used, provided that they are physiologically acceptable. Suitable acids for converting chitosan to salt form are acetic acid, tartaric acid, malic acid, citric acid, lactic acid, 2-pyrrolidone-5-carboxylic acid, benzoic acid or salicylic acid. Preferably, low molecular weight hydroxycarboxylic acids are used, such as, for example, glycolic acid or lactic acid.

In addition, amphoteric polymers can be used as polymers enhancing the action of the active substance according to the invention. The term “amphoteric polymers” encompasses polymers containing both free amino groups and free groups —COOH or free groups —SO ₃ H in the molecule, and capable of forming internal salts, and zwitterionic polymers containing quaternary ammonium groups and COO in the molecule ^- - or —SO ₃ O ^- groups, and polymers containing —COOH groups or —SO ₃ H groups and quaternary ammonium groups.

Examples of usable amphoteric polymers of the invention are acrylic resin, is marketed under the name of Amphomer ^®, which is a copolymer tret.butilaminoetilmetakrilata, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of: acrylic acid, methacrylic acid and their esters.

Another example of polymers employed according to the invention is, for example, commercially available under the name of Merquat ^® 280 Polyquaternium-22, which is a copolymer of dimethyl-diallilammoniyhlorida and acrylic acid.

Other amphoteric polymers used according to the invention are those compounds mentioned in GB Patent Laid-open Publication GB 2104091, European Patent Laid-open Patent Applications EP 47714, EP 217274 and EP 283817 and German Patent Application Laid-Open No. 2817369.

Preferably used amphoteric polymers are those polymers that consist mainly of:

(a) monomers with quaternary ammonium groups of the general formula (VII):

in which R ²² and R ²³ , independently from each other, mean hydrogen or a methyl group and R ²⁴ , R ²⁵ and R ²⁶ , independently from each other, are an alkyl group with 1-4 carbon atoms, Z is an NH group or an oxygen atom , n is an integer from 2 to 5, and A ^(-) is an anion of an organic or inorganic acid, and

(b) carboxylic acid monomers of the general formula (VIII):

in which R ²⁷ and R ²⁸ , independently of one another, are hydrogen or a methyl group.

These compounds according to the invention can be used both in free form and in salt form obtained by neutralizing polymerizates, for example, alkali metal hydroxide. As regards the details of the preparation of these polymerizates, reference can be made to the contents of German Patent Application Laid-Open No. DE 3929973. Most preferred are those polymers using type (a) monomers in which R ²⁴ , R ²⁵ and R ²⁶ are methyl groups, Z is an NH group, and A ^(-) is a halide ion, methoxy sulfate ion or ethoxysulfate ion. A particularly preferred monomer (a) is acrylamido-propyltrimethylammonium chloride. As the monomer (b) for the above polymers, acrylic acid is preferably used.

A preferred polymer of this kind is, for example, Polyquaternium-47 polymer is supplied to the market under the name of Merquat ^® 2001, Calgon firm.

In a third embodiment, the agent of the invention may further comprise nonionic care polymers.

Suitable nonionic polymers are, for example:

- shellac;

- siloxanes, which can be both water-soluble and water-insoluble. Both liquid and non-liquid siloxanes are suitable, and by non-liquid siloxanes are meant compounds whose boiling point at normal pressure is above 200 ° C. Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane; polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane; ethoxylated polydialkylsiloxanes, as well as polydialkylsiloxanes containing amino and / or hydroxyl groups;

- glycoside-substituted silicones according to European patent application EP 0612759 B1.

According to the invention, it is also possible that the composition used contains several, in particular two, different leaving charge polymers with the same charge and / or one ionic polymer and one amphoteric and / or nonionic polymer.

The term “care polymer” according to the invention also means special polymer compositions, such as spherical polymer powder. Various methods are known for producing such microspheres from various monomers, for example by means of a special polymerization process or by dissolving the polymers in a solvent and spraying into an environment in which the solvent can escape or diffuse from the particles. Such a method is known, for example, from European patent application EP 466986 B1. Suitable polymerizates are, for example, polycarbonates, polyurethanes, polyacrylates, polyolefins, polyesters or polyamides. Particularly suitable are such spherical polymer powders whose initial particle diameter is less than 1 μm. Such products based on polymethacrylate copolymers are commercially available, for example, under the trademark Polytrap ^® Q-6603 (Dow Corning). Another polymer powder, for example based on polyamides (nylon 6, nylon 12), is commercially available with a particle size of 2-10 μm (90%) and a specific surface area of about 10 m ² / g under the trademark Orgasol ^® 2002 DU Nat Cos (Atochem S.A., Paris). Other spherical polymer powders suitable for the purposes of the invention are, for example, polymethacrylates (Micropearl M) from SEPPIC or (Plastic Powder A), NIKKOL, copolymers of styrene and divinylbenzene (Plastic Powder FP), NIKKOL, polyethylene and polypropylene powder (ACCUREL EP 400 ) from AKZO or silicone polymers (Silicone Powder X2-1605) from Dow Corning or also spherical cellulose powder.

Typically, the care polymers are contained in the agent used according to the invention in an amount of preferably from 0.01 to 10% by weight, based on the weight of the agent as a whole. An amount of from 0.1 to 5% by weight, in particular from 0.1 to 2% by weight, is particularly preferred.

Other components

To obtain a dyeing agent according to the invention, dye intermediates are introduced into a suitable carrier containing water. For coloring hair, such carriers are, for example, creams, emulsions, gels, as well as surfactant-containing foam solutions, for example shampoos, foam aerosols or other compositions suitable for application to hair.

The dyeing agent according to the invention, in addition, may contain all active substances, additives and excipients known for such compositions. In many cases, the dyeing agent contains at least one other surfactant, and in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. The person skilled in the art can further check the possible effect of various surfactants on the activity of the enzymatic system of the invention, for example, by a simple preliminary test.

In a preferred embodiment of the present invention, keratin fiber dyes use a combination of anionic and nonionic surfactants or a mixture of anionic and amphoteric surfactants.

However, in some cases, it may be useful to choose surfactants from amphoteric or nonionic surfactants, since they usually have little effect on the dyeing process according to the invention.

Suitable anionic surfactants in the compositions of the invention are all anionic surfactants intended for use on the human body. They are characterized by the content of water-soluble anionic groups, for example, such as carboxylate, sulfate, sulfonate or phosphate groups, and lipophilic alkyl groups with approximately 10-22 carbon atoms. The molecule may additionally contain glycol or polyglycol ether groups, ester groups or ether groups and amido groups, as well as hydroxyl groups. Examples of suitable anionic surfactants are existing in each case in the form of sodium, potassium and ammonium salts, as well as mono-, di- and trialkanolammonium salts with two or three atoms in the alkanol group:

- straight chain fatty acids with 10-22 carbon atoms (soaps);

- ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a straight chain alkyl group with 10-22 carbon atoms, and X is 0 or from 1 to 16;

- acyl sarcosides with 10-18 carbon atoms in the acyl group;

- acyl taurides with 10-18 carbon atoms in the acyl group;

- acyl isothionates with 10-18 carbon atoms in the acyl group;

- mono- and dialkyl ethers of sulfosuccinic acid with 8-18 carbon atoms in the alkyl group and alkylpolyoxyethylated monoesters of sulfosuccinic acid with 8-18 carbon atoms in the alkyl group and with 1-16 hydroxyethyl groups;

- straight chain alkanedisulfonates with 12-18 carbon atoms;

- straight-chain alpha olefin sulfonates with 12-18 carbon atoms;

- methyl ester of alpha-sulfocarboxylic fatty acid containing from 12-18 carbon atoms;

- alkyl sulfates and sulfates of alkyl polyglycol ethers of the formula RO (CH ₂ —CH ₂ O) _x —SO ₃ H, in which R is preferably a straight chain alkyl group with 10-18 carbon atoms and X is zero or 1 to 12;

- a mixture of surface-active hydrosulfonates according to German patent application DE-A-3725030;

- sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether according to German patent application DE-A-3723354;

- sulfonates of unsaturated fatty acids with 12-24 carbon atoms and 1-6 double bonds according to German patent application DE-A-3926344;

- ester of tartaric acid and citric acid with alcohols, the addition products of approximately 2-15 moles of ethylene oxide and / or propylene oxide to fatty alcohols with 8-22 carbon atoms;

- protein acid concentrates;

- cocosmonoglyceride sulfates;

- amido ether sulfates.

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

Nonionic surfactants contain as hydrophilic groups, for example, polyol groups, polyalkylene glycol ether groups or a combination of polyol and polyalkylene glycol ether groups. Such compounds are, for example:

- products of the addition of 2-30 moles of ethylene oxide and / or 0-5 moles of propylene oxide to straight chain fatty alcohols with 8-22 carbon atoms, to fatty acids with 12-22 carbon atoms and to alkyl phenols with 8-15 carbon atoms in the alkyl group ;

- mono - and diesters of fatty acids with 12-22 carbon atoms with the products of the addition of 1-30 moles of ethylene oxide to glycerin;

- C ₈ -C ₂₂ -alkylmono- and oligoglycosides and their ethoxylated analogues, as well as

- addition products of 5-60 moles of ethylene oxide to castor oil and hardened castor oil.

In addition, zwitterionic surfactants can be used, especially as shared surfactants. Zwitterionic surfactants are those surfactants which contain in the molecule at least one quaternary ammonium group and at least one —COO ^(-) or —SO ₃ ^(-) group. Particularly suitable zwitterionic surfactants are so-called betaines, such as N-alkyl-N, N-dimethylammonium glycinate, for example cocosalkyl dimethyl ammonium glycinate; N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example cocosacylaminopropyl dimethyl ammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, in each case with 8-18 carbon atoms in the alkyl group or acyl group, as well as cocosacylaminoethyl-ethyl-ethyl-ethyl-ethyl-ethyl . A preferred zwitterionic surfactant is a fatty acid amide derivative known under the INCI name cocamidopropyl betaine. Ampholytic surfactants are particularly suitable as shared surfactants. Ampholytic surfactants are understood to mean such surfactants which contain, in addition to one alkyl group with 8-18 carbon atoms or one acyl group, at least one free amino group and at least one —COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acid, N-alkyl imidodipropionic acids, N-hydroxyethyl-N-alkyl-amidopropyl glycines, N-alkyl taurins, N-alkyl sarcosines, 2-alkyl aminopropyl amines acids and alkylaminoacetic acids in each case with about 8-18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocosalkylamino propionate, cocosacylaminoethylaminopropionate and acyl sarcosine with 12-18 carbon atoms in the acyl group.

Particularly quaternary ammonium compounds such as ester quaternary ammonium compounds and amido amines are used as cationic surfactants according to the invention.

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyl trimethylammonium chloride, dialkildimetilammoniyhlorid and trialkilmetilammoniyhlorid, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, laurildimetilammoniyhlorid, laurildimetilbenzilammoniyhlorid and tritsetilmetilammoniyhlorid and imidazole compounds, Quaternium-27, known under the INCI-name and Quaternium-83. The long alkyl chains of the above surfactants preferably contain 10-18 carbon atoms.

Under ester quaternary ammonium compounds are meant known substances containing at least one ester functional group, and at least one quaternary ammonium group as an element of the structure. Preferred ester quaternary ammonium compounds are quaternary ester salts of fatty acids with triethanolamine, quaternary ester salts of fatty acids with di-ethanolalkylamines and quaternary ester salts of fatty acids with 1,2-dihydroxypropyl dialkyl amines. Such products are commercially available, for example, under the trademarks of Stepantex ^® , Dehyquart ^® and Armocare ^® . Examples of such ester quaternary ammonium compounds are Armocare ^® VGH-70, N, N-bis (2-palmitoyloxyethyl) -dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35.

Alkylamidoamines are prepared by the conventional method of amidation of natural or synthetic fatty acids and a fraction of fatty acids with dialkylamino amines. Particularly useful compounds of the invention of this group are stearamidopropyldimethylamine, available on the market under the symbol Tegoamid ^® S18.

Other cationic surfactants used according to the invention are quaternary protein hydrolysates.

Cationic silicone oils are also suitable, for example, those available on the market Q2-7224 (manufacturer Dow Corning; stabilized trimethylsilylamodimethicone), Dow Corning 929 Emulsion emulsion (containing hydroxylamine modified silicone, also referred to as amodimethicone), SM-2059 (manufacturer General Electric ), SLM-55067 (manufactured by Wacker), as well as Abil ^® -Quat 3270 and 3272 (manufactured by Th. Goldschmidt; dicentric polydimethyloxanes, Quaternium-80).

An example of a quaternary sugar derivative used as a surfactant is the commercial product Glucquat ^® 100, according to the INCI nomenclature "Lauryl Metyl Gluceth-10 Hydroxpropyl Diamonium Chloride".

As for the compounds with alkyl groups used as a surfactant, in each case we are talking about individual substances. However, as a rule, upon receipt of such a substance, it is preferable to start from natural raw materials of plant or animal origin, resulting in a mixture of substances with different lengths of alkyl chains, depending in each case on a particular raw material.

As surfactants, which are products of the addition of ethylene oxide and / or propylene oxide to fatty alcohols or derivatives of such addition products, both products with a “normal” homologous distribution and products with a narrow homologous distribution can be used. By “normal” homologous distribution is meant mixtures of homologs obtained by the reaction of fatty alcohol and alkylene oxide when used as catalysts, alkali metals, alkali metal hydroxides or alkali metal alcoholates. A narrow homological distribution is obtained when, for example, hydrotalcites, alkaline earth metal salts of carboxylic acids containing ether groups, alkaline earth metal oxides, alkaline earth metal hydroxides or alkaline earth metal alcoholates are used as catalysts. The use of products with a narrow homologous distribution may be preferable.

In addition, the agent according to the invention preferably comprises at least one alkalizing agent. Preferred alkalizing agents are ammonia, monoethanolamine, isopropylamine, isopropanolamine, 2-amino-2-methylpropan-1-ol, an alkali metal hydroxide, especially sodium hydroxide or potassium hydroxide and, in particular, arginine, lysine and histidine. Particularly preferred according to the invention are dyeing agents containing monoethanolamine, 2-amino-2-methylpropan-1-ol, an alkali metal hydroxide, in particular sodium hydroxide or potassium hydroxide, and especially arginine, lysine and histidine.

In addition, the dyeing agent according to the invention can preferably also contain a conditioning (moisturizing) active substance selected from the group consisting of cationic surfactants, alkylamido amines, paraffin oils, vegetable oils and synthetic oils. As for cationic surfactants, it is possible to refer to the aforementioned species.

Suitable conditioning agents are, in addition, silicone oils, in particular dialkyl and alkylaryl siloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, as well as their hydroxyalkylated and quaternary analogues. Examples of such silicones are products marketed by Dow Corning under the code names DC 190, DC 200, DC 344, DC 345 and DC 1401, as well as marketable products Q2-7224 (manufacturer Dow Corning; stabilized trimethylsilylamodimethicone), emulsion Dow Corning ^® 929 Emulsion (containing hydroxyamine-modified silicone, also called Amodimethicone), SM-2059 (manufactured by General Electric); SLM-55067 (manufacturer Wacker), as well as Abil ^® -Quat 3270 and 3272 (manufacturer Th. Goldschmidt; dimetric polydimethylsiloxane, Quaternium-80).

Paraffin oils synthetically prepared oligomeric alkenes, as well as vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach oil are equally suitable as conditioning active substances.

Suitable hair conditioning compounds are also phospholipids, for example soya lecithin, egg lecithin and cephalins.

In addition, the compositions used according to the invention preferably contain at least one oil component.

Suitable oil components according to the invention are, in principle, all water-insoluble oils and fats, as well as mixtures thereof with hard paraffins and waxes. According to the invention, water-insoluble are those substances whose solubility in water at 20 ° C is less than 0.1 wt.%. The melting point of the individual oil and fat components is preferably below about 40 ° C. Particularly preferred according to the invention may be such oily and fatty components that are liquid at room temperature, that is, at temperatures below 25 ° C. However, when using several oil and fat components, as well as, if necessary, hard paraffins and waxes, as a rule, it is already sufficient if a mixture of oil and fat components, as well as, if necessary, paraffins and waxes satisfies these conditions.

A preferred group of oil components are vegetable oils. Examples of such oils are sunflower oil, olive oil, jojoba soybean oil, rapeseed oil, almond oil, orange oil, wheat germ oil, peach oil and liquid components 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 suitable group of compounds used as oil components according to the invention are liquid paraffin oils and synthetic hydrocarbons, as well as a di-n-alkyl ether with a total number of carbon atoms between 12 and 36, in particular from 12 to 24 carbon atoms. Such as, for example, 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, as well as di-tert-butyl ether, di-isopentyl ether, di -3-ethyldecyl ether, tert-butyl n-octyl ether, isopentyl n-octyl ether and 2-methyl-pentyl n-octyl ether. Compounds sold on the market as commodity products may be preferred: 1,3-di (2-ethylhexyl) cyclohexane (Cetiol ^® S) and di-n-octyl ether (Cetiol ^® ОЕ).

Equally suitable according to the invention, the oil components are esters of fatty acids and fatty alcohols. Preferred are monoesters of fatty acids with alcohols containing 3-24 carbon atoms. This group of substances refers to products of esterification of fatty acids with 6-24 carbon atoms (for example, such as caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid , stearic acid, isostearic acid, oleic acid, elaidic acid, petrozelinic acid, linoleic acid, linolenic acid, eleostearic acid, arachinic acid, gadoleic acid, behenic acid and erucic acid, as well as their technical mixtures, which are formed, for example, during the decomposition of natural fats and oils under pressure, during the oxidation of aldehydes from Relos oxysynthesis, or during the dimerization of unsaturated fatty acids with alcohols, such as, for example, isopropyl alcohol, capron 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, pe roselinyl alcohol, linolyl alcohol, linolenyl alcohol, eleostearyl alcohol, arachilic alcohol, gadoleyl alcohol, behenyl alcohol, erucil alcohol and brassidyl alcohol, as well as their technical mixtures, for example, methyl esters based on hydrogenation under high pressure and based on them or aldehydes formed during Rehlen oxosynthesis, and also formed as a monomer fraction in the dimerization of unsaturated fatty alcohols. Particularly preferred according to the invention are isopropyl myristate, isononanoic acid alkyl ester with 16-18 carbon atoms in the alkyl (Cetiol ^® SN), stearic acid 2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tri-caprylate, coconut / caprylate coconut fatty alcohol and n-butyl stearate.

In addition, the oil components used according to the invention are also dicarboxylic acid esters such as di-n-butyl adipate, di (2-ethylhexyl) adipate, di (2-ethylhexyl) succinate and di (isotridecyl) acelaate, as well as diol esters such as ethylene glycol dioleate, ethylene glycol diisotride decanoate, propylene glycol di (2-ethyl hexanoate), propylene glycol di isostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol di caprylate, such as tearate.

Finally, fatty alcohols with 8-22 carbon atoms can also be used as active oil components according to the invention. Fatty alcohols can be saturated or unsaturated and straight chain or branched. Suitable for use in the sense of the invention are, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, erucane alcohol, ricinole alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, laethyl alcohol, cetyl alcohol arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, as well as Gerbe alcohols, and their enumeration is given as an example and should not be of a limiting nature. However, fatty alcohols are preferably obtained from natural fatty acids, and their preparation can be carried out in the usual way by reducing fatty acid esters. Fats of fatty alcohols obtained 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 fatty acid esters derived from products are also suitable for use according to the invention. their transesterification with the corresponding alcohols, and, therefore, representing a mixture of various fatty alcohols.

The oil components are used in the dyeing agents according to the invention, preferably in an amount of from 0.05 to 10 wt.%, In particular from 0.1 to 2 wt.%.

Other active substances, excipients and additives are, for example:

- structuring agents, such as maleic acid and lactic acid;

- protein hydrolysates, in particular proteins of elistin, collagen, keratin, milk protein, soy and wheat proteins, their condensation products with fatty acids, as well as quaternary protein hydrolysates;

- perfume oils, dimethyl isosorbide and cyclodextrins;

- solvents and dissolution promoting agents such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol;

- active substances that improve the structure of the fiber, in particular mono-, di- and oligosaccharides, such as, for example, glucose, galactose, fructose, fruit sugar and lactose;

- Quaternary amines, such as methyl-1-alkylamidoethyl-2-alkyl-imidosolinium methosulfate;

- antifoams, such as silicones;

- dyes for tinting funds;

- active substances that prevent peeling, such as Proctone Olamine, Zink Omadine and Climbazol;

- light stabilizers, especially benzophenone derivatives, cinnamic acid derivatives and triazines;

- pH regulators, for example, such as ordinary acids, especially flavoring acids and bases;

- active substances, such as allantoin, pyrrolidone carboxylic acids and their salts, for example bisabolol;

- vitamins, provitamins and intermediates of vitamins, in particular, groups A, B ₃ , B ₅ , B ₆ , C, E, F and H;

- plant extracts, such as extracts of green tea, oak bark, nettle, witch hazel, hop, chamomile, burdock rhizome, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needles, horse chestnut, Santal tree, juniper, coconut , mango, apricot, lemon, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadow cress, thyme, yarrow, thyme, lemon balm, stalnik, coltsfoot, marshmallow, meristem, ginseng and ginger rhizomes;

- cholesterol;

a consistency regulator, such as a sugar ester, a polyol ester or a polyol alkyl ether;

- fats and waxes such as spermaceti, beeswax, montan wax and paraffin;

- alkanolamides of fatty acids;

- complexing agents such as ethylenediaminetetraacetic acid (EDTA), nitrile triacetic acid (NTA), β-alanine diacetic acid and phosphonic acids;

swelling and penetration agents such as glycerin, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, urea, as well as primary, secondary and tertiary phosphates;

- silencers such as latex, styrene / polyvinyl pyrrolidone (PVP) and styrene / acrylamide copolymers;

- pearlescent glittering agents, such as ethylene glycol mono- and distearate, as well as PEG-3 polyethylene glycol distearate;

- pigments;

- stabilizers of hydrogen peroxide and other oxidizing agents;

- blowing agents such as mixtures of propane and butane, nitrous oxide (N ₂ O), dimethyl ether, carbon dioxide and air;

- antioxidants and conservatives.

As for the other optional components, as well as their amounts used, it is possible to refer to the reference book known to the specialist, for example, reference book B.Kh.Schrader, Grundlagen und Rezepturen der Kosmetika, 2, Auflage, Huthig Buch Verlag, Heidelberg 1989.

It is advisable to mix the enzyme composition with the composition of intermediates of dyes immediately before hair coloring. The resulting ready-to-use hair dye preparation should have a pH value preferably in the range from 4 to 10, in particular from 6 to 9, most preferably from 7 to 8.5. In addition, the most preferable were low-viscosity formulations for use with a viscosity of less than 3000 MPa · s (Brookfield viscometer, spindle 4, 20 rpm, 20 ° C). The operating temperature during use may be between 10 ° C. and 50 ° C., preferably between 20 ° C. and 35 ° C. At the end of the exposure period of about 30 minutes, the hair dye is removed by rinsing with dyed hair. Subsequent shampooing is no longer necessary if a strong surfactant-containing carrier, for example a coloring shampoo, is used.

According to the invention, in order to further increase the effectiveness of the agent according to the invention, it may be preferable, after treating the fibers with the agent according to the invention, to carry out the final fiber treatment with a solution containing a small amount of hydrogen peroxide. The solution may be prepared, for example, in the form of a shampoo or conditioner. A finishing agent of this type typically contains hydrogen peroxide in a concentration of between 0.01 and 0.5% by weight.

In another embodiment of the present invention, it may be preferable to prepare the agent, in particular, as a separately prepared enzyme composition without antioxidants and / or complexing agents, since they can block the action of the enzyme.

The second object of the present invention is a method for dyeing keratin fibers, according to which the agent according to the invention is applied to the fibers and again washed off at the end of the exposure period.

A third object of the present invention is a method for dyeing keratin fibers, according to which, in the first stage, a composition containing components (A), (C) and (D) is applied to the fibers, after the period of exposure to the fibers, if necessary, washed, and in the second stage to the fibers applying a composition containing component (B). According to the invention, it is equally possible that the method according to which at the first stage the fibers are treated with a composition containing component (B), after the exposure period of the fiber is washed, if necessary, and immediately after that a composition containing components (A), (C) and ( D)

A fourth aspect of the present invention is the use of the agent of the invention for oxidative dyeing of keratin fibers.

A fifth object of the present invention is a kit for dyeing keratin fibers, comprising at least one first composition, containing in a cosmetically acceptable carrier:

(A) at least one dye intermediate;

(C) at least one surfactant is a sugar selected from the group including:

- alkyl and alkenyl oligoglycosides and

- N-alkyl polyhydroxyalkylamides of fatty acids, and

(D) at least one reducing agent,

and a second composition containing in a cosmetically acceptable carrier

(B) at least one enzyme capable of catalyzing the oxidation of a dye intermediate.

The following examples should illustrate the invention in more detail.

Examples

In the following examples, unless otherwise indicated, quantitative data are given in mass percent.

I) The composition of the gels for dyeing

Dyeing Gel 1: Natrosol ^® 250 HR ¹ 2.0 Emulgin ^® B2 ² 0.5 Plantacare®1200 UP ³ 0.5 Lamesoft ^® PO65 ⁴ 0.2 Trisodium citrate dihydrate 0.5 2,4,5,6-tetraaminopyrimidine sulfate 0.1 p-toluylene diamine sulfate 0.1 4-amino-3-methylphenol 0.25 N-aminophenol 0.1 4-chlororesorcinol 0.12 2-amino-3-hydroxypyridine 0.13 Monoethanolamine up to pH 7 Water up to 100

¹ hydroxyethyl cellulose (INCI name: Hydroxyethylcellulose) (Hercules);

² cetyl stearyl alcohol containing about 20 units of ethylene oxide (INCI name: Ceteareth-20) (Cognis);

³ alkyl-1,4-glucoside with 12-16 carbon atoms in the alkyl (about 50-53% of the active substance) (INCI name: Layryl Glucuside) (Cognis);

^{4 a} mixture of oleic acid monoglycerides and alkyl polyglucosides (water content approximately 32-35%, INCI name: Glucuside Clyceryl Oleate, Aqua (Water)) (Cognis).

Dyeing Gel 2: Natrosol ^® 250 HR 2.0 Plantacare ^® 1200 UP 0.5 Lamesoft ^® PO65 0.2 Polymer W 37194 ⁵ 0.1 Trisodium citrate dihydrate 0.5 2,4,5,6-tetraaminopyrimidine sulfate 0.1 1- (β-hydroxyethyl) -p-phenylenediamine sulfate 0.1 4-amino-3-methylphenol 0.1 4-chlororesorcinol 0.1 2-amino-3-hydroxypyridine 0.13 Rodol 9R Base ⁶ 0.1 Monoethanolamine up to pH 7 Water up to 100

⁵ copolymer of sodium salt of acrylic acid and acrylamidopropyl-trimethylammonium chloride with a Phenonip preservative (about 19-21% of the active substance, INCI name: Acrylamidopropyl-Trimonium Chlorid / Acrylates Copolymer) (Stockhausen)

⁶ 2-amino-6-chloro-4-nitrophenol.

Dyeing Gel 3: Natrosol ^® 250 HR 2.0 Emulgin ^® B2 0.5 Plantacare ^® 1200 UP 1,0 Lamesoft ^® PO65 0.5 N-acetyl-L-cysteine 0.15 2,4,5,6-tetraaminopyrimidine sulfate 1,5 p-phenylenediamine sulfate 0.2 4-amino-2-aminomethylphenol dihydrochloride 0.05 2-methylresorcinol 1,0 1- (β-hydroxyethylamino) -4-methyl-2-nitrobenzene 0.1 L-arginine 1,0 Monoethanolamine up to pH 7 Water up to 100

Dyeing Gel 4: Natrosol ^® 250 HR 2.0 Emulgin ^® B2 0.5 Plantacare ^® 1200 UP 0.5 Lamesoft® PO65 0.2 Trisodium citrate dihydrate 0.5 2,4,5,6-tetraaminopyrimidine sulfate 0.2 4,5-diamino-1- (β-hydroxyethyl) pyrazole 0.05 4-amino-3-methylphenol 0.4 2-methylresorcinol 0.2 2,7-dihydroxynaphthalene 0.6 4-chlororesorcinol 0.2 Lysine 0.2 Isopropanolamine up to pH 7 Water up to 100

Dyeing Gel 5: Natrosol ^® 250 HR 2.0 Emulgin ^® B2 0.5 Plantacare ^® 1200 UP 0.5 Lamesoft ^® P065 0.2 N-acetyl-L-cysteine 0.2 p-toluylene diamine sulfate 1,1 p-aminophenol 0.1 2-methylresorcinol 0.1 2,7-dihydroxynaphthalene 0.3 5,6-dihydroxyindolehydrobromide 0.2 m-aminophenol 0.06 2-methylamino-3-amino-6-methoxypyridine 0.02 2-amino-3-hydroxypyridine 0.01 Resorcinol 0.2 Monoethanolamine up to pH 7 Water up to 100

Dyeing Gel 6: Natrosol ^® 250 HR 2.0 Emulgin ^® B2 0.5 Plantacare ^® 1200 UP 1,5 Trisodium citrate dihydrate 0.2 N-acetyl-L-cysteine 0.2 p-toluylene diamine sulfate 0.6 Bis (2-hydroxy-5-aminophenyl) methane 0,03 2-methylresorcinol 0,07 N-aminophenol 0,03 4-chlororesorcinol 0.18 Resorcinol 0.1 Histidine 0.5 Monoethanolamine up to pH 7 Water up to 100

Dyeing Gel 7: Carbopol ^® 934 ⁷ 1,5 Emulgin ^® B2 0.5 Plantacare ^® 1200 UP 1,5 Polymer JR 400 ⁸ 0.5 Trisodium citrate dihydrate 0.5 2,4,5,6-tetraaminopyrimidine sulfate 0.2 p-toluylene diamine sulfate 0.9 4-amino-2-aminomethylphenol dihydrochloride 0.4 2-methylresorcinol 0.25 2,7-dihydroxynaphthalene 0.6 4-chlororesorcinol 0.24 5,6-dihydroxyindolehydrobromide 0.2 m-aminophenol 0,03 L-arginine 1,0 Isopropanolamine up to pH 7 Water up to 100

⁷ carboxyvinyl polymer (INCI name: Carbomer) (Goodrich)

⁸ Quaternary Hydroxyethyl Cellulose (INCI Name: Polyquaternium-10) (Amerchol)

Dyeing Gel 8: Carbopol ^® 934 ⁷ 1,0 Emulgin ^® B2 0.2 Emulgin ^® B1 ⁹ 0.2 Plantacare ^® 1200 UP 0.5 Lamesoft ^® PO65 0.2 Tripotassium citrate dihydrate 0.5 2,4,5,6-tetraaminopyrimidine sulfate 0.7 p-toluylene diamine sulfate 0.4 2- (β-hydroxyethylamino) -p-phenylenediamine sulfate 0.1 3-methyl-4-aminophenol 0.5 2-methylresorcinol 0.5 2,7-dihydroxynaphthalene 0.16 4-chlororesorcinol 0.1 2-amino-3-hydroxypyridine 0.5 Base Rodol 9R Base 0.1 Histidine 0.2 Monoethanolamine up to pH 7 Water up to 100

⁹ cetyl stearyl alcohol containing about 12 units of ethylene oxide (INCI name: Ceteareth-12) (Cognis);

Dyeing Gel 9: Natrosol ^® 250 HR 2.0 Emulgin ^® B2 0.2 Emulgin ^® B1 0.2 Plantacare ^® 1200 UP 1,5 Lamesoft ^® PO 65 0.2 Merquat ^® 280 ¹⁰ 0.8 Trisodium citrate dihydrate 1,0 2,4,5,6-tetraaminopyrimidine sulfate 0.6 p-toluylene diamine sulfate 0.02 3-methyl-4-aminophenol 0.6 4-chlororesorcinol 0,03 2-amino-3-hydroxypyridine 0.5 1- (β-hydroxyethylamino) -4-methyl-2-nitrobenzene 0.1 Isopropanolamine up to pH 7 Water up to 100

¹⁰ copolymer of dimethyldiallylammonium chloride and acrylic acid (about 35% of the active substance, INCI name: Polyquaternium-22) (Chemoviron).

Dyeing Gel 10: Aculyn ^® 22 ¹¹ 2.0 Emulgin ^® B2 0.5 Plantacare ^® 1200 UP 0.5 Lamesoft ^® PO65 0.2 Trisodium citrate dihydrate 0.5 Tripotassium citrate dihydrate 0.5 2,4,5,6-tetraaminopyrimidine sulfate 0.6 p-toluylene diamine sulfate 0.27 2,6-di (β-hydroxyethylamino) toluene 0.4 3,5-diamino-2,6-dimethoxypyridine 0.5 Sodium Lye up to pH 7 Water up to 100

^{11 A} copolymer of methacrylic acid ester with ethoxylated stearyl alcohol with a degree of hydroxyethylation of 20 and acrylic acid (approximately 30% of the active substance, INCI name: Acrylates / Steareth-20 Methacrylate Copolymer) (Rohm & Haas).

Dyeing Gel 11: Natrosol ^® 250 HR 3.0 Emulgin ^® B2 0.5 Plantacare ^® 1200 UP 1,5 Lamesoft ^® PO65 0.2 Trisodium citrate dihydrate 0.5 p-toluylene diamine sulfate 1,1 1,3-bis (2 ', 4'-diaminophenoxy) propanhydrochloride 0.4 m-aminophenol 0.1 2-methylamino-3-amino-6-methoxypyridine 0.2 2-amino-4- (β-hydroxyethylamino) anisole sulfate 0.2 Monoethanolamine up to pH 7 Water up to 100

II) Enzymes

a) Laccase

Used laccase from Rhus vernificera, Sigma company. The laccase activity is determined according to the manufacturer's data so that one unit [1U] corresponds to the amount of laccase, which gives ΔA ₅₃₀ 0.001 per minute with a pH of 6.5 and 30 ° C in 3 ml of a reaction solution with syringaldacin as a substrate.

In each case, an amount of laccase was used which, under the above conditions, shows an activity of 280,000 units [U].

b) Ascorbate oxidase

Ascorbate oxidase from Cucurbita species, manufactured by Roche-Diagnostics, was used. The activity of ascorbate oxidase is determined so that one unit of [1U] corresponds to the amount of ascorbate oxidase that catalyzes in a phosphate buffer solution (monophosphate KH ₂ PO ₄ 0.1 mol / l; disodium phosphate Na ₂ HPO ₄ 4 mmol / l; ethylene di- minetetraacetic acid (EDTA) 0.5 mmol / L) oxidation of 1 μmol of L-ascorbic acid for one minute at pH 5.6 and 25 ° C (according to the definition of commercial products from Roche-Diagnostics). The determination is carried out spectroscopically to reduce the absorption at 245 nm.

In each case, an amount of ascorbate oxidase is used which, under the above conditions, shows an activity of 100,000 units [U].

c) Bilirubin oxidase

Bilirubin oxidase from Myrothecium verrucaria, Sigma, was used. The activity of bilirubin oxidase is determined so that one unit of [1U] corresponds to the amount of bilirubin oxidase, which catalyzes the oxidation of 1 μmol of bilirubin at pH 8.4 and 37 ° C for one minute.

In each case, an amount of bilirubin oxidase was used which, under the above conditions, shows an activity of 1000 units [U].

d) uricase

Used uricase from Arthobacter globiformis, firm Sigma. The activity of uricase is determined so that one unit of [1U] corresponds to the amount of uricase that catalyzes the conversion of 1 μmol of uric acid to allantoin at pH 8.5 and 25 ° C for one minute.

In each case, an amount of uricase was used which, under the above conditions, shows an activity of 25,000 units [U].

Ill) Dyeing

Enzymes a) to c)

60 g of an appropriate dyeing gel from 1 to 11 was adjusted to pH 7 by means of a 10 ml solution with potassium diphosphate / potassium monophosphate buffer (K ₂ HPO ₄ / KH ₂ PO ₄ ) containing enzymes a) -c) mentioned in point II) activity. The mixture was applied to human hair (Kerbing, naturally white, 4 g of dye for 0.5 g of hair), rubbed and left at room temperature for 30 minutes. Then the hair was rinsed and dried.

Enzyme g)

60 g of dyeing gel from 1 to 11 were mixed with 0.35 g of uric acid and the amount of uricase indicated in paragraph II). Diluted to 70 g with twice distilled water. Subsequent dyeing was carried out similarly to the method described for enzymes a) to c).

The results of each dyeing can be taken from the table below.

Color tone (color tone) Laccase Ascorbate oxidase Bilirubin oxidase Uricase Dyeing Gel 1 Savrasovy Autumn brown Autumn brown Light golden brown Dyeing Gel 2 Autumn red Red brown Autumn red Mahogany color Dyeing Gel 3 Garnet red Garnet red Garnet red Garnet red Dyeing Gel 4 Medium brown Light brown Medium brown Chocolate brown Dyeing Gel 5 Dark brown Medium dark brown Medium dark brown Brown Dyeing Gel 6 Light golden brown Golden brown Golden brown Medium brown Dyeing Gel 7 Nut brown Tan Tan Medium brown gold Dyeing Gel 8 Red copper Copper red Copper gold Copper Dyeing Gel 9 Copper Copper brown Copper gold Copper gold Dyeing Gel 10 Dark violet Dark violet Dark violet Violet Dyeing Gel 11 The black The black The black Dark grey

Additional example

In the following examples of dyeing gels, unless otherwise indicated, quantitative data are given in mass percent.

Component Composition 12 a (according to the invention) Composition 12 b (comparative) Natrosol ^® 250 HR 2.0 2.0 Emulgin ^® B2 0.5 0.5 Plantacare ^® 1200 UP 0.5 0.5 Lamesoft ^® PO65 0.2 - Merquat ^® 20.01 LMW 0.5 0.5 Trisodium citrate dihydrate 0.5 0.5 2,4,5,6-tetraaminopyrimidine sulfate 0.7 0.7 p-toluylene diamine sulfate 0.4 0.4 4-amino-3-methylphenol 0.5 0.5 Hydrochloric acid (2M) 2.0 2.0 2-methylresorcinol 0.4 0.4 2,7-dihydroxypyridine 0.2 0.2 4-chlororesorcinol 0.1 0.1 2-amino-3-hydroxypyridine 0.4 0.4 Base Rodol 9R Base 0.1 0.1 Monoethanolamine up to pH 7 up to pH 7 Water up to 100 up to 100

Component Composition 13 a (according to the invention) Composition 13 b (comparative) Natrosol ^® 250 HR 2.0 2.0 Emulgin ^® B2 0.5 0.5 Plantacare ^® 1200 UP 0.5 0.5 Lamesoft ^® PO65 0.2 - Merquat ^® 2001 LMW 0.5 0.5 Trisodium citrate dihydrate 0.5 0.5 2,4,5,6-tetraaminopyrimidine sulfate 0.1 0.1 p-toluylene diamine sulfate 0.1 0.1 4-amino-3-methylphenol 0.2 0.2 Hydrochloric acid (2M) 1,0 1,0 4-chlororesorcinol 0.1 0.1 2-amino-3-hydroxypyridine 0.1 0.1 m-aminophenol 0.1 0.1 Base Rodol 9R Base 0.1 0.1 Monoethanolamine up to pH 7 up to pH 7 Water up to 100 up to 100

Component Composition 14 a (according to the invention) Composition 14 b (comparative) Natrosol ^® 250HR 2.0 2.0 Emulgin ^® B2 0.5 0.5 Plantacare ^® 1200 UP 0.5 0.5 Lamesoft ^® PO65 0.2 - Merquat ^® 2001 LMW 0.5 0.5 Trisodium citrate dihydrate 0.5 0.5 p-toluylene diamine sulfate 1,0 1,0 4-amino-3-methylphenol 0.1 0.1 Hydrochloric acid (2M) 0.6 0.6 2-methylresorcinol 0.1 0.1 2,7-dihydroxypyridine 0.3 0.3 4-chlororesorcinol 0.1 0.1 2-amino-3-hydroxypyridine 0.004 0.004 2-methylamino-3-amino-6-methoxypyridine 0.02 0.02 Resorcinol 0.2 0.2 Monoethanolamine up to pH 7 up to pH 7 Water up to 100 up to 100

The commercial product "Merquat ^® 2001 LMW" is a low molecular weight polymer quaternary ammonium chloride obtained by copolymerization of acrylic acid, methacrylate and methacrylamidopropyltrimonium chloride (INCI name: Polyquaternium-47) (Nalco). The remaining used trading products have the values indicated in examples 1 to 11.

60 g of a suitable dye gel from 12 a to 14 b was adjusted to pH 7 using a 10 ml solution with potassium diphosphate / potassium monophosphate buffer (K ₂ HPO ₄ / KH ₂ PO ₄ ) containing laccase from Rhus vernificera, Novo Nordisk company with activity after mixing the dyeing gels and the enzyme solution 40 units [40 LAMU, i.e. laccase Myceliophthora units] on 8 g of the product.

The mixture was applied to human hair (Kerbing, naturally white, 4 g of dye for 0.5 g of hair), rubbed and left at room temperature for 30 minutes. Then the hair was rinsed and dried.

A. Experience in color intensity

Dry hair obtained as a result of the above staining step was subjected to colorimetric measurement. In this case, the color intensity obtained by processing the means according to the invention was taken as a control value of 100%. The results of the experiment are summarized in the following table:

Recipe Based Agent No. Color intensity (option a, according to the invention) Color intensity (option b, comparative) 12 one hundred% 78% 13 one hundred% 89% fourteen one hundred% 92%

The above data clearly indicate that when using a means for dyeing keratin fibers, containing as a component component an incomplete fatty acid glyceride, an unexpectedly increased color intensity is achieved.

B. Experience in resistance to washing

Washed hair used in the above experiment on the color intensity, 6 times using conventional, commercially available shampoo, followed by drying. Repeated the above colorimetric measurement, and the experimental data on the color intensity were taken as control values of 100%. The data obtained are summarized in the following table:

Recipe Based Agent No. Resistance to washing (option a, according to the invention) Resistance to washing (option b, comparative) 12 81% 52% 13 75% 68% fourteen 82% 75%

The above data clearly indicate that when using a means for dyeing keratin fibers containing an incomplete fatty acid glyceride as a component, an unexpectedly increased resistance to washing is achieved.

Claims (17)

1. Means for dyeing keratin fibers, containing in a cosmetically acceptable carrier (A) at least one dye intermediate; (B) at least one enzyme capable of catalyzing the oxidation of a dye intermediate, (C) at least one surfactant is a sugar selected from the group formed by: alkyl oligoglycosides and Fatty acid N-alkyl polyhydroxyalkylamides, (D) at least one reducing agent, and (E) at least one partial fatty acid glyceride. 2. The tool according to claim 1, characterized in that as an intermediate of the dye (A), it contains at least one component - the developer. 3. The tool according to one of claim 1 or 2, characterized in that as an intermediate of the dye (A) it contains at least one derivative of indoline. 4. The tool according to one of claims 1 to 3, characterized in that it contains at least one color-forming component. 5. The tool according to one of claims 1 to 4, characterized in that it further comprises at least one direct dye. 6. The tool according to one of claims 1 to 5, characterized in that as a reducing agent it contains an alkali metal salt of citric acid, in particular sodium citrate, and / or N-acetyl-L-cysteine. 7. The tool according to claim 6, characterized in that as a reducing agent it contains N-acetyl-L-cysteine. 8. The tool according to one of claims 1 to 7, characterized in that it further comprises at least one thickener. 9. The tool according to claim 8, characterized in that the thickener is an anionic or nonionic polymer. 10. The tool according to one of claim 8 or 9, characterized in that as a thickener it contains at least one cellulose derivative. 11. The tool according to one of claims 1 to 10, characterized in that it further comprises a polymer for care. 12. The tool according to one of claims 1 to 11, characterized in that it contains at least one other surfactant. 13. The tool according to item 12, characterized in that it contains a nonionic or amphoteric surfactant. 14. The tool according to one of claims 1 to 13, characterized in that it contains at least one alkalizing agent. 15. The tool according to 14, characterized in that as an alkalizing agent it contains monoethanolamine, isopropylamine, isopropanolamine, 2-amino-2-methylpropan-1-ol, arginine, histidine or alkali metal hydroxide, especially sodium or potassium hydroxide . 16. The tool according to one of claims 1 to 15, characterized in that it has a pH value of from 7 to 8.5. 17. A kit for dyeing keratin fibers, comprising at least one first composition, containing in a cosmetically acceptable carrier (A) at least one dye intermediate; (C) at least one surfactant is a sugar selected from the group formed alkyl oligoglycosides, and N-alkyl polyhydroxyalkylamides of a fatty acid, and (D) at least one reducing agent, (E) at least one partial fatty acid glyceride, and a second composition containing in a cosmetically acceptable carrier (B) at least one enzyme capable of catalyzing the oxidation of a dye intermediate.