WO2007051504A1

WO2007051504A1 - Composition for colouring keratin-containing fibres

Info

Publication number: WO2007051504A1
Application number: PCT/EP2006/008766
Authority: WO
Inventors: Georg KNÜBEL; Wolfgang Benicke; Horst Höffkes
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2005-11-03
Filing date: 2006-09-08
Publication date: 2007-05-10
Also published as: DE102005052912A1

Abstract

Composition for the colouring of keratin fibres, in particular human hair, comprising, in a cosmetically acceptable carrier, at least one direct dye of the formula (I), where X is halogen, Ak is C1- to C4-alkylene or C1- to C4-monohydroxyalkylene, R1, R2, R5 and R6 are in each case independently of one another hydrogen, halogen or a branched or unbranched C1- to C4-alkyl group and R3 and R4 are in each case independently of one another hydrogen, a branched or unbranched C1- to C4-alkyl group, a methoxy or ethoxy group, a group R‘R‘‘N-, in which R‘ and R‘‘ independently of one another are a hydrogen atom, a C1-C4-alkyl group, a C1-C4-hydroxyalkyl group or a C2-C4-dihydroxyalkyl group, or are an amide radical, use of corresponding compositions for colouring keratin fibres and a method for colouring keratin fibres by applying such a composition to the fibres to be coloured, and a specific compound of the formula (I).

Description

"Agent for dyeing keratinous fibers"

The present invention relates to agents for coloring keratinic fibers containing specific bis (hydroxyalkyl) amino-substituted azo dyes and a process for dyeing hair using these agents.

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 the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components.

Good oxidation dye precursors are primarily intended to meet the following requirements: They must form the desired color shades in sufficient intensity and authenticity in the oxidative coupling. You must also have a good Aufziehvermögen on the fiber, especially in human hair no significant differences between strained and freshly regrowed hair may exist (leveling ability). 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 have a natural color shade on the hair receive. In practice, therefore, combinations of different developer and / or coupler components are usually used.

For further nuancing direct dyes are added. These are also called direct pullers. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair. In the event that only temporary dyeing is desired, dyeing or tinting agents which contain direct dyes without the addition of oxidation dyes as the coloring component are the means of choice. Again, a natural color shade can often only be obtained if colorants are used which contain various substantive dyes.

Some of the known substantive dyes, on their own or in combination with other dyes or components commonly added to hair dyes, may sometimes be sensitizing in persons with sensitive skin.

There is therefore a constant need for new, improved dye components which allow the realization of the widest possible color spectrum and are also unproblematic in terms of toxicology and dermatology.

An important class of substantive dyes are the so-called azo dyes. This group of dyes comprises a greater number of compounds than all other classes of dyes together. The field of application of these azo dyes is also far. The use for textile or paper dyeing is also known, as is the use for dyeing human hair. Of course, not every known azo dye is of course suitable for every dyeing purpose. The dyes must be stable under the respective dyeing conditions, give the desired dyeing result, can be incorporated into suitable formulations and meet different toxicological conditions.

US-A 5,593,459 discloses dyeing textile fibers with basic, disperse or soluble dyes wherein sufficient anionic surfactant is added to the dyeing composition and the pH is adjusted to dissolve and release the dye is protonated. Corresponding dyeing compositions are also suitable, inter alia, for dyeing human hair. Suitable disperse dyes generally describe azo dyes which can have a wide variety of different substitution patterns. The general formula 1 includes, inter alia, bis (hydroxyalkyl) amino-substituted azo dyes, which may include, among others, nitro and halo substituents. An indication that certain azo dyes would be particularly suitable for dyeing keratinous fibers, however, is not found. In addition, the dyes are used exclusively in protonated form.

The object of the present invention was to provide new agents for dyeing keratinic fibers based on direct-acting azo dyes, wherein the dyes used should meet the necessary requirements, in particular with regard to the toxicological and dermatological properties, and should allow dyeings in a broad color spectrum with good fastness properties ,

It has now been found that special bis (hydroxyalkyl) amino-substituted azo dyes, which additionally have a nitro and at least one halogen substituent, meet the stated requirements to a high degree and are therefore excellently suitable as substantive dyes in hair dyes.

A first subject of the present invention are therefore agents for dyeing keratinic fibers, in particular human hair, containing in a cosmetically acceptable carrier at least one substantive dye of the formula (I),

in which

- X stands for halogen,

- Ak is C ₁ - to C ₄ -alkylene or C ₁ - to C ₄ -monohydroxyalkylene, - R ¹ , R ² , R ⁵ and R ⁶ are each independently hydrogen, halogen or a branched or unbranched Ci to C ₄ alkyl group and

- R ³ and R ⁴ are each independently hydrogen, a branched or unbranched C _r to C ₄ alkyl group, a methoxy or ethoxy group, a group R ¹ R ¹¹ N-, wherein R ¹ and R "independently of one another atom is hydrogen, a Ci-C ₄ alkyl group, a hydroxyalkyl group, or a ₄ dC C ₂ -C ₄ - dihydroxyalkyl stand, or a group of formula (II)

wherein R ^{7 is} a CrC ₄ alkyl group.

According to the invention, keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the colorants 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.

In the following, examples of the groups or radicals mentioned as substituents in the context of this application will be mentioned. Examples of halogen are fluorine, chlorine and bromine, with chlorine being preferred. Examples of C _r C ₄ -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. Examples of corresponding C 1 -C ₄ -alkylene radicals are methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene and tert-butylene. As examples of a Ci-C ₄ -hydroxyalkyl group hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and 4-hydroxybutyl can be mentioned. Examples of a C ₂ -C ₄ -dihydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group.

The direct-acting dye of the formula (I) is preferably those compounds in which X is chlorine. Furthermore, preference is given to those substantive dyes of the formula (I) in which Ak is methylene or ethylene, preferably ethylene, and / or in which R ¹ , R ² , R ⁵ and R ^{6 are} each hydrogen.

R ³ and R ⁴ are each independently of one another hydrogen, methyl, ethyl, methoxy, ethoxy or a group of the formula (II) where R ^{7 is} methyl.

Particular preference is given to using those substantive dyes in which all substituents have the preferred meanings just mentioned.

The hair colorants according to the invention contain the direct dye (s) of the formula (I) preferably in an amount of 0.005 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total colorant.

The substantive dyes of the formula (I) can be prepared by conventional organic methods and are partially commercially available. Thus, for example, 2-chloro-4-nitroaniline can be converted under acidic conditions at low temperatures with sodium nitrite into the corresponding diazonium salt and then reacted with a bis (hydroxyalkyl) amino-substituted aromatic.

In addition to the substantive dyes of the formula (I), the agents according to the invention preferably also contain one or more further substantive dyes of a different structure. By suitable combination of different substantive dyes a variety of different shades can be achieved. The staining result can be specifically adjusted so that a very natural or a fashionable, artificially acting color of the hair is obtained.

Suitable further substantive dyes are, for example, nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. 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 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, and 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis- (ß- hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4 methyl 2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-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.

Furthermore, the agents according to the invention can contain, as further direct drawers, a cationic substantive dye. Particularly preferred are

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

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

(C) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned for example in EP-A2-998 908, which is explicitly referred to 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 (DZ1), (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 trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct dyes.

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

The other substantive dyes are preferably added to the hair colorant according to the invention in an amount such that the total amount of substantive dye, ie the total amount of substantive dyes of the Formula (I) and other substantive dyes, 0.1 to 20 wt .-%, preferably 0.1 to 5 wt .-%, each based on the total colorant.

In a particular embodiment of the invention, the colorants further contain at least one oxidation dye precursor. In this embodiment, the agent according to the invention contains at least one developer component and optionally additionally at least one coupler 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-aminopyrazole 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 tolerable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (E 1)

in which

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

G ² is an atom of hydrogen, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy (C ₁ - to C ₄ ) -alkyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl, C ₁ to C ₄ hydroxyalkoxy, C ₁ to C ₄ acetylaminoalkoxy, C ₁ to C ₄ mesylaminoalkoxy or C ₁ to C ₄ carbamoylaminoalkoxy;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to one another, they may together have a bridging α, ω-alkylenedioxo group, for example a To form ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the developer components are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, 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 according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are especially the amino groups, C ₁ - to C ₄ monoalkylamino, C ₁ - to C ₄ dialkylamino group, C ₁ - to C ₄ -Trialkylammoniumgruppen, C ₁ - to C ₄ - Monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine , 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, _1- dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxy-ethyl) -p-phenylenediamine, 4-N, N-bis (β-hydroxyethyl) -arnino 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-acetylamino-ethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino 3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, N- ( 4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine 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, are a hydroxyl or NH ₂ radical, which, by a C ₁ is optionally substituted by a Ci to _C4 alkyl group - is substituted to C ₄ -hydroxyalkyl radical and / or by a bridge Y, or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, of one or more nitrogen-containing groups and / or one or more Heteroatoms such as oxygen, sulfur or nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or C ₁ - to C ₈ - alkoxy, 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 -hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that the compounds of the formula (E2) contain only one bridging Y per molecule and - the compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

Preferred bimanric developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-diethyl-N, N'-bis (4 ¹ -amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propane-2 ol, N, N ^l-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.

Particularly preferred double bases of formula (E2) are N ₁ N ¹ - bis (.beta.-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol, bis - (2-hydroxy-5-aminophenyl) -methane, 1, 3-bis- (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1 , 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecan or one of its physiologically acceptable salts. Bis (2-hydroxy-5-aminophenyl) methane is a most preferred dinuclear developing agent of formula (E2).

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 C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy -, (Cr to _C4) alkyl is a C ₁ - to C ₄ aminoalkyl radical, a hydroxy (Cr to _C4) alkylamino group, a d- to _C4 -Hydroxyalkoxyrest, a C ₁ - to C ₄ hydroxy - alkyl (C _r to C ₄ ) aminoalkyl or a (di-C ₁ - to C ₄ alkylamino) - (C ₁ - to C ₄ ) - alkyl radical, and

G ¹⁴ is a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ -j- AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ - cyanoalkyl radical,

G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -mono-hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and

G ¹⁶ is hydrogen or a halogen atom.

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

Preferred p-aminophenols of the formula (E3) are in particular p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxy-methylamino-4-aminophenol , 4-amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxy ethoxy) -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-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino -2- (diethylaminomethyl) phenol and their physiologically acceptable salts.

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 developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

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

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

Preferred pyrazole derivatives are, in particular, the compounds described in 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-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4.5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-i-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl 4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino 1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-i-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-isopropyl-pyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3.5 Diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

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

in which:

G ^17, G ^18, G ¹⁹ and G ²⁰ are independently a hydrogen atom, a d- to _C4-alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ Polyhydroxyalkyl radical is 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 (d- to C ₄₎ alkylamino (C ₁ - to C ₄₎ alkyl, a di - [(C _r to C ₄₎ alkyl] - (C _r to C ₄₎ aminoalkyl, wherein the dialkyl Optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C _r to C ₄ ) - aminoalkyl, the X radicals are independently an Wasserst offatom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a (C ₁ -, alkyl to C ₄₎ a Di - - to C ₄₎ alkylamino (C ₁ to C ₄ aminoalkyl), wherein the dialkyl residues optionally - [(C _r to C ₄₎ alkyl] - (C ₁ form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ - hydroxyalkyl) -aminoalkyl radical, an amino radical, a C ₁ - to C ₄ - Alkyl or di- (C ₁ to C ₄ -hydroxyalkyl) -amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value O, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0 when p + q is 2, n is 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

When the pyrazole [1,5-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 shown, for example, in the following scheme:

Among the pyrazolo [1, 5-a] -pyrimidines of the above formula (E4) may be mentioned in particular:

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

2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;

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

2,7-dimethyl-pyrazolo [1,5-a] -pyrimidine-3,5-diamine;

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

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

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

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

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

5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1, 5-a] -pyrimidine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

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

The compositions according to the invention for dyeing keratinic fibers may contain not only a developer component but also at least one coupler component. In this way, the color spectrum, which can be achieved with the colorants according to the invention, expand again.

As the coupler components, for example, m-phenylenediamine derivatives, naphthols, resorcin and resorcinol derivatives, pyrazolones and m-aminophenol derivatives can be used. Suitable coupler substances are in particular 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinomonomethylether, 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.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, 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 ', 4'-diaminophenoxy) -propane, 1-methoxy-2-amino-4- (2'-hydroxybenzene) ethylamino) benzene, 1,3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis- (2'-hydroxyethyl-amino) -1-methylbenzene, 2 - ({3 - [(2 -Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} - amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2- ( {3 - [(2-Hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5 -methylphenylamine 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,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine , 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy 4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2- Hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3- dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxy-pyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4 -hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or

Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene and their physiologically acceptable salts. Particularly preferred 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-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 2- ({3 - [(2 -Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-

Hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol and 2 - [(3-morpholino -4-yl-phenyl) amino] ethanol.

The hair colorants of this embodiment of the invention preferably contain both the developer components and the coupler components in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, based in each case on the entire colorant. In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proved to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1 : 2, may be included.

In addition to the abovementioned components, the colorants according to the invention may contain at least one precursor of a naturally-analogous dye. Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of naturally-analogous dyes. These groups may carry further substituents, e.g. Example in the form of 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 and / or indoline derivative.

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

in the independently of each other

G ₁₉ is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

G _2O is hydrogen or a -COOH group, where the -COOH group may also be in the form of a salt with a physiologically compatible cation,

G ₂₁ is hydrogen or a C 1 -C ₄ -alkyl group,

- G ₂₂ stands for hydrogen, a CrC ₄ alkyl group or a group -CO-G ₂₄ wherein G ₂₄ represents a C _r C ₄ alkyl group, and

- G ₂₃ is one of the groups mentioned under G ₂₂ , and 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-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

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

in the independently of each other

G ₂₅ is hydrogen, a C _r C ₄ alkyl group or a CrCrHydroxyalkylgruppe,

G ₂₆ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

G ₂₇ is hydrogen or a C 1 -C ₄ -alkyl group,

- G ₂₈ is hydrogen, a dC ^ alkyl group or a group -CO-G ₃₀ , in which G ₃₀ is a Ci-C ₄ alkyl group, and

- G ₂₉ is one of the groups mentioned under G ₂₈ , 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 especially the 5,6 -Dihydroxyindol.

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 inorganic or organic acids, for. As the hydrochlorides, the sulfates and hydrobromides, are used. 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. It is not necessary for the stated dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the hair dyeing compositions according to the invention, due to the production process for the individual dyes, minor amounts may contain other components, as far as they do not adversely affect the coloring result or 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, as well as the "European Inventory of Cosmetic Raw Materials", Issued 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 registered association, Mannheim, reference is made.

The colorants according to the invention may furthermore contain all active ingredients, additives and auxiliaries customary 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 anionic, 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 the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps ) 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 carbon atoms and x = O or 1 to 16, acylsarcosides having 10 to 18 C Atoms in the acyl group, acyl taurides having 10 to 18 carbon atoms in the acyl group, acyl isethionates having 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester with 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 having 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,

Blends 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 adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C 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 ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Nonionic surfactants contain as hydrophilic group z. For example, a polyol group, a polyalkylene glycol ether 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 1 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group, C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 mol

Ethylene oxide with glycerine,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs and

Addition products of 5 to 60 moles of ethylene oxide with castor oil and 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 using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

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

And C ₁₀ alkyl groups, mainly of C ₁₂ - - and C ₄ alkyl groups, essentially of C ₈ - to C ₆ -alkyl or C consisting essentially of alkyl polyglycosides are those in which R 'is essentially of C ₈ are particularly preferred ₁₂ - to C ₁₆ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding 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 ingredient of the preparations according to the invention in the event that an effect of a perfume oil on the hair which exceeds 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 those surface-active compounds which carry in the molecule at least one quaternary ammonium group and at least one -COO ^H or -SO ₃ ^ -G group. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinates, for example cocoacylaminopropyldimethylammoniumglycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethyl- hydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytes. Ampholytes are surface-active compounds which, apart from a C ₈ -C ₈ - alkyl or acyl group containing in the molecule at least one free amino group and at least one -COOH or _-SO3H group and are capable of forming inner salts. Examples of suitable ampholytes are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidoproylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Especially preferred ampholytes are N-cocoalkylaminopropionate, cocoacylaminoethyl-aminopropionate and

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, 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. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl ammonium chloride, Lauryldimethylbenzylammoniumchlorid and Tricetylmethylammonium- chloride, as well as known under the INCI names Quaternium-27 and Quaternium-83 imidazolium compounds. 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 a 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 trade names Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-ethyl Palmitoyloxy-) dimethylamrnoniumchlorid, 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. An inventively particularly suitable compound from this group of substances that available under the name Tegoamid ^® S 18 commercially stearamidopropyl di- represents methylamine.

Further cationic surfactants which can be used according to the invention 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 trimethylsilylamodimethicone), 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 Quatemium- 80).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl GIu- Ceth-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, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates 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 is preferred.

Furthermore, the colorants according to the invention may contain further active ingredients, auxiliaries and additives, for example nonionic polymers such as, for example, 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-dimethyldiallylammonium chloride copolymers, dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinylalcohol .

zwitterionic and amphoteric polymers, for example acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate / tert-butylaminoethylmethacrylamide hydroxypropyl methacrylate copolymers, anionic polymers, 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 arabicum, karaya gum, locust bean gum, linseed gums, dextrans, celulose derivatives, e.g. For example, methyl cellulose, hydroxyalkyl cellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. Bentonite or fully synthetic hydrocolloids such as e.g. Polyvinyl alcohol, structurants such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

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

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

fiber-structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate defoamers such as silicones,

Dyes for staining the agent,

Antidandruff active ingredients such as Piroctone Olamine, 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 also bisabolol, vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, Orange, Grapefruit, Sage, Rosemary, Birch, Mallow, Meadowfoam, Quendel, Yarrow, Thyme, Melissa, Hominy, Coltsfoot, Marshmallow, Meristem, Ginseng and Ginger root, Cholesterol,

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

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

Stabilizers for hydrogen peroxide and other oxidizing agents, propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air, antioxidants.

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, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

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

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

On the presence of oxidizing agents, for. B. H ₂ O ₂ , can be dispensed with, especially if the agent according to the invention contains no oxidation dye precursors. Even if the agent according to the invention contains oxidizable oxidation dye precursors or indole or indoline derivatives in air, oxidizing agents can be dispensed with without problems in such a case. However, it may u. It may be desirable to add hydrogen peroxide or other oxidizing agents to the compositions of the invention for achieving the shades that are lighter than the keratin-containing fiber to be dyed. Oxidizing agents are generally used in an amount of 0.01 to 6% by weight, based on the application solution. A preferred oxidizing agent for human hair is H ₂ O ₂ . Mixtures of several oxidizing agents, such as a combination of hydrogen peroxide and peroxodisulfates of the alkali and alkaline earth metals or from iodide ion sources, such as alkali metal iodides and hydrogen peroxide or the aforementioned peroxodisulfates, can be used. The oxidizing agent or the oxidizing agent combination can be used according to the invention in conjunction with oxidation catalysts in the hair dye. Oxidation catalysts are, for example, metal salts, metal chelate complexes or metal oxides, which allow a slight change between two oxidation states of the metal ions. Examples are salts, chelate complexes or oxides of iron, ruthenium, manganese and copper. Other possible oxidation catalysts are enzymes. Examples of suitable enzymes are peroxidases, which can markedly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention, which with the help of atmospheric oxygen the Oxidation dye precursors directly oxidize, such as the laccases, or generate in situ small amounts of hydrogen peroxide 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 oxido reductases in combination with the specific substrates, eg

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 their salts,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or their salts,

- choline oxidase and choline,

- amino acid oxidase and amino acids.

In a particular embodiment of the present invention, the agent for dyeing keratin-containing fibers therefore contains at least one oxidizing agent, in particular H ₂ O ₂ , preferably in an amount of from 0.01 to 6% by weight, based on the total agent.

In the event that the agent of the invention contains an oxidizing agent and dye precursors, the actual hair dye is conveniently prepared immediately prior to 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 of 6 to 12. Unless explicitly stated otherwise, the pH values given in this document are to be understood as the pH values at 25 ° C. Particularly preferred is the use of the hair dye in a weakly alkaline medium. The application temperatures can be in a range between 15 and 40 ⁰ C. After a contact time of 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, such as a dyeing shampoo was used. In particular, with hair that is difficult to dye, the dye-containing preparation can also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes can then - optionally after an intermediate rinse - applied the oxidation component. After a further period of exposure of 10 to 20 minutes, then rinsed and nachshampooniert if desired. 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 second subject of the present application is the use of the agents according to the invention for dyeing keratinic fibers.

A third object of the present invention is a process for dyeing keratinic fibers, in particular human hair, wherein an agent according to the invention is applied to the keratinic fibers and rinsed out again after a contact time or washed out with a shampoo.

The compound of the formula (I) _{1 in} which X is chlorine, Ak is ethyl, R ¹ , R ² , R ⁵ and R ^{6 are} each hydrogen, R ^{3 is} methoxy and R ^{4 is} an acetamide radical, is hitherto unknown. This compound, which may be referred to as Λ / - {5- [bis (2-hydroxyethyl) amino] -2 - [(ε) - (2-chloro-4-nitrophenyl) diazenyl] -4-methoxyphenyl} acetamide, is therefore also the subject of the present invention.

The invention will be further elucidated with reference to the following examples, which examples are intended to facilitate the understanding of the principle of the invention and should not be taken as limiting. embodiments

Unless otherwise stated, the following percentages are by weight.

1 Synthesis of the dyes

1.1 2 - [{4 - [(E) - (2-chloro-4-nitrophenyl) -diazenyl] -phenyl} (2-hydroxy-ethyl) -amino] -ethanol (1)

17.4 g of 2-chloro-4-nitroaniline were suspended in 60 ml of 5N HCl and stirred overnight. To the resulting yellow suspension, 100 g of ice were added, and added dropwise at -9 C to ⁰ -3 ⁰ C a solution of 6.9 g of sodium nitrite in 28 ml water over 15 min. The mixture was stirred at 0 - 3 ⁰ C for 2 h and filtered the resulting diazonium salt solution in a coolable dropping funnel.

In a 2 liter beaker, 18.1 g of N-phenyldiethanolamine were suspended in 38 ml of HCl (10%) and placed in 20 ml of water and 300 g of ice. At -3 ⁰ C, the resulting appropriately cooled diazonium salt solution was added dropwise over 15 min and stirred at 0 ⁰ C for 1 h. The precipitated product was filtered off with suction, washed neutral with water and dried in vacuo.

Yield: 27.4 g (75% of theory)

1.2 / V- {5- [bis (2-hydroxyethyl) amino] -2 - [(E) - (2-chloro-4-nitrophenyl) diazenyl] phenylacetamide (2)

17.4 g of 2-chloro-4-nitroaniline were suspended in 60 ml of 5N HCl and stirred overnight. To the resulting yellow suspension, 100 g of ice were added, and added dropwise at ⁰ -9 C to -3 ° C, a solution of 6.9 g of sodium nitrite in 28 ml water over 15 min. The mixture was stirred at 0 - 3 ⁰ C for 2 h and filtered the resulting diazonium salt solution in a coolable dropping funnel.

In a 2 l beaker, 23.8 g of 3 ^' - [bis (2-hydroxyethyl) amino] acetanilide were suspended in 38 ml of HCl (10%) and placed in 20 ml of water and 300 g of ice. At -3 ⁰ C, the resulting appropriately cooled diazonium salt solution was added dropwise over 15 min and Stirred at 0 ° C for 1 h. The precipitated product was filtered off with suction, washed neutral with water and dried in vacuo.

Yield: 36.2 g (86% of theory)

1.3 2 - [{4 - [(ε) - (2-chloro-4-nitrophenyl) diazenyl] -3-methylphenyl} (2-hydroxyethyl) amino] ethanol (3)

In a 2 liter beaker, 19.5 g of m-tolyldiethanolamine were suspended in 38 ml of HCl (10%) and placed in 20 ml of water and 300 g of ice. At -3 ⁰ C, the resulting appropriately cooled diazonium salt solution was added dropwise over 15 min and stirred at 0 ^G C for 1 h. The precipitated product was filtered off with suction, washed neutral with water and dried in vacuo.

Yield: 36.1 g (95% of theory)

1.4 / V- {5- [bis (2-hydroxyethyl) amino] -2 - [(E) - (2-chloro-4-nitrophenyl) diazenyl] -4-methoxyphenyl} acetamide (4)

17.4 g of 2-chloro-4-nitroaniline were suspended in 60 ml of 5N HCl and stirred overnight. 100 g of ice were added to the yellow suspension thus obtained and, at -9 ° C. to -3 ° C., a solution of 6.9 g of sodium nitrite in 28 ml of water was added dropwise over 15 minutes. The mixture was stirred at 0 - 3 ° C for 2 h and filtered the resulting diazonium salt solution in a coolable dropping funnel.

In a 2 l beaker, 26.8 g of 3 ^' - [bis (2-hydroxyethyl) amino] -4 ^' methoxyacetanilide were suspended in 38 ml of HCl (10%) and placed in 20 ml of water and 300 g of ice. At -3 ° C, the resulting appropriately cooled diazonium salt solution was added dropwise over 15 min and stirred at 0 ° C for 1 h. The precipitated product was filtered off with suction, washed neutral with water and dried in vacuo. Yield: 26.0 g (58% of theory)

2 Preparation of the colorants

For the preparation of the colorant was based on three different cream bases. An anionic, a nonionic and a cationic cream base were used which had the following compositions:

Anionic cream base:

Hydrenol D ^® ¹ 2.0 wt .-%

Lorol® ^® tech. ² . 2.0% by weight

Akypo Soft RLM ^45N®3 2.2% by weight

Propylparaben 0.1% by weight

Methylparaben 0.3% by weight

Ammonium sulfate 2.0% by weight

Conc. Ammonia ad pH 9

Water ad 100% by weight

¹ C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

² C ₁₂ -i ₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis)

³ lauryl alcohol 4.5 EO acetic acid sodium salt (at least 22% active ingredient content, INCI name: sodium laureth-5 carboxylates) (Chem-Y)

Nonionic cream base:

Stenol 16/18 ^® ⁴ 13.8% wt .-

Coconut oil ^®5 4.6% by weight

Eumulgin ^® ⁶ B2 4.0% wt .-

Water ad 100% by weight

⁴ C _16-18 fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis)

⁵ C ₁₂ -i ₈ fatty alcohol (INCI name: Coconut Alcohol) (Cognis)

⁶ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis) Cationic cream base:

Stenol 16/18 ^® ⁴ 8.0% wt .-

Eumulgin ^® B1 ⁷ 2.0 wt .-%

Dehyquart ^® ^A-8 CA 4.0 wt .-%

Water ad 100% by weight

⁷ Cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis)

⁸ trimethylhexadecylammonium chloride (about 24-26% active ingredient, INCI name: Aqua (Water), Cetrimonium Chloride) (Cognis)

For the preparation of the colorants 12.5 g of a cream base were weighed in a 250 ml beaker and melted at 85 ⁰ C.

In each case, 250 mg of a substantive dye obtained according to Synthesis Instructions 1.1 to 1.4 were suspended in about 5 ml of a mixture of distilled water and ethanol or dissolved by heating. In addition, in each case 250 mg of ammonium sulfate were dissolved in about 3 ml of water. These solutions were mixed with the respective melted cream base and stirred cold (<30 ⁰ C).

Then ammonia (25% ammonia solution) was added until the pH was between 9 and 10 and made up to 25 g with water.

3 colorations

One strand of hair about 1 g in weight and 25 g each of the prepared cream-shaped colorants were placed on one watch glass each time and the hair strands were well embedded in the dyeing creams. After 30 minutes (± 1 minute) Reaction time at room temperature were taken from the strands of hair, rinsed with water and finally shampooed once with Texapon ^® NSO. ⁹ The strands of hair were air-dried and their color was determined and recorded under the daylight lamp (color tester HE240A) (Taschenlexikon der Farben, A. Komerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag, Zurich, Göttingen). ⁹ lauryl ether sulfate, sodium salt (about 27.5% active ingredient; INCI name:

Sodium Laureth Sulfate) (Cognis)

The results obtained in the staining investigations are shown in Table 1 below:

Table 1 :

Claims

Patent claims

1. An agent for dyeing keratinic fibers, in particular human hair, comprising in a cosmetically acceptable carrier at least one substantive dye of the formula (I),

in which

- X stands for halogen,

Ak is C ₁ -C ₄ -alkylene or C ₁ -C ₄ -monohydroxyalkylene,

- R ¹ , R ² , R ⁵ and R ⁶ are each independently hydrogen, halogen or a branched or unbranched d- to C ₄ alkyl group and

- R ³ and R ⁴ are each independently hydrogen, a branched or unbranched C ₁ - to C ₄ alkyl group, a methoxy or ethoxy group, a group R ¹ R ¹¹ N-, wherein R 'and R "are independently is a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C 8 -hydroxyalkyl group or a C ₂ -C ₄ -dihydroxyalkyl group, or a group of the formula (II)

wherein R ^{7 is} a CrC ₄ alkyl group.

2. Composition according to claim 1, characterized in that it contains a direct dye of the formula (I), wherein X is chlorine.

3. Composition according to one of claims 1 or 2, characterized in that it contains a direct dye of the formula (I), wherein Ak is methylene or ethylene, preferably ethylene.

4. Composition according to one of claims 1 to 3, characterized in that it contains a direct dye of the formula (I), wherein R ¹ , R ² , R ⁵ and R ^{6 are} each hydrogen.

5. Composition according to one of claims 1 to 4, characterized in that it contains a direct dye of the formula (I), wherein R ³ and R ^{4 are} each independently hydrogen, methyl, ethyl, methoxy, ethoxy or a group of the formula (II) wherein R ^{7 is} methyl.

6. Composition according to one of claims 1 to 5, characterized in that it further contains at least one of the substantive dyes of the formula (I) different substantive dye.

7. Composition according to one of claims 1 to 6, characterized in that it contains at least one oxidation dye precursor.

8. Use of an agent according to one of claims 1 to 7 for dyeing keratinic fibers, in particular human hair.

9. A process for dyeing keratinous fibers, in particular human hair, characterized in that an agent according to one of claims 1 to 7 applied to the keratinic fibers and rinsed again after a contact time or washed out with a shampoo.

10. A compound of the formula (I) in which X is chlorine, Ak is ethyl, R ¹ , R ² , R ⁵ and R ^{6 are} each hydrogen, R ^{3 is} methoxy and R ^{4 is} an acetamide radical.