EP1771150A1 - Cationic azo compounds as direct dyes for the colouring of keratin fibres - Google Patents

Abstract

The invention relates to cationic azo compounds of general formula (I), where X = O, S, Y = N, CR5, R1 = for example, H, R3 = for example, C6-12 aryl, C7-13 aralkyl or C7-13 alkaryl and R2, R4, R5 = for example, H, used as direct dyes for colouring human hair.

Description

 Cationic azo compounds as direct dyes for coloring keratinic fibers

The present invention relates to agents for coloring keratinic fibers containing specific cationic azo compounds, to processes for dyeing fibers, in particular hair with these agents, and to the use of the cationic azo compounds for this purpose.

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

The developer components are usually primary aromatic amines having a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives ¬ sets.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4, 5, 6-tetraminopyrimidine, p-aminophenol. N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5 , 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4- hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N, N'-bis (4-amino-phenyl) -diaminopropan-2-ol.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used. Suitable coupler substances are, in particular, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl 3-aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

In addition, direct dyes are of great importance for the dyeing of keratin fibers. Here, for example, cationic dyes can be used, which are applied directly to them in a dyeing agent for keratinous fibers.

WO 95/01772 relates to a process for coloring keratinous fibers in which cationic dyes are used. Among others, azo dyes can be used which have an indole radical and a thiazole radical or oxazole radical, see structures (1) and (9) of WO 95/01772. In the indole residue, however, the 2-position according to this document can not be substituted by groups containing aromatic nuclei. The described cationic substantive dyes are used only as a combination of different substantive dyes for dyeing hair.

EP-A-0 875 620 relates to a process for coloring melamine fibers. In particular melamine-formaldehyde fibers are dyed, which are needed in flame retardant applications. It is described that also articles made of melamine fibers in combination with protein fibers can be used for flame retardancy. For this purpose, mixtures of melamine fibers with protein fibers or animal fibers can be used. Examples include wool, silk, cashmere, mohair and rabbit hair. The coloring of human hair is not discussed. The used Dyes are selected from direct dyes, non-metallated acid dyes, metalated acid dyes, disperse disperse dyes, and mixtures thereof. According to Example IA is a mixture of melamine fibers and p-aramid fibers with CI. Colored in Direct Red 79. According to Example HC CI Basic Red 29 is used. On combinations of these dyes with other dyes is not discussed in the document.

Direct dyes can be an alternative to oxidation dyes or complement their property profile. Good oxidation dye precursors are to form the desired color shades in sufficient intensity and fastness in the oxidative coupling. They should also have a good Aufziehvermögen on the fiber, in particular in human hair no significant differences between strained and freshly regrown hair should exist (leveling). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm liquids. Finally, if applied as a hair dye, they should not stain the scalp too much and above all they should be safe in terms of toxicology and dermatology. Furthermore, the coloring achieved by bleaching should be easily removed from the hair, if it does not meet the individual wishes of each person and should be reversed.

But with a developer component or a special coupler / developer combination, it is usually not possible to obtain a natural color shade on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used with each other and with direct dyes. There is therefore a constant need for new, improved dye components, e.g. Direct dye components that allow achievement of the above property profile and are also unproblematic in terms of toxicology and dermatology.

The object of the present invention was therefore to provide direct dyes, in particular for dyeing human hair, which are particularly useful in human hair dyeing Combined with oxidation dye precursors meet the requirements placed on these systems, including in terms of toxicological and dermatological properties, and allow colorations in a wide range of colors with good fastness properties.

In particular, substantive dyes are to be provided for dyeing human hair, which cause a red color.

It has been found according to the invention that specific cationic azo compounds satisfy the requirements imposed on substantive dyes for dyeing human hair to a high degree. They are particularly advantageously used in agents for oxidative dyeing of keratinic fibers, in particular human hair, since they can be advantageously combined with oxidation dye precursors.

They show a brilliant Nuancenausfall, very good wash fastness, a very good leveling power and a good cold wave fastness.

A first subject of the invention is therefore the use of cationic azo compounds of the general formula (I)

with the meaning

XO, S

YN, CR ⁵ ,

R ^{1 is} H, halogen, NO ₂ , C ₆ -i2-aryl, C7.13-ara.kyl. C ₇ .i ₃ alkaryl, Ci _-6 -

Alkyl, which are optionally substituted by: -OH, halogen, -CN, -NO _2, optionally OH-substituted Ci _-4 - alkoxy, -NH _2, -NHR, -NR ₂ are each independently optionally substituted with R OH-substituted Ci-4-alkyl,

R ³ C ₆ i2-aryl, _C7 .i ₃ aralkyl or C ₇ "i ₃ alkaryl, which are optionally substituted by -OH, halogen, -CN, -NO _2, optionally OH-substituted Ci- ₄ - alkoxy, -NH _2, -NHR, -NR ₂ are each independently optionally substituted with R OH-substituted Ci _-4 - alkyl,

R ^2, R ^4, R ⁵ are independently H, Ci _-6 alkyl, Ci- ₆ hydroxyalkyl, C ₂ - ₆ - alkoxyalkyl, Ci. ₆ aminoalkyl, C ₂ i ₀ alkylaminoalkyl, _C3-I2 -. Dialkylaminoalkyl, C _{6] 2} aryl, C ₇ .i ₃ aralkyl or C ₇ i ₃ alkaryl,

as a direct dye for dyeing human hair.

A further subject is the use of cationic azo compounds of the general formula (Ia)

with the meaning

XO, S

YN, CR ⁵ ,

R ^{1 is} H, halogen, NO ₂ , C ₆ -i ₂ -aryl, C ₇ .13 -ra.-alkyl. C7. ₁ 3-A.kary., C ,. ₆ -

Alkyl, which are optionally substituted by: -OH, halogen, -CN, -NO ₂ , optionally OH-substituted C _M - alkoxy, -NH ₂ , -NHR, -NR ² with R each independently of one another optionally OH-substituted C _M alkyl,

R ³ H, Ci. _6- alkyl, Cj-β-hydroxyalkyl, C ₂ . ₆ alkoxyalkyl, C _-6 -

Aminoalkyl, C i _{0 2-} alkylaminoalkyl, C ₃ i ₂ -Dialkylamin9alkyl, _C6-I2 - aryl, C ₇ .i3 aralkyl or C ₇ "i ₃ alkaryl, which are optionally substituted by -OH, halogen, -CN, -NO _2, optionally OH-substituted Ci _-4 alkoxy, -NH _2, -NHR, -NR ² are each independently optionally substituted with R OH-substituted Ci _-4 - alkyl,

R ^2, R ^4, R ⁵ are independently H, Ci _{-6 alkyl;} C _I-6 -Hy droxyalkyl, C ₂ - ₆ - alkoxyalkyl, Ci-6-aminoalkyl, C i _{0 2-} alkylaminoalkyl, C. _{3 12} - dialkylaminoalkyl, _C6 "i ₂ aryl, C _7- ι ₃ -aralkyl or C ₇ .i ₃ alkaryl,

as a direct dye for dyeing human hair.

The definition of the cationic azo compounds of the general formulas (I) and (Ia) differ in the breadth of the definition of the radical R ³ .

The cationic azo compounds of the formulas (I) and (Ia) are particularly advantageously used as substantive dyes in agents for the oxidative dyeing of keratinic fibers, in particular human hair.

The invention also relates to agents for dyeing human hair, which contain in a cosmetically acceptable carrier as substantive dye at least one cationic azo compound of the general formula (I).

In addition, the invention relates to agents for the oxidative coloring of keratinic fibers, in particular human hair, in a cosmetically acceptable carrier Oxidation dye precursors and at least one cationic azo compound of the general formula (Ia).

According to the invention, keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the oxidation dyes according to the invention are primarily suitable for dyeing keratin fibers, in principle, there is nothing to prevent their use in other fields, in particular in color photography.

Examples of the C ₁ -C ₆ -alkyl groups which are mentioned as substituents in the compounds used according to the invention, preferably C ₁ -C ₄ -alkyl groups which may be linear or branched, are the groups methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl , Ethyl and methyl are preferred alkyl groups. As a preferred Cj to C ₆ - (mono) hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. C ₂ - ₆ -Alkoxyalklyreste have a total of 2 to 6 carbon atoms, which are spread on the alkoxy and the alkyl radical. It can thus be present in the alkoxy or alkyl radical in each case up to 5 carbon atoms. It is preferably a c _1-3 -alkoxy-C _1-3 -alkyl radical, particularly preferably C 1-2 -alkoxy-C 1-2 -alkyl radical. Both the alkoxy and the alkyl moiety may be linear or branched. They are preferably linear. Ci _-6 -Aminoalkylreste, preferably Ci. ₄ -Aminoalkylreste, C ₂ -i _ö -Alkylaminoalkylreste, preferably C ₂ . _6- Alkylaminoalkylreste and C ₃ .12 Dialkylaminoalkylreste, preferably C ₃ .Q-Dialkylaminoalkylreste can each have linear or branched alkyl radicals. Each individual alkyl group preferably has 1 to 3 carbon atoms. The alkyl radicals present in the respective groups are preferably as defined above for the pure alkyl radicals.

If radicals are optionally substituted, depending on the number of carbon atoms in the alkyl or alkoxy radical, preferably 1 to 3, particularly preferably 1 or 2, in particular a substituent, may be present. Substituents may be present for R ¹ and R ³ , some of which may in turn be substituted by -OH. Preferably, only one of these further OH substituents is present. C _M -alkyl radicals and Cj _-4 - Alkoxy radicals are in turn linear or branched, preferably linear, and particularly preferably ethyl or methyl. If one of the radicals R ² to R ^{5 contains} a hydroxyl group bonded to an alkylene radical, the hydroxyl group is preferably terminal, and the alkylene radical is linear. A hydroxyethyl radical is thus preferably a 2-hydroxyethyl radical.

Aryl radicals are preferably phenyl radicals. Aralkyl radicals are an alkyl radical substituted by an aryl radical. Alkaryl radicals contain an aryl radical which is substituted by an alkyl radical. The aryl radical is also preferably a phenyl or phenylene radical.

A preferred aralkyl radical is a benzyl radical. A preferred alkaryl radical is a tolyl radical.

The cationic azo compounds of the general formulas (I) and (Ia) are usually present as a salt with corresponding counterions, in particular physiologically acceptable anions. For example, the counterions may be halide ions, in particular chloride or sulfate, phosphate, nitrate, acetate, hydrogen sulfate, hydrogen phosphate, dihydrogen phosphate.

Halogen is generally F, Br, Cl or I, preferably Cl or Br.

Particularly preferably, an azo compound of the general formulas (I) or (Ia) has a total of not more than four OH groups, preferably not more than two OH groups. There are in the azo compound of the general formulas (I) or (Ia) preferably at most four nitrogen atoms, more preferably at most two nitrogen atoms in the radicals R ¹ - R ⁵ before. Overall, apart from the hydroxyl groups, in the azo compound of the general formula (I) are preferably a maximum of two further oxygen atoms.

Preferred meanings of the radicals are listed below. According to one embodiment of the invention R ¹ is hydrogen or C _| C ₄ alkyl, in particular hydrogen.

According to one embodiment of the invention Y is CR ⁵ where R ⁵ is hydrogen or C) - ₄ alkyl. In this case, R ⁵ is particularly preferably hydrogen.

According to one embodiment of the invention R ² and R ⁴ denote Ci _-4 alkyl, particularly preferably methyl.

According to one embodiment of the invention, R ^{3 is} phenyl, benzyl or tolyl, in particular phenyl.

X is particularly preferably sulfur.

In accordance with the invention, Basic Red 29 is particularly preferably used. This substantive dye corresponds to the formulas (I) and (Ia) with the meanings R ^{1 is} hydrogen, X is sulfur, Y is CH, R ² , R ^{4 is} methyl, R ^{3 is} phenyl, where the counterion is a chloride ion.

Human hair dyeing compositions according to the invention contain, in a cosmetically acceptable carrier as substantive dye, at least one cationic azo compound of the general formula (I) as defined above. Preferred agents of this type are described, for example, in DE-A-102 59 849.

According to the invention, particular preference is given to an agent for the oxidative dyeing of keratinic fibers, in particular human hair, which contains oxidation dye precursors and at least one cationic azo compound of the general formulas (I) or (Ia) in a cosmetically acceptable carrier. Preferably, the agent contains at least one developer component and at least one coupler component, as exemplified below.

The composition of the invention may contain one or more, for example at least two different azo compounds of the general formulas (I) or (Ia). The azo compounds of the formulas (I) or (Ia) can be prepared by conventional organic methods.

The compositions according to the invention for coloring keratinic fibers or human hair contain the at least one azo compound of the general formulas (I). or (Ia) preferably in an amount of 0.02 to 5 wt .-%, particularly preferably 0.1 to 2 wt .-%, based on the finished composition.

The agent for coloring keratinous fibers can be selected from any suitable agents that are particularly suitable for dyeing human hair. A cosmetically acceptable carrier used is in particular an otherwise customary carrier of agents for dyeing human hair. Apart from the azo compounds of the general formulas (I) or (Ia), the colorants according to the invention may be composed according to known colorants or contain the usual ingredients for them. Examples of further suitable and inventively preferred ingredients are given below.

Compositions according to the invention may contain the following ingredients as indicated

Have quantities.

Developer 0.05 - 5% ^"

Coupler 0.05 - 5%

Surfactants, emulsifiers 0.1 - 20%

Fatty alcohols and other emulsifiers 0.5 - 20%

Complexing agent 0.05 - 10%

Buffering agent 0.1 - 10%

Solubilizer + solvent 0.5 - 15% pH adjuster as needed

Perfume oils 0,1 - 0,6%

Polymers 0.1 - 5%

Water 50 - 98% Suitable colorant compositions are described, for example, in DE-U 1-29911819, DE-A-011 25 451, DE-Ul-201 114036, Kosmetik, ed. W. Umbach, 2nd ed. 1995, G. ^" Thieme Verlag Stuttgart, New York described.

In addition to the azo compounds of the formulas (I) or (Ia), the colorants according to the invention may further comprise at least one developer component.

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

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

in which

G ¹ represents a hydrogen atom, a Cr to C ₄ alkyl group, a Cr to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (Ci to C ₄₎ - alkoxy _(C) - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C 1 to C 4 alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a 'hydrogen atom, a Cr to C ₄ alkyl group, a Cr to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl _s a (Cr to C ₄₎ - Alkoxy (C 1 to C ₄ ) alkyl or C 1 to C ₄ alkyl substituted with a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C _r to C ₄ alkyl radical, a Cr bis - C ₄ -

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

Hydroxyalkoxy, C 1 -C ₄ -acetylaminoalkoxy, C 1 -C ₄ -

Mesylaminoalkoxy radical or a Ci- to C ₄ -carbamoylammoalkoxy radical;

G is a hydrogen atom, a halogen atom or a Cj- to C ₄ -

Alkyl radical or when G ³ and G ⁴ are ortho to each other, they can together form a bridging α, co-alkylenedioxo group, such as a

To form ethylenedioxy group.

Examples of the Cp to C ₄ -alkyl radicals mentioned as substituents in the compounds are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. Preferred C 1 -C ₄ -alkoxy radicals are, for example, a methoxy or an ethoxy group. Furthermore, as a preferred example of a Cr to C ₄ -Hy droxyalkylgruppe a hydroxym ethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of formula (El) are especially the amino groups, Ci to CrMonoalkylaminogruppen, Ci to C ₄ dialkylamino, C) - to C ₄ - trialkylammonium, Cr to C ₄ -Monohydroxyalkylaminogruppen, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (III) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2.6 Diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine. N, N-dimethyl-p-phenylenediamine. NN-diethyl-p- phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-

Hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-

Hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine ₅ wherein, instead of 3-methylphenyl, phenyl or C] _-6 -alkylphenyl are generally present, and 5,8-diaminobenzo-1,4-dioxane and its physiologically tolerated salts.

P-phenylenediamine derivatives of the formula (II) which are very particularly preferably used according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N-bis- (β-hydroxyethyl) -p-phenylenediamine.

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

Among the binuclear developer components which can be used in the dyeing compositions according to the invention, mention may be made in particular of the compounds corresponding to the following formula (E2) and their physiologically tolerated salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ -ReSt ₅ which is optionally substituted by a C 1 - to C ₄ -alkyl radical, by a C 1 - to C ₄ -

Hydroxyalkyl radical and / or is substituted by a bridge Y or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or a

Alkylene ring containing one or more nitrogen-containing groups and / or one or more heteroatoms. like ^' oxygen, sulfur or

Nitrogen atoms can be interrupted or terminated and may be substituted by one or more hydroxyl or C 1 to C 5 alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to

C ₄ - polyhydroxyalkyl radical, a C] - to C ₄ -Aminoalkylrest or a direct

Connection to the bridge Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G "and G ¹² are each independently

Hydrogen atom, a direct bond to the bridging Y or a Ci- to C ₄ -

Alkyl radical, with the provisos that the compounds of formula (E2) contain only one bridge Y per molecule and the compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom. The substituents used in formula (E2) are defined analogously to the above statements.

Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-amino-phenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (.beta.-hydroxyethyl) -N, N'-bis (4-aminophenyD-tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N'- bis (4 ^t -amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p- phenylenediamine and l, 10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred double bases of formula (E2) are N, N'-bis (.beta.-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -l, _{3-diamino-propan-2-ol>} Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol ₅ N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiologically tolerable salts.

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

in which: G ¹³ represents a hydrogen atom, a halogen atom, a Ci to C ₄ alkyl radical, a Ci to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C _r to C ₄₎ alkoxy ( C _r to C ₄₎ alkyl, a Ci to C ₄ alkylamino aminoalkyl group, a hydroxy (Ci to _C4), a C] - to C ₄ -Hydroxyalkoxyrest, a Ci to C ₄ hydroxyalkyl (C _r to C ₄ ) aminoalkyl or a (di-Ci- bis

C ₄ alkylamino) - (C 1 to C ₄ ) alkyl, and

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

C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a

(C 1 -C ₄ ) -alkoxy (C 1 -C ₄ ) -alkyl radical, a C 1 -C ₄ -aminoalkyl radical or a C 1 -C ₄ -cycloalkyl radical,

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

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

G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (E3) are defined analogously to the above statements.

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- (β-hydroxyethoxy) -phenol, 4- Amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) -phenol, 4- Amino-2- (α, β-dihydroxyethyl) -phenol, 4-amino-2-fluorophenol, 4-amino-2-chloro-phenol, 4-amino-2,6-dichloro-phenol, 4-amino-2- (diethylaminomethyl ) -phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) -phenol. Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

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

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

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- Triaminoρyrimidin.

Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 Diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diamino-pyrazole, 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-hydrazino-pyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole , 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole. 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole. 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) - -amino-l, 3-dimethylpyrazole, 3,4,5-triaminopyrazole, l methyl-3,4,5-triaminopyrazole-, 3,5- -Diamino4-m «thyi = 4 ^j iie.thyiäminopy_razol and 3, 5-Diamino -4- (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole [1,5-a] pyrimidine of the following formula (E4) and its tautomeric _forms; if a tautomeric equilibrium exists:

in which:

G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a CJ to C ₄ alkyl radical, an aryl radical, a Ci to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ polyhydroxyalkyl a (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl radical, a C 1 -C ₄ -aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical, a , alkylamino alkyl (Ci to C ₄₎ a Di - - Ci- to C ₄₎ [(Ci to _C4) alkyl] - (Ci.r ... to C ₄₎ - aminoalkyl radical, wherein the Dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ - hydroxyalkyl or a di- (Ci- to C ₄ ) - [hydroxyalkyl] - (C] - to C ₄ ) - Aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a Ci- to C- _4- alkyl radical, an aryl radical, a Ci- to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ] - to C4-aminoalkyl, one (Cj- bis C ₄ ) alkylamino (C 1 to C ₄ ) alkyl, a di - [(C ₁ to C ₄ ) alkyl] (C ₁ to C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally have a carbon cycle or form a heterocycle having 5 or 6 chain members, a C 1 to C ₄ hydroxyalkyl or a di- (C 1 to C ₄ hydroxyalkyl) aminoalkyl group, a Amino group, a CJ to C ₄ -alkyl- or di- (C, - to C ₄ hydroxyalkyl) has -amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i is 0, 1, 2 or 3, p has the value 0 or 1, q has the value Ö or 1 and n has the value 0 or 1. it with the proviso that the sum of p + q is not equal to 0, if p + q is equal to 2, n has the value 0 , and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or

NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or

(3.7);

The substituents used in formula (E4) are defined analogously to the above recitations.

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

Among the pyrazolo [l, 5-a] -pyrimidines of the above formula (E4) can be mentioned in particular:

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

2,5-dimethylpyrazolo [l, 5-a] pyrimidine-3,7-diamine;

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

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

3-aminopyrazole [l, 5-a.] -Pyrirnidin-5-ol;

2- (3-aminopyrazole [l, 5-a] pyrimidin-7-ylamino) ethanol;

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

2 - [(3-aminopyrazolo [l ₅ 5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amine 9] -ethanol;

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

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

2 ₅ 6-dimethylpyrazolo [l, 5-a] pyrimidine-3,7-diamine;

3-Amino-7-dimethylamino-2,5-dimethylpyrazole [l, 5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

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

In a further preferred embodiment, the inventive colorants contain at least one coupler component.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are, in particular, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethyl ether, m-phenylenediamine, 1-phenyl 3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2 ', 4'-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 Chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Further preferred coupler components according to the invention are m-aminophenol and its derivatives, for example 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol. 3-Amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3

Trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) amino-2-methylphenol, 3 - (Diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives, such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ^l , 4'-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-methyl) hydroxyethylamino) benzene, 1,3-bis- (2 ', 4'-diaminophenyl) -propane, 2,6-bis- (2'-hydroxyethylamino) -1-methylbenzene, 1-amino-3-bis- (2' hydroxyethyldimethylbenzene, 2 - {({3- [2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 2- ({3- [2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - [(3-morpholin-4-ylphenyl) amino] ethanol, o-diaminobenzene and its derivatives such as 3, 4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or Trihydroxybenzolderivate such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol. 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3 , 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diammo-2,6-dimethoxypyridine,

Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5

Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene, morpholine derivatives such as ό-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-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2- Amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1 (2 ') hydroxyethyl) -arnino-3,4-methylenedioxybenzene.

Particularly preferred further coupler components according to the invention are 1-naphthol, 1,5-, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4- Chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine. 2 - {({3- [2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3- [2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino ) ethanol and 2 - [(3-methylpyrin-4-ylphenyl) amino] ethanol.

Particularly suitable according to the invention are the following components:

p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, 1- (2-hydroxyethyl) -2,5-diaminobenzene, 1- (2-hydroxyethyl) -4,5-diaminopyrazole ₅ bis- (2-hydroxy-5 -aminophenyl) methane, 4-amino-2 - [(5-amino-2-hydroxyphenyl) methyl] phenol x 2HCl.

In a further embodiment of the present invention, the colorants may contain at least one precursor of a naturally-analogous dye. As precursors of naturally-analogous dyes such indoles and indolines are preferably used, the at least one hydroxy or amino group. preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. B. in the form of a Etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole derivative and / or indoline derivative.

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

in the independently

- R ^! stands for hydrogen, a C] -C ₄ alkyl group or a Cj-C / _t-alkyl hydroxy group,

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

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

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

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

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

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxy-indoline and in particular the 5,6-Dihydroxyindolin. Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (IIb),

in the independently of each other

- R ¹ represents hydrogen, a Ci-C ₄ alkyl group or C) -C ₄ hydroxyalkyl group,

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

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

- R ⁴ is hydrogen, a C JC ₄ -AlkVl group or a group -CO-R ⁶ , in which R ⁶ is a C) -C ₄ alkyl group, and

R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular the 5 , 6-dihydroxyindole.

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with anorga¬ African or organic acids, eg. Hydrochlorides, sulfates and hydroxides. mide. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment, it may be preferred according to the invention to use the indoline or indole derivative in colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; Very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.

In addition to the inventive m-phenylenediamine derivatives of the formula (I), the colorants according to the invention may, in a further preferred embodiment of the present invention, for shading one or more further substantive

Dyes contain. Such other substantive dyes are common

Nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or

Indophenole. Preferred further substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC

Yellow 5, HC Yellow 6, HC Yellow 12. Acid Yellow 1, Acid Yellow 10, Acid Yellow

23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC

Red Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN,

Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50,

HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9,

Acid black 1, and acid black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3

Nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1 -

(2 ¹ -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-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-

Hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The compositions of the invention may contain a further cationic substantive dye. Particularly preferred are

(a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems substituted with a quaternary nitrogen group such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, to which reference is explicitly made at this point in claims 6 to 11 are called.

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

CH ₃ SO ₄ ^"

Cl ^"

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

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

The compositions according to the invention according to this embodiment preferably contain the entire substantive dyes in an amount of from 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations of the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, Catechu, Sedre and alkano root are included.

It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair colorants according to the invention, due to the production process for the individual dyes, in minor amounts, further components may be included, as far as these are not detrimental to the dyeing result or for other reasons, such as toxicological, must be excluded.

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

The colorants according to the invention may furthermore contain all active ingredients, additives and auxiliaries known for such preparations. In many cases, the colorants contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from arionic, zwitterionic or nonionic surfactants.

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

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH. in which R is a linear alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16. Acylsarcosides having 10 to 18 C atoms in the acyl group, acyl taurides having 10 to 18 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the acyl group Alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 carbon atoms, linear alpha-olefin sulfonates having 12 to 18 carbon atoms, alpha sulfo fatty acid methyl esters of fatty acids with 12 to 18 C atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354, ^'

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide onto fatty alcohols having 8 to 22 C atoms.

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

Nonionic surfactants contain as hydrophilic group z. B. a polyol group, a polyalkylenglykolethergruppe or a combination of polyol and Polyglykolether- group. Such compounds are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 C atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,

C.sub.2-C.sub.22-fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,

C8-C ₂ 2-alkyl mono- and oligoglycosides and their ethoxylated analogs and

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

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

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

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

Particular preference is given to those alkylpolyglycosides in which R ¹ consists essentially of C 1 - and C -alkyl groups, essentially of C 1 - and C ¹ -alkyl groups, essentially of C ₈ - to C ₆ -alkyl groups or essentially of C _n - to C ₆ - Alkyl groups. As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. , Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1.1 to 1.4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an action of the Parrumöl on the hair beyond the duration of the hair treatment is desired.

The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds are distinguished be¬, a -COO ^ in the molecule at least one quaternary ammonium group and at least - or -Sθ ₃ ^{( "-).} Wearing group Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl Iridazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine. Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which contain, in addition to a C 1 -C 6 -alkyl or acyl group in the molecule, at least one free arrino group and at least one -COOH or -SO ₃ H group and which makes it possible to form internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C] _2- 18 acyl sarcosine.

According to the invention, the cationic surfactants used may in particular be those of the type of the quaternary ammonium compounds, the esterquats and the amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the brands Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare® ^® VGH-70, an N, N-bis (2-Palmitoyloxy- ethyl) dimethyl ammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A erfm- dung as particularly suitable compound from this group of substances that available under the brand Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine. Further inventively usable cationic surfactants are the quaternized protein hydrolysates.

Also suitable in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodine ethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80.).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, it is possible to use both products having a "normal" homolog distribution and those having a narrowed homolog distribution. By "normal" homolog distribution are meant mixtures of homologues which are used in the reaction of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates obtained as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with narrow homolog distribution may be preferred.

Furthermore, colorants according to the invention may contain further active compounds, auxiliaries and additives such as, for example, nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups Dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate-quaternized dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate Copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid Copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol, Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates, parrum oils, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-l-alkylamidoethyl -2-alkylimidazolinium methosulfate

Defoamers such as silicones, dyes for coloring the agent,

Antidandruff active ingredients such as Piroctone oil amines, zinc Omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,

Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat , Kiwi, melon, orange. Grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm. Toadstool, coltsfoot, marshmallow. Meristem, ginseng and ginger root ,. - cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

Fatty acid alkanolamides,

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phospho-acids,

- swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,

- pigments,

Stabilizing agent for Wassserstoffperoxid and other oxidizing agents, _r propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, _CO2 and air,

Antioxidants, included.

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, Basics and Formulations of Cosmetics, j2. Edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

The agents according to the invention preferably contain the dye precursors in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the dye precursors into a powdery or tablet-like formulation.

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

The actual oxidative dyeing of the fibers can be carried out in principle with atmospheric oxygen. However, preference is given to using a chemical oxidizing agent, especially if, in addition to the dyeing, a lightening effect on human hair is desired. Suitable oxidizing agents are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate. However, according to the invention, the oxidation colorant can also be applied to the hair together with a catalyst which promotes the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

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

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

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

Glucose oxidase and D-glucose,

Glycerol oxidase and glycerin. Pyruvate oxidase and pyruvic acid or its salts, alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and its salts, tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and Amino acids.

The actual hair dye is expediently prepared immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range from 6 to 12. Particularly preferred is the use of the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After a contact time of usually 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is omitted if a strong surfactant-containing carrier, e.g. a dyeing shampoo was used.

In particular, with hair that is difficult to dye, the preparation with the dye precursors may also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the product is then rinsed and, if desired, shampooed again. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to effect a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent. A third object of the present invention is a process for dyeing keratinic fibers, in particular human hair, in which a hair colorant according to the invention is applied to the fibers and rinsed off again after a contact time.

The invention is further illustrated by the following examples.

B e i s p e e l e

To prepare the following recipe examples, these substantive dyes were used:

N-N'-bis (2-hydroxyethyl) -2-nitro-1,4-phenylenediamine Violet 1,4 D

2-Amino-6-chloro-4-nitrophenol Rodol 9R Base

N '- (2-hydroxyethyl) amino-2-nitro-4-aminobenzene HC Red 3 l- (2-hydroxyethylamino) -2-nitrobenzene HC Yellow 2

2 - [(2-Amino-4-nitrophenyl) amino] -ethanol HC Yellow 5

4-amino-2-nitrodiphenylamine HC Red 1

2-nitro-4'-hydroxydiphenylamine HC Orange 1

N ₅ N, N'-tris (2-hydroxyethyl) -2 -nitro- 1, 4-phenylenediamine HC Blue 2

4 - [(3-hydroxypropyl) amino] -3-nitrophenol HC Red BN

4 - [(2-hydroxyethyl) amino] -3-nitrophenol HC Red B 54

(4-Methylamino-1-naphthyl) bis- (4-diethylaminophenyl) -carbenium chloride Basic Blue 7

3 - [(4-Amino-6-bromo-5,8-dihydro-l-hydroxy-8-imino-5-oxo-

2-naphthyl) amino] -1- [N, N, N-trimethylammonio] benzene chloride Basic Blue 99

[8 - [(4-aminophenyl) azo] -7-hydroxy-2-naphthyl] trimethyl ammonium chloride Basic Brown 16

[8 - [(4-Amino-3-nitrophenyl) azo] -7-hydroxy-2-naphthyl] trimethylammonium chloride Basic Brown 17 l-Methyl-4 - [(methylphenylhydrazono) methyl] -pyridinium methylsulfate Basic Yellow

87

2 - [(4-Aminophenyl) azo] -1,3-dimethyl-1H-imidazolium chloride Basic Orange

31

2- (4-dimethylamino-phenylazo) -l, 3-dimethyl-3H-imidazol-l-ium-

Chloride Basic Red 51

[7-Hydroxy-8 - [(2-methoxyphenyl) azo] -2-naphthyl] trimethyl ammonium chloride Basic Red 76

3 - [(4,5-dihydro-3-methyl-5-oxo-l-phenyl-lH-pyrazol-4-yl) azo] - l- [N ₅ N ₅ N-trimethylammonio] benzene chloride Basic Yellow

57

(4-Amino-3-methylphenyl) bis- (4-aminophenyl) -carbenium chloride Basic Violet 14

4 - [(2-Hydroxy-1-naphthyl) azo] benzenesulfonic acid sodium Salt Acid Orange 7

Naphthalene-2,7-Disulfonic Acid Sodium Salt Acid Black 1

2 - [(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl) -amino] -5-methyl-benzenesulfonic acid sodium Salt Acid Violet 43

5-amino-4-hydroxy-3- (phenylazo) naphthalene-2,7-disulfonic acid

Sodium Salt Acid Red 33

3.6-Bis- (diethylamino) -9- (2,4-disulfophenyl) -xanthylimide sodium, inner salt Acid R.ed 52

The following raw materials were used to prepare the following recipe examples:

Texapon ^® NSO Sodium Lauryl Sulfate (INCI: Sodium Lauryl Sulfate)

(Cognis Germany)

Lorol® ^® techn. Ci ₂ -Ci8 fatty alcohol (INCI name: Coconut

Alcohol) (Cognis Germany)

Polychol ^® 5 lanolin alcohol with 5 EO units (INCI)

Name: Laneth-5) (Croda)

Eumulgin ^® Bl cetylstearyl alcohol with 12 EO units (INCI

Name: Ceteareth-12) (Cognis Germany)

Eumulgin ^® B2 Cetylstearylalkohol with about 20 EO units (INCI

Designation: Ceteareth-20)

Eumulgin ^® RO 40 ethoxylated castor oil (INCI name: PEG-40

Castor OiI) (Cognis Germany)

Stenol ^® 1618 _{C) 6-} i8 fatty alcohol (INCI name: Cetearyl

Alcohol) (Cognis Germany)

Dehydol ^® 100 (INCI name: Laureth-10) (Cognis

Germany) Akypo ^® RLM 45 N ca. 82% active substance (INCI name: Sodium Laureth-5 Carboxylate) (KAO) Dehyton ^® K NJN-dimethyl-N-CCG-Cig-cocamidopropyl) - ammoniumacetobetain (ca. 30% active substance; INCI Designation: Aqua (Water), Gocamidopropyl Betaine) (Cognis Germany),, '

Amine oxide WS 35 N, N-dimethyl-N (C ₈ -i ₈ -coco-sacyl-amidopropyl) ami> N-oxide, 35% active substance (INCI name: Cocamidopropylamine Oxide) (Goldschmidt)

Dehyquart ^® A trimethylhexadecylammonium chloride, approx. 27% active ingredient (INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis Germany)

Dehyquart® ^® F 75 fatty alcohol Methyltriethanolammoniummethylsulfat- dialkyl mixture (INCI name: distearoyl ethyl Hydroxyethylmonium methosulfate, Cetearyl Alcohol) (Cognis Germany)

Dow Corning 345 EU ^® decamethylcyclopentasiloxane (INCI name: Cyclomethicone) (Dow Corning) Lipoxol ^® 400 MED polyethylene glycol (INCI name: PEG-8) (Sasol) Nutrilan ^® Keratin W enzymatically derived hydrolyzate merino wool (INCI name: Aqua ( Water), Hydrolyzed Keratin, Phenoxyethanol, Methalparaben, Butylparaben, Ethylparaben, Propylparaben) (Cognis Germany)

AMinor A 15 C _13-15 -Alkylethercarboxylatmonoethanolamid (INCI name: Trideceth-2 Carboxamide MEA) (KAO)

Phenonip * ¹ about 27% active ingredient, (INCI name: phenoxyethanol, methylparaben, ethylparaben, propylparaben, butylparaben) (Clariant)

AMP 95 2-amino-2-methylpropanol (Dow) Carbopol ^® ETD 2001 polyacrylic acid (INCI name: Carbomer) (Noveon) Aculyn ^® 22 (INCI name: Acrylates / Steareth-20

Methacrylate Copolymer) (Rohm & Haas) Aculyn ^® 33 (INCI name: Acrylates Copolymer) (Rohm & Haas) Merquat ^® 280 dimethyldiallylammonium chloride-acrylic acid copolymer (INCI name: Polyquaternium-22) (Nalco)

Merquat ^® 100 poly (dimethyldiallylammonium chloride) (INCI

Designation: Polyquaternium-6) (Nalco) Natrosol ^® 250 HR hydroxyethyl cellulose (INCI name:

Hydroxyethyl cellulose) (Hercules) Polymer JR 400 ^{Φ ■} quaternized hydroxyethyl cellulose (INCI

Designation: Polyquaternium-10) (Amerchol) Mirapol ^® A 15 Poly [N- (3- (dimethylammonium) propyl] -N '- [3- ethyleneoxyethylene-dimethylammonium) propyl] - urea dichloride (INCI name:

Polyquaternium-2) (Rhodia)

Luviskof K30 polyvinylpyrrolidone (INCI name: PVP) (BASF)

Geliderm ^® 3000 P coconut fatty acid collagen hydrolyzate sodium salt

(INCI name: Sodium Cocoyl Hydrolyzed Collagen) (DGF German Gelatine Factories Stoess)

Tegoami <f © S 18 N _s N-Dimethyl-N'-stearoyl-1,3-diaminopropane (INCI name: Stearamidopropyl Dimethylamine) (Degussa)

Gluadin ^ AGP KL wheat protein hydrolyzate (INCI name:

Hydrolyzed Wheat Protein) (Cognis Germany) Henna neutral Cassia auriculata, leaves dried and ground. (INCI name: Cassia Auriculata (Linne) Cassia Auriculata Leaf Powder) (Paul Müggenburg GmbH)

Henna red Lawsonia inermis, leaves dried and ground, coloring ingredient 2-Hydroxy-l, 4-naphthoquinone (INCI name: Lawsonia Inermis (Linne) Henna Extract) (Paul Müggenburg GmbH)

Kukui Nut Oil (INCI name: Kukui Nut OiI Aleurites Moluccana (Linne)) (Worlee)

Silkair 100 silk protein (INCI name: SiIk Serica (Linne)) (Ikeda Bussan Kaisha)

Turpinal SL ^® 1-hydroxyethane 1, 1 diphosphonic acid (INCI

Name: Etidronic Acid, Aqua (Water)) (Solutia)

Sodium water glass 40/42 sodium silicate (Cognis Germany)

foam tint

The following foam toning agents according to Table 1 were prepared and formulated in a pressure-release container with a propane-butane mixture as blowing agent.

Table 1

2 g of a foam tint according to Table 1 were each left for 0.5 g of human hair strand (Kerling, Natunveiß) over a period of 20 minutes. The hair was then rinsed and dried. The strands of hair were dyed as follows:

Recipe No. Color

1 brownish copper

2 reddish copper toning lotion

The following tint lotions according to Tables 2 and 3 were prepared:

Table 2

Continuation Table 2

Table 3

2.0 g of a tinting lotion according to Table 2 or 3 was left for 0.5 g each human hair strand (Kerling, natural white) over a period of 20 minutes. The hair was then rinsed and dried. The strands of hair were dyed as follows:

Recipe No. Color

3 garnet red

4 dark red

5 warm browns

6 bright red

color conditioner

The following color conditioners according to Table 4 were prepared:

Table 4

Continuation Table 4

2.0 g of a color conditioner according to Table 4 were each left for 0.5 g of human hair strands (Kerling, natural white) over a period of 20 minutes. The hair was then rinsed and dried. The strands of hair had a full feel and a silky sheen and were dyed as follows:

Recipe No. Color

7 bright violet

8 honey colors

9 bright red Powder Hair Color

Powder hair colors are prepared in the form of a fine powder (sieve fraction 0.05-1.0 nm) according to Table 5:

Table 5

Continuation Table 5

For each coloration, 25 g of a powder according to Table 5 were mixed with 60 ml of hot water. After the resulting dye mixture had cooled to a temperature of 40 ° C., 2.0 g of the dye mixture were applied to 0.5 g of a human hair strand (Kerling, natural white) and rinsed off again after a contact time of 30 minutes. The strands dyed with the dye mixtures according to Table 5 were dried and obtained the following colorations:

Recipe No. Color

10 sandalwood colors

1 1 intense violet

Oxidation hair

The following coloring creams are prepared according to Table 6:

Table 6: Dyeing creams

Continuation Table 6

Table 7: Oxidizing agent preparation

Shortly before use, a coloring cream according to Table 6 was mixed with the oxidizing agent preparation according to Table 7 in a weight ratio of 1: 1. X g of this mixture was left on Y g of a human hair strand (Kerling natural white) for 30 minutes at 32 ° C on the hair and then rinsed. The strand of hair was dried and the color result was assessed.

Nuance No. Color

12 intense red

13 intense violet

14 intense copper

Claims

claims

1. Use of cationic azo compounds of the general formula (I)

with the meaning

XO, S

YN ₅ CR ⁵ ,

R ¹ H H., H HaiIloogen, NO ₂ , C ₆ .i ₂ -aryl, C ₇ . ₁₃ -Aralkyl, C ₇ , ₃ -Alkaryl, C ,. ₆ - alkyl, which are optionally substituted by:

-OH, halogen, -CN, -NO _2, OH, optionally substituted Ci _-4 - alkoxy, -NH _2, -NHR, -NR ₂ are each independently optionally substituted with R OH-substituted Ci _-4 alkyl,

R ^{3 is} C ₆ .i ₂ -aryl, C _7. .I3-aralkyl or C _7-13 -alkaryl, which are optionally substituted by:

-OH, halogen, -CN, -NO _2, optionally OH-substituted Ci _-4 - alkoxy, -NH _2, -NHR, -NR _2, where R are each independently optionally OH-substituted C _"4 alkyl,

R ^2, R ^4, R ⁵ are independently H, Ci _-6 alkyl, Ci _-6 hydroxyalkyl, C _2-6 - Alkoxyalky] Ci. _δ -Aminoalky], C ₂ -jo-alkylaminoalkyl. C _3-12 - dialkylaminoalkyl, C ₆ .i ₂ aryl, C _7- C i ₃ or aralkyl. _{7 ] 3} -karyari. as a direct dye for dyeing human hair.

2. Use according to claim 1, characterized in that in the azo compounds of the general formula (I) R ³ C ₆ .i2-Aryl.

3. Use according to claim 1 or 2, characterized in that in the azo compounds of the general formula (I) R ^{1 is} hydrogen or C | _-4 alkyl.

4. Use according to one of claims 1 to 3, characterized in that in the azo compounds of the general formula (I) Y is CR ⁵ with R ^{5 is} hydrogen or Ci-4-alkyl.

5. Use according to one of claims 1 to 4, characterized in that in the azo compounds of the general formula (I) R ² and R ^{4 is} C- _M- alkyl.

6. means for coloring human hair, contained in a cosmetically acceptable _. Carrier as substantive dye at least one cationic azo compound of the general formula (I) as defined in any one of claims 1 to 5.

7. Use of cationic azo compounds of the general formula (Ia)

with the meaning XO, S

YN, CR ⁵ ,

R ^{1 is} H, halogen, NO ₂ , C ₆ .i ₂ -aryl, C ₇ -... _3- aralkyl, C ₇ -ion- _3- alkaryl, C) _-6 -

Alkyl, which are optionally substituted by:

-OH, halogen, -CN, -NO _2, optionally OH-substituted Ci _-4 - alkoxy, -NH _2, -NHR, -NR ² are each independently optionally substituted with R OH-substituted Cm-alkyl,

R ³ H, Ci. _6- alkyl, C ,. ₆ hydroxyalkyl, C ₂ - ₆ alkoxyalkyl, Cu ₆ -

Aminoalkyl, C _{2, 0} -alkylaminoalkyl, C ₃ -i ₂ -dialkylaminoalkyl, CO-I ₂ -aryl, C _{7, 3-} aralkyl, or C ₇ -i ₃ -alkaryl, which are optionally substituted by:

-OH, halogen, -CN, -NO _2, optionally OH-substituted CM-alkoxy, -NH _2, -NHR, -NR ^2, where R are each independently optionally OH-substituted Ci- ₄ alkyl,

R ² , R ⁴ , R ^{5 are} independently -H, Ci. _6- alkyl, C |. ₆ hydroxyalkyl, C _2-6 - alkoxyalkyl, _{Ci-6-aminoalkyl,} C i _{0 2-} alkylaminoalkyl, _C3-I2 - dialkylaminoalkyl, C ₆ -i ₂ aryl, C ₇ .i ₃ -aralkyl or C ₇ .i ₃ -alkaryl,

as a direct dye in oxidative dyeing agents for keratinous fibers, especially human hair.

8. Use according to claim 7, characterized in that means _6- i ₂ aryl in the azo compounds of the general formula (Ia) R ³ C.

9. Use according to claim 7 or 8, characterized in that in the azo compounds of the general formula (Ia) R ^{1 is} hydrogen or C]. ₄ alkyl.

10. Use according to one of claims 7 to 9, characterized in that in the azo compounds of the general formula (Ia) Y CR ⁵ with R ^{5 is} hydrogen, Ci. ₄ alkyl.

11. Use according to any one of claims 7 to 10, characterized in that in the azo compounds of the general formula (Ia) R ² and R ^{4 is} Ci- ₄ alkyl.

12. A composition for the oxidative dyeing of keratinic fibers, in particular human hair, comprising in a cosmetically acceptable carrier at least one oxidation dye precursor and at least one cationic azo compound of the general formula (Ia) as defined in any one of claims 7 to 11.

13. Composition according to claim 12, characterized in that it contains at least one developer component and at least one coupler component.

14. Composition according to claim 12 or 13, characterized in that as developer components primary aromatic amines having a further, located in the para or ortho position, free or substituted hydroxy or amino group. Diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, 2,4,5,6-tetraaminopyrimidine and its derivatives and mixtures thereof can be used.

15. Composition according to one of claims 12 to 14, characterized in that m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols and mixtures thereof are used as the coupler components.

16. A method for dyeing human hair, wherein an agent according to claim 6 is applied to the hair and rinsed again after a contact time.

17. A process for dyeing keratinous fibers, wherein an agent according to any one of claims 12 to 15 is applied to the fibers and rinsed again after a contact time.