WO2007073923A1 - Hair colourants - Google Patents

Abstract

Agents for colouring keratin-containing fibres, in particular human hair, comprising, in a cosmetic carrier, a combination of (A) at least one compound according to formula (I) or hydrate thereof, in which R1 is a (C1-C6)-alkyl group, (C2-C6)-alkenyl group, aryl group, aryl-(C1-C6)-alkyl group or heteroaryl-(C1-C6)-alkyl group, R2 and R3, in each case independently of one another, are a hydrogen atom, a halogen atom, a (C1-C6)-alkyl group, a (C1-C8)-alkoxy group, hydroxy-(C1-C6)-alkoxy group, hydroxy group, nitro group, aryl group, trifluoromethyl group, amino group, which may be substituted by (C1-C6)-alkyl groups, or (C1-C6)-acyl group, and A? is a physiologically compatible anion, (B) is at least one heterocyclic, CH-acidic compound and (C) at least one aromatic aldehyde derivative different from compounds of the formula (I) are particularly well suited for obtaining intense colourations. Particularly on an inhomogeneous substrate, such as an unevenly damaged hair fibre, a uniform colouration is obtained which has excellent fastness.

Description

"Hair dye"

The invention relates to an agent for dyeing keratin-containing fibers, in particular human hair, containing specific formyl-substituted quinolinium derivatives in combination with heterocyclic, CH-acidic compounds and aromatic aldehyde derivatives, the use of this combination for dyeing keratinhaltiger fibers, and a method for dyeing keratin-containing fibers, in particular human hair.

For the dyeing of keratin-containing fibers, either direct dyes or oxidation dyes, which are formed by oxidative coupling of one or more developer components with one another or with one or more coupler components, are generally used. Coupler and developer components are also referred to as oxidation dye precursors.

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

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-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4- aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine are generally used. used derivatives. Suitable coupler substances are in particular α-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol , 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 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, 3-amino-6-methoxy-2 -methylamino-pyridine and 3,5-diamino-2,6-dimethoxypyridine.

For other common dye components, reference is expressly made to the series "Dermatology" by Ch. Culnan, H. Maibach, Marcel Dekker Inc., New York, Basel, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chap. 7, pages 248-250 (Direct-Dye), and Chap. 8, pp. 264-267 (oxidation dyes), as well as the European Inventory of Cosmetic Raw Materials, 1996, published by the European Commission, available in floppy form from the Federal Association of German Industrial and Trade Companies for Pharmaceuticals, Reform Goods and Personal Care, Mannheim ,

Although intensive dyeings with good fastness properties can be obtained with oxidation dyes, the development of the color is generally carried out under the influence of oxidizing agents such. H ₂ O ₂ , which in some cases may result in damage to the fiber. Still problematic is the provision of oxidation hair dyeings in the red region with sufficient fastness properties, in particular with very good washing and rubbing fastnesses. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors can sometimes have a sensitizing effect on persons with sensitive skin. Direct dyes are applied under gentler conditions, but their disadvantage lies in the fact that the dyes often have only insufficient fastness properties.

Another way to stain keratin-containing fibers is through the use of stains containing a combination of component

A compounds containing a reactive carbonyl group with component B compounds selected from (a) CH-acidic compounds and (b) compounds having a primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. The corresponding dyeing method (referred to below as oxo dyeing) is described, for example, in the publications WO-A1-99 / 18916, WO-A1 -00 / 38638, WO-A1-01 / 34106 and WO-A1-01/47483. The resulting dyeings have partially color fastness on the keratin-containing fiber, which are comparable to those of the oxidation dyeing. The Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has an acceptable brilliance and color depth. The aforementioned components A and B, hereinafter referred to as Oxofarbstoffvorprodukte, are generally not themselves dyes, and are therefore each alone taken not for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process. However, it is also possible to use corresponding developer and / or coupler-type oxidation dye precursors with or without the use of an oxidizing agent under compounds of component B. Thus, the oxo staining method can be readily combined with the oxidative staining system.

The publications DE-A1-19962875 and DE-A1-19745356 relate to formyl-substituted quinolinium derivatives in hair dyes.

In the publication H. Baumann et al., Liebigs Ann. Chem., 1968, 717, 124-136, reactions of pyrimidones are described as methylene bases. A hair dye containing 1, 2-dihydro-2-oxo-pyrimidinium derivatives or the use of the disclosed hemicyanines for dyeing keratin-containing fibers is not suggested here.

German patent application DE-A1-2047431 describes cationic methine dyes for dyeing anionically modified fibers, such as acid-modified polyesters or acrylonitrile polymers. For the preparation of the cationic methine dyes, inter alia, 3,4-dihydro-3-methyl-4-methylene-quinazol-2-one and 1, 3,6-trimethyl-4-methylene-pyrimidin-2-one and mandatory terephthalaldehyde are used.

German patent application DE-A1-2165913 describes a process for producing bleaching images using photosensitive dyes proposed. The claimed photosensitive dyes belong to the class of pyrimidone and thiopyrimidone dyes, respectively.

German Patent Application DE-A1-102 41 076 proposes 1,2-dihydro-2-oxopyrimidinium derivatives in combination with reactive carbonyl compounds as agents for coloring keratin fibers. However, these means are still in need of improvement with regard to the authenticity of the dyeings obtained therewith, in particular light and wash fastness.

It is known from document DE-A1-2165913 that the dyes based on the pyrimidones are photosensitive.

None of the abovementioned publications discloses the combination of dye precursors for oxo dyeing described in greater detail below according to the invention. If C, H-acidic compounds are dyed together with an aldehyde on hair, brilliant and brilliant colorations can be obtained. In the development of nuances on differently damaged hair strands (leveling strands), the combinations of the prior art have weaknesses in the leveling ability. There is therefore still a need for colorants which provide an acceptable, uniform dyeing result even for consumers with hair that has been damaged in part or differently.

In an unpredictable manner, it has now been found that use of the triple combinations according to the invention, especially on partially damaged hair strands, provides dyeings with high color fastness, uniformity and excellent leveling properties. This uniformity in color fading is present both directly after the dyeing process and after several washes, creating a great advantage over the two combinations according to the prior art.

A first subject of the invention are therefore agents for dyeing keratin-containing fibers, in particular human hair, containing in a cosmetic carrier a combination of (A) at least one compound according to formula (I) or its hydrate

wherein R ^{1 represents} a (d-CeJ-alkyl group, (C ₂ -C ₆ ) -alkenyl group, aryl group, aryl (C _r C ₆ ) -alkyl group or heteroaryl (C _r C ₆ ) -alkyl group,

R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a (C 1 -C ₆ ) alkyl group, a (C 1 -C 4 alkoxy group, hydroxy (C 1 -C ₆ ) alkoxy group, hydroxy group, nitro group, aryl group, trifluoromethyl group, amino group, and the like by (CrCeJ-alkyl groups may be substituted, or (Ci-C ₆ ) acyl group and

A ~ means a physiologically acceptable anion

(B) at least one heterocyclic, CH-acidic compound and

(C) at least one aromatic aldehyde derivative other than compounds of formula (I).

The compounds of the formula (I) are present in aqueous carriers in chemical equilibrium with the hydrates of the formula (Ia). This is exemplified below:

The hydrates can be isolated and are also suitable for use in the colorants of the invention.

Preferred compounds according to formula I are those in which the formyl group -CHO is bonded in the 2- or 4-position. A is according to formula I preferably halide, benzenesulfonate, p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, perchlorate, sulfate, hydrogensulfate, tetrachlorozincate or N-oxide of quinoline, particularly preferably a p-toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, methylsulfate or benzenesulfonate ion. The preferred anion is the p-toluenesulfonate ion.

R ¹ according to formula I is preferably a (C 1 -C ₆ ) -alkyl group.

The compounds of the formula I are particularly preferably selected from the group consisting of the benzenesulfonates, p-toluenesulfonates, methanesulfonates, trifluoromethanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides and / or tetrachlorozincates of 4-formyl-1-methylquinolinium and 2-formyl 1-methylquinolinium. 4-formyl-i-methyl-quinolinium p-toluenesulfonate and 2-formyl-1-methyl-quinolinium p-toluenesulfonate and the hydrates of the abovementioned compounds are very particularly preferred compounds of the formula I.

As CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected. According to the invention, CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.

The heterocyclic, CH-acidic compound is selected from at least one compound of the formula (II) and / or (III) and / or (IV)

wherein

R ⁴ and R ⁵ are independently a linear or cyclic C ₁ -C ₆ - alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-CrC ₆ - alkyl group, a CrC _6- hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl group, a group R ¹ R ¹¹ N- (CH ₂ ) _P -, wherein R ¹ and R ¹¹ independently represent a hydrogen atom a C _r C ₄ alkyl group, a d ^ -hydroxyalkyl group or an aryl-C _r C ₆ alkyl group, wherein R ¹ and R "together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p stands for a number 2, 3, 4, 5 or 6,

R ⁶ and R ⁷ independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, where at least one of the radicals R ⁶ or R ⁷ denotes a C ₁ -C ₆ -alkyl group,

R ⁸ represents a hydrogen atom, a C _r C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -Ce hydroxyalkoxy group, a group R ^1, R ^{1 v} N- (CH _{2) q} - wherein R ¹ "and R ^IV are independently a hydrogen atom, an alkyl group CrC ₆ alkyl group, a C _r C ₆ hydroxyalkyl group, or an aryl-C _r C ₆ and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ⁸ together with one of the radicals R ⁶ or R ^{7 can form} a 5- or 6-membered aromatic ring which optionally substituted with a halogen atom, a CrC ₆ alkyl group, a Ci-C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy group, a hydroxyalkoxy-CRCE, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH _{2) S} -, wherein R ^V and R ^VI are each independently a hydrogen atom, a CrC ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group or an aryl-C _r C ₆ - alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,

Y ¹ represents an oxygen atom, a sulfur atom or a group NR ^V ", in which R ^v " represents a hydrogen atom, an aryl group, a heteroaryl group, a C 1 -C ₆ -alkyl group or a C 1 -C ₆ -arylalkyl group,

X ^" is a physiologically acceptable anion,

Het is an optionally substituted heteroaromatic,

• X ¹ represents a direct bond or a carbonyl group.

R ⁹ and R ¹⁰ either together with the nitrogen atom form a saturated or unsaturated 5- or 6-membered ring or independently represent a (C ₁ -C ₄ ) alkyl group, a (C ₂ -C ₆ ) -alkenyl group, an aryl group, a Aryl (C _r Ce) alkyl group, a (C ₂ -C ₆ ) hydroxyalkyl group, a (C ₂ -C ₆ ) polyhydroxyalkyl group or a group R ¹ R ¹¹ N- (CH ₂ ) n, -, wherein R ¹ and R ¹¹ independently represent a hydrogen atom, a (C _r C ₆ ) alkyl group, a (CrC ₆ ) alkenyl group or an arylC _r C ₆ alkyl group, wherein R ¹ and R ¹¹ together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and

• R ¹¹ is a hydrogen atom, a (C _{r C6)} alkyl, one alkyl group (C ₂ -C ₆₎ alkenyl group, an aryl group, an aryl (CrC ₆₎ a (C ₂ -C ₆₎ - Hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R '' R ^lv N- (CH ₂ ) _n -, wherein R ¹ "and R ^IV independently of one another represent a hydrogen atom, a (C ₁ -C ₆ ) - alkyl group, a (C ₁ -C ₆ ) alkenyl group or an aryl-CrC ₆ alkyl group, wherein R ^MI and R ^ιv together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 2, 3, 4, 5 or 6.

In the following, examples of the groups or radicals mentioned as substituents in the context of this application will be mentioned. Examples of C 1 -C 6 -alkyl radicals are the groups methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of corresponding cyclic alkyl groups are cyclopentyl and cyclohexyl. examples for preferred C ₂ -C ₆ alkenyl radicals are vinyl and allyl. C ₁ -C ₆ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. The methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl groups are examples of CrC-alkoxycarbonyl groups; the methoxycarbonyl and ethoxycarbonyl groups are particularly preferred. Furthermore, as preferred examples of a C ₁ -C ₆ -hydroxyalkyl group, there may be mentioned hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyethyl to be named. A 2-hydroxyethyl group is particularly preferred. The methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxybutyl and methoxyhexyl groups are examples of C ₁ -C ₆ -alkoxy C ₁ -C ₆ -alkyl groups according to the invention. Examples of a C ₂ -C ₆ polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group. A preferred hydroxyC _r C ₆ alkoxy group is the 2-hydroxyethoxy group. Preferred aryl groups are phenyl, naphthyl and biphenyl. Examples of halogen atoms are F, Cl, Br or I atoms, with Cl atoms being particularly preferred. Preferred C _r C ₆ aminoalkyl groups are the aminomethyl, aminoethyl and aminopropyl groups. Preferred aryl-C 1 -C 6 -alkyl groups are benzyl and 2-phenylethyl. The aminomethyl, 2-aminoethyl, 3-aminopropyl, 2-dimethylaminoethyl, diethylaminomethyl, dimethylaminomethyl, 2-methylaminoethyl, dimethylamino, piperidinomethyl, pyrrolidinomethyl, morpholinomethyl and amino groups are examples of a group R'R "N- (CH ₂ ) n-, with the diethylaminomethyl, piperidinomethyl, 2-dimethylaminoethyl, dimethylamino and amino groups being particularly preferred.""Examples of a heteroaryl group are pyrrolidyl, 2-furyl, 2-thienyl, 4-pyridyl. 3-pyridyl, 2-pyridyl, triazolyl and 1-imidazolyl Examples of a heterocyclic C _1-4 -alkyl group are pyrrolidino- (C _1-4 ) -alkyl, piperidino- (C _1-4 ) -alkyl, morpholino- (C _1-4 ) alkyl, 2-furyl (C _1-4 ) alkyl, 2-thienyl (C _1-4 ) alkyl, 4-pyridyl (C _1-4 ) alkyl, 3- Pyridyl (C _1-4 ) alkyl, 2-pyridyl (C _1-4 ) alkyl, triazolyl (C _1-4 ) alkyl and 1-imidazolyl (C _1-4 ) alkyl.) A preferred C _{1 The 4-} carboxypropylene group is the 3-carboxypropyl group The groups 1-carboxypropylene and 1-carboxyethylene are b Preferred carboxy (C 1 -C ₄ ) alkylene groups. The other terms used are derived according to the invention from the definitions given here. Preferably, the compounds of formula II are selected from one or more compounds of the group of salts with physiologically acceptable

Counterion X ^" , which is formed from salts of the

1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-oxo-pyrimidinium,

1, 2-dihydro-1,3-diphenyl-4-methyl-2-oxo-pyrimidinium,

1-allyl, 2-dihydro-3,4,6-trimethyl-2-oxo-pyrimidinium,

1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium,

1, 2-dihydro-1, 3,4,6-tetramethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4,6-dimethyl-2-thioxopyrimidiniums,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium _l

1, 2-dihydro-1,3-diphenyl-4,6-dimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3,4-trimethyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-1, 3-diphenyl-4-methyl-2-thioxo-pyrimidinium,

1, 2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and

1, 2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium.

By definition, the physiologically acceptable anions X ^" according to formula (II) may not only carry a negative charge, but may also have a charge number greater than 1. In the latter case, the anions X ^{" of} the salt form are preserved to maintain electroneutrality by formulating a stoichiometric coefficient of less than 1 described before the name of the anion. The physiologically acceptable anions are preferably selected from halide, 0.5 sulfate, hydrogen sulfate, 0.5 carbonate, bicarbonate, 1/3 phosphate, 0.5 hydrogen phosphate, dihydrogen phosphate, Carboxylate, such as lactate, citrate or tartrate. Particularly preferably X "is chloride, bromide or a carboxylate counterion, in particular lactate, citrate or tartrate.

The compounds of formula II according to the invention are CH-acidic compounds. They are in chemical equilibrium with their corresponding enamine form. With the aid of a base, the corresponding enamines can be specifically prepared from the compounds of the said formulas by deprotonation on the carbon atom of the activated methyl groups in the 4- or 6-position. As an example, this deprotonation is illustrated below. Compounds according to formula IIa are examples of the enamine forms according to the invention of the compounds of the formula (II) which are included in the scope of protection.

(N) (IIa)

According to the invention, compounds of the formula (III) are particularly suitable for those in which the radical Het according to formula III is derived from one of the heteroaromatic compounds furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine , 1, 2,3-triazine, 1, 2,4-triazine, 1, 3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline, isoquinoline, cinnoline, phthalazine , Quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, purine, pteridine and coumarin, wherein the aforementioned heteroaromatics have at least one group selected from a Halogen atom, a nitro group, a thio group, a thio (C _r C ₆ ) alkyl group, a heteroaryl group, an aryl group, a (C _r C ₆ ) alkyl group, a (C ₁ -C ₆ ) alk oxy group, a hadroxy group, a (C ₂ -C ₆ ) hydroxyalkyl group, a (C ₂ -C ₆ ) polyhydroxyalkyl group, a (Ci-C ₆ ) alkoxyl (CrC ₆ ) alkyl group, an aryl (dC ₆ ) - alkyl group, an amino group, a (C ₁ -C 16 -monoalkylamino group, a (C ₁ -C ₆ ) dialkylamino group, a dialkylaminoalkyl group - (CH ₂ ) _O -NR ¹ R ", wherein n is an integer of 2 and 6, and R 'and R "is independently a linear or branched alkyl group, which may optionally together form a ring, may be substituted.

Preferably, the compounds of formula III are selected from at least one member of the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl 3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5 Fluoro-2-thenoyl) - acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) - acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2- (1, 2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1 / - / - benzimidazol-2-ylacetonitrile, IH-benzothiazole -2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methyl-indole-3 -oyl) -acetonitrile, δ-cyanoacetyl-T-methoxy-methylcoumarin, 2- (2-isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2-phenyl-5,6-benzoquinoline) 4-oyl) -acetonitrile, 2- (quinoxalin-2-yl) -acetonitrile, 2- (cumaron-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) -2,3- tert-Butyl dihydro-1-benzofuran-2-carboxylate, 2- (6-hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and 2- (1-phenyl-1, 4- dihydrothiochromo [4,3-c] pyrazole-3-oyl) -acetonitrile.

When the compounds of the formula (IV) according to the invention are nitrogen atom-containing compounds, the known salts can be prepared as acid addition salts in many cases from these in a customary manner. All statements of this document and, accordingly, the scope claimed cover both the compounds present in free form and their water-soluble, physiologically tolerated salts. Examples of such salts are the hydrochlorides, hydrobromides, sulfates, phosphates, acetates, propionates, citrates and lactates. The hydrochlorides and the sulfates are particularly preferred. The same applies to the amino-containing compounds of the formula (IV).

Preferred compounds of the formula (IV) are selected from the representatives in which the radicals R ⁶ and R ⁷ according to formula (IV) together with the nitrogen atom form a saturated 5- or 6-membered ring. This ring in turn may optionally contain an oxygen atom and / or optionally a plurality of nitrogen atoms in the skeleton. Particularly preferred examples of such rings are piperidinyl, morpholinyl and pyrrolidinyl.

It is inventively preferred that the heterocyclic, CH-acidic compounds is selected from at least one compound of the group consisting of

where X ^"stands for a physiologically acceptable anion, in particular for the representatives described above.

The aromatic aldehyde derivative is preferably selected according to the invention from compounds of the formula (V)

wherein

• R ^{1 *} , R ^{2 *} and R ^{3 *} independently represent a hydrogen atom, a halogen atom, a C _r C ₆ alkyl group, a hydroxy group, a C ₁ -C ₆ alkoxy group, a CrCβ dialkylamino group, a di (C ₂ -C ₆ - hydroxyalkyl) amino group, a DKCrCe-alkoxy-CRCE-alkylJaminoguppe, a CrC ₆ -Hydroxyalkyloxygruppe, a C ₁ -C ₆ -AIkOXy- (C ₂ -C ₆₎ - alkyloxy group, a sulfonyl group, a carboxy group , a sulfonic acid group, a sulfonamido group, a sulfonamide group, carbamoyl group, a C ₂ -C ₆ acyl group or a nitro group,

Z 'is a direct bond or a vinylene group,

• R ^{4 *} and R ^{5 *} represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

The radicals R ^{1 *} , R ^{2 *} and R ^{3 *} according to formula (V) are preferably, independently of one another, a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, a C ₁ -C ₆ -alkoxy ^ CrCeJ-alkyloxy group, a C ₁ -C ₆ - dialkylamino group, a di (C ₂ -C ₆ -hydroxyalkyl) amino group, a di (C ₁ -C ₆ -BIkOXy-C ₁ - C ₆ alkyl) or a C aminoguppe _r C ₆ -hydroxyalkyloxy group.

The radical R ^{1 *} according to formula (V) is preferably a hydroxy group.

The group Z 'according to formula (V) is preferably a direct bond.

The aromatic aldehyde derivatives are particularly preferably selected from at least one compound selected from the group consisting of

The colorants according to the invention give intensive dyeings even at physiologically compatible temperatures of below 45.degree. They are therefore particularly suitable for dyeing human hair. For use on human hair, the colorants can usually be incorporated into an aqueous cosmetic carrier. Suitable hydrous cosmetic carriers are for. As creams, emulsions, gels, foam aerosols or surfactant-containing foaming solutions such. As shampoos or other preparations which are suitable for use on the keratin fibers. If necessary, it is also possible to incorporate the colorants in anhydrous carrier. In this context, it is conceivable to integrate the ingredients in a powdered or tablet-like formulation, which is dissolved in water before use.

The cosmetic carriers are especially aqueous or aqueous-alcoholic.

An aqueous cosmetic carrier contains at least 50% by weight of water. For the purposes of the present invention, aqueous-alcoholic cosmetic carriers are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alkyl alcohol, 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.

Keratin fibers are wool, furs, feathers and especially human hair to understand. The colorants of the invention can in principle but also for dyeing other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers such. As regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose can be used.

These preferred or particularly preferred representatives of the compounds of the formula (V) are again preferably _{% combined} with the abovementioned preferred compounds of the formulas (I) and of the formulas (II) and / or (III) and / or (IV).

The above-mentioned compounds of the formula I, the heterocyclic, CH-acidic compounds, and the aromatic aldehyde derivatives are each preferably in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total colorant, used.

In a further embodiment, the agents according to the invention may additionally contain at least one developer component and optionally at least one coupler component as oxidation dye precursors. However, it is preferred to formulate the agents according to the invention free of oxidation dye precursors, in particular if the risk of allergies for para-allergic persons is to be minimized.

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 (E1)

in which

G ¹ is a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

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

AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -

Alkyl radical containing a nitrogen-containing group, a phenyl or a 4'-

Aminophenylrest is substituted;

G ² is a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

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

AIkOXy- (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 radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a 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 each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ to C ₄ hydroxyalkyl group, there may be mentioned a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is especially prefers. 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, d- to C ₄ monoalkylamino, C ₁ - to C ₄ dialkylamino, C _r to C ₄ - trialkylammonium groups, C ₁ - to C ₄ -Monohydroxyalkylaminogruppen, 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, 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-acet ylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine 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-phenylenediarine and N, N bis (.beta.-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 dinuclear developing 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), as well as theirs Physiologically acceptable salts:

in which:

Z ¹ and Z ² independently of one another, are a hydroxyl or NH ₂ radical, which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C to C ₄ - substituted 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, which is 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 optionally substituted by one or more hydroxyl or C ₁ - to C ₈ -Al koxyreste, or a direct bond, G ⁵ and G ⁶ are independently 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 of one another represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the 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 according to the invention 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'-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 ¹ -diethyl-N, N ' bis (4'-amino-3'-methylphenyl) ethylenediamine, bis (2-hydroxy-5-aminophenyl) methane, N, N'-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.

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, Bis (2-hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis- (2 ', 5'-diaminophenyl) - 1, 4,7,10-tetraoxadecane or one of its physiologically acceptable 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 C ₁ - to C ₄ -alkyl radical, a d- to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (Cr to _C4) alkoxy (C _r to C ₄₎ alkyl, d- a to C ₄ aminoalkyl radical, a hydroxy (C _r to C ₄₎ alkylamino group, a C ₁ - to C ₄ -Hydroxyalkoxyrest, a C ₁ - to C ₄ - Hydroxyalkyl (C ₁ -C ₄ ) -aminoalkyl radical or a (C ₁ -C ₄ -alkylamino) (C ₁ -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-alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,

G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

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

G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (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-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 chlorophenol, 4-amino-2,6-dichlorophenol, 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 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- (ß-

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 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 -Triaminopyrimidin.

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 _I 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4.5- Diamino-i, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole _> 4, 5-diamino-1- (β-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-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 pyrazolo [1,5-a] pyrimidine of the following formula (E4) and their tautomeric forms, provided that a tautomeric equilibrium exists:

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical is a (C _r to C ₄₎ alkoxy (Cr to _C4) alkyl, a

C ₁ - to C ₄ -Aminoalkylrest, optionally substituted by an acetyl Ureid- or a

Sulfonyl radical may be protected, a (C ₁ - to C ₄₎ alkylamino (Ci to C ₄₎ - alkyl group, a di - [(C _r to C ₄₎ alkyl] - (Cr to C ₄₎ aminoalkyl radical, where the dialkyl

Radicals optionally have a carbon cycle or a 5 or 6 heterocycle

Form chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) -

[Hydroxyalkyl] - (C _r to C ₄ ) aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a C ₁ - to

C ₄ alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -

Polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a (C ₁ - to C ₄ ) -alkylamino radical

(C ₁ - to C ₄ ) -alkyl radical, a di-E (C ₁ - to C ₄ ) alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical, where the dialkyl radicals optionally have a carbon cycle or a heterocycle with 5 or 6 chain members, form a C ₁ - to C ₄ hydroxyalkyl or a di- (C ₁ - to C ₄ hydroxyalkyl) aminoalkyl group, an amino group, 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 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0, if p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7); when p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (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 a 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 coupler components optionally contained in the agents according to the invention are preferably selected from 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 2,4-

Diaminophenoxyethanol, 1, 3-bis (2 ', 4'-diaminophenoxy) propane ₁ 1-methoxy-2-amino-

4- (2'-hydroxyethylamino) benzene, 1, 3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3 bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 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 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 1-hydroxy-3,4-methylenedioxybenzene,

1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene.

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 and 2,6-dihydroxy-3,4-dimethylpyridine.

As precursors of naturally-analogous dyes, within the scope of a further embodiment, preference is furthermore given to using those indoles and indolines in the agents according to the invention which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring. 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 such an embodiment, the colorants contain at least one indole and / or indoline derivative.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IN-1),

in the independently of each other

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

G ²² 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 ²³ is hydrogen or a

- G ²⁴ is hydrogen, a C _r C ₄ alkyl group or a group -CO-G ²⁶ , in which G ²⁶ is a CrC ^ alkyl group, and

G ²⁵ represents one of the groups mentioned under G ²⁴ , 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-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 (IN-2),

(IN 2)

in the independently of each other

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

G ²⁸ is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,

- G ²⁹ is hydrogen or an alkyl group ₄ C _r C,

G ³⁰ is hydrogen, a C _r C ₄ alkyl group or a group -CO-G ³² , in which G ³² is a C 1 -C ₄ alkyl group, and

- G ³¹ stands for one of the groups mentioned in G ³⁰ ,

- 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, the colorants according to the invention for further modifying the color shades in addition to the compounds according to the invention additionally contain conventional substantive dyes, such as nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having 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 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 as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (.beta.-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (.beta.-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 ¹ - 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 may preferably contain a cationic substantive dye. Particularly preferred are

(a) cationic triphenylmethane dyes such as Basic

Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well 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, are claimed in claims 6 to 11.

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

CH ₃ SO ₄ ^'

(DZ1) (Basic Yellow 87)

Cl ^"

(DZ2)

(DZ3) (Basic Orange 31)

(DZ5) (Basic Red 51)

(DZ8)

The compounds of the formulas (DZ1), (DZ3) and (DZ5) 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 particularly preferred substantive dyes.

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

Furthermore, the preparations according to the invention may also contain naturally occurring dyes such as those found in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, sawnwood, madder root, catechu, seder and alkano root.

It is not necessary that the optionally contained substantive dyes each represent uniform compounds. Rather, in the colorants according to the invention, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, eg. As toxicological, must be excluded.

To obtain further and more intense colorations, the compositions according to the invention may additionally contain color enhancers. The color intensifiers are preferably selected from the group consisting of piperidine, piperidine-2-carboxylic acid, piperidine-3-carboxylic acid, piperidine-4-carboxylic acid, pyridine, 2-hydroxypyridine, 3-hydroxypyridine, A- Hydroxypyridine, imidazole, 1-methylimidazole, arginine, histidine, pyrrolidine, proline, pyrrolidone, pyrrolidone-5-carboxylic acid, pyrazole, 1, 2,4-triazole, piperazidine, their derivatives and their physiologically acceptable salts.

The color intensifiers mentioned above can be used in an amount of 0.03 to 65 mmol, in particular 1 to 40 mmol, in each case based on 100 g of the total colorant.

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. If the agent according to the invention contains air-oxidizable oxidation dye precursors or indole or indoline derivatives, oxidizing agent 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 wt .-%, 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 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, eg Pyranose oxidase and eg 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.

Furthermore, the compositions according to the invention may contain all known in such preparations active ingredients, additives and excipients. In many cases, the colorants contain at least one surfactant, with both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. 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 as. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 or 3 C atoms in the alkanol group,

linear fatty acids with 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

Is an alkyl group having 10 to 22 C atoms and x is 0 or 1 to 16,

Acylsarcosides having 10 to 18 C atoms in the acyl group,

Acyltaurides having 10 to 18 C atoms in the acyl group,

Acyl isethionates having 10 to 18 C atoms in the acyl group, Sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 C atoms, linear alpha Olefinsulfonate with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and Alkylpolyglykolethersulfate the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in the R is a preferably linear alkyl group with 10 to 18 C atoms and x = O 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 to 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.

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^H or -SO ₃ ^H group in the molecule. 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-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacylaminoethylhydroxyethylcarboxymethyl- glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name Cocamidopropyl Betaine. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C _8-18 -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-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-co kosalkylaminopropionat, cocoacylaminoethyl aminopropionate and C _2- I8- sarcosine.

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 onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms

Atoms and alkylphenols having 8 to 15 C atoms in the alkyl group,

C _12-22 fatty acid mono- and diesters of addition products of 1 to 30 mol

Ethylene oxide with glycerine,

C _{8-22 alkyl} mono- and oligoglycosides and their ethoxylated analogs,

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

Castor oil,

Addition products of ethylene oxide with sorbitan fatty acid esters

Addition products of ethylene oxide to fatty acid alkanolamides.

Examples of the cationic surfactants which can be used in the agents according to the invention are, in particular, quaternary ammonium compounds. Preferred are ammonium halides such as Alkyltrimethylarnmoniumchloride, Dialkyldimethylammoniumchloride and Trialkylmethylammoniumchloride, z. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates. Also suitable according to the invention are cationic silicone oils, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) , SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

Alkylamidoamines, in particular fatty acid amidoamines, such as the ^{stearylamidopropyldimethylamine} obtainable under the name Tego ^Amid® S 18, are distinguished not only by a good conditioning action but also by their good biodegradability.

Also very good biodegradability are quaternary Esterverbindungen, so-called "esterquats", alkyldialkoyloxyalkylammoniummethosulfate such as those sold under the trade name Stepantex® ^® methylhydroxy-.

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

The compounds containing alkyl groups used as surfactants may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

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 are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides as catalysts be used. The use of products with narrow homolog distribution may be preferred.

The pH of the composition according to the invention is usually between 2 and 11, preferably between 8 and 10.

Further active agents, auxiliaries and additives are, 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 dimethylaminoethyl 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 Butylaminoethylmethacryla ^ -hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate tat / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabicum, karaya gum, locust bean gum, linseed gums, dextrans, celulose derivatives, eg. For example, methyl cellulose, hydroxyalkyl cellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,

Structureants such as glucose and maleic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins, and silicone oils,

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, Solubilizers such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,

Anti-dandruff agents such as Piroctone Olamine and Zinc Omadine, other pH adjusters,

Active substances such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and their salts, plant extracts and vitamins, cholesterol, light stabilizers,

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

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, opacifiers such as latex,

Pearlescing agents such as ethylene glycol mono- and distearate,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air and antioxidants.

The constituents of the cosmetic carrier are used to prepare the compositions of the packaging unit according to the invention in amounts customary for this purpose; z. B. emulsifiers in concentrations of 0.5 to 30 wt .-% and thickening agents in concentrations of 0.1 to 25 wt .-% of the total colorant used.

A second subject of the present invention relates to a process for dyeing keratin-containing fibers, in particular human hair, wherein an agent of the first subject of the invention applied to the keratin fibers, left on the fiber for some time, usually about 15-30 minutes, and then rinsed again or washed out with a shampoo. During the contact time of the agent on the fiber, it may be advantageous to assist the dyeing process by supplying heat. The heat can be through an external heat source, such as warm air of a hot air blower, as well as, especially when a hair coloring on live subjects, by the body temperature of the subject done. In the latter case, usually the part to be dyed is covered with a hood.

In this case, the compounds of formula I _1, the heterocyclic, CH-acidic compounds and the aromatic aldehyde derivatives, in particular their above-mentioned preferred and particularly preferred representatives as coloring components either simultaneously applied to the hair or else sequentially, ie in a multi-step process , it is irrelevant which of the components is applied first. The optionally contained ammonium or metal salts can be added to the compounds of the formula I or the other components according to the invention. Between the application of the individual components can be up to 30 minutes time interval. Pre-treatment of the fibers with the saline solution is also possible.

Before applying the agent according to the invention in the process according to the invention, it may be desirable to subject the keratin-containing fiber to be dyed to a pretreatment. The time sequence of the pretreatment step required for this purpose and the application of the agent according to the invention need not be in immediate succession, but there may be a period of up to a maximum of two weeks between the pretreatment step and the application of the agent according to the invention. For this purpose, several pre-treatment methods are suitable. The fiber is preferred

V1 before the application of the bleaching agent according to the invention or V2 before the use of the oxidative staining agent according to the invention

subjected.

In pretreatment V1, the keratin-containing fiber is treated with a bleaching agent. The bleaching agent contains, in addition to an oxidizing agent, such as usually hydrogen peroxide, preferably at least one inorganic persalt effective as an oxidation and bleach booster, such as a peroxydisulfate of sodium, potassium or ammonium. Dyes according to the method according to the invention obtained by the pre-treatment V1 a special brilliance and color depth. In the context of pretreatment V2, an agent containing the aforementioned oxidation dye precursors as developer and optionally coupler components and optionally mentioned derivatives of indole or indoline is applied to the fiber and after a contact time optionally with the addition of aforementioned suitable oxidizing agents on the hair for 5-45 minutes leave the core fiber. Thereafter, the hair is rinsed. By the subsequent application of the agent according to the invention existing oxidation dyeings can be given a new shade of shade. If the color shade of the agent according to the invention is selected in the same shade of the oxidative dyeing, then the dyeing of existing oxidation dyeings can be refreshed by the process according to the invention. It turns out that the color refreshing or shading according to the method of the invention is superior to color refreshing or shading alone with conventional substantive dyes in the color brilliance and color depth.

If the colorant according to the invention additionally contains hydrogen peroxide or a hydrogen peroxide-containing oxidant mixture as the oxidizing agent, the pH of the hydrogen peroxide-containing hair colorant is preferably in a pH range from pH 7 to pH 11, particularly preferably pH 8 to pH 10. The oxidizing agent can be used immediately before use mixed with the hair dye and the mixture applied to the hair. If the compounds of the formula I ₁ are applied to the hair in the heterocyclic, CH-acidic compounds and the aromatic aldehyde derivatives in a two- to multistage process, the oxidizing agent must be used in one of the process stages together with the corresponding coloring component. For this purpose, it may be preferable to formulate the oxidizing agent with one of the coloring components in a container.

The compounds according to formula I, the heterocyclic, CH-acidic compounds and the aromatic aldehyde derivatives can either be stored separately or together, either in a liquid to pasty preparation (aqueous or anhydrous) or as a dry powder. If the components are stored together in a liquid preparation, it should be substantially anhydrous to reduce the reaction of the components. In the separate storage, the reactive components are intimately mixed with each other just before use. At the troc During storage, a defined amount of warm (3O ⁰ C to 8O ⁰ C) water is usually added before use and a homogeneous mixture is produced.

A third subject of the invention is the use of a composition of the first subject of the invention for dyeing keratin-containing fibers, in particular human hair.

All preferred and optional parameters of the first and second subject of the invention apply mutatis mutandis for the subject invention two and three.

B e i s p e e l e

All quantities given in the example formulations provided by standard production methods are, unless otherwise indicated,% by weight, based on the weight of the corresponding formulation. The following raw materials were used:

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

² C _12-18 fatty alcohol (INCI name: Coconut Alcohol) (Cognis)

³ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

⁴ (75% by weight of active substance, INCI name: PEG-40 Hydrogenated Castor OiI) (BASF)

⁵ cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis)

⁶ sodium lauryl ether sulfate (27% active ingredient INCI: Sodium Laureth Sulfate) (Cognis Germany)

⁷ alkyl polyglucoside carboxylate sodium salt; 30% active ingredient (invention) (sodium carboxymethyl (C ₀ - C ₁₆₎ alkyl glucoside) (Cognis Germany)

⁸ N, N-dimethyl-N- (C ₈ -C ₁₈ -cocoamidopropyl) -ammoniumacetobetaine (about 30% of active substance, INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis Germany)

⁹ polyacrylic acid (INCI name: Carbomer) (Noveon)

¹⁰ 1-Hydroxyethane-1, 1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

¹¹ about 40% active ingredient (INCI name: Sodium Silicate) (Cognis Germany)

¹² 30% by weight of active substance in water (INCI name: Arylates Copolymer) (Rohm & Haas)

¹³ Hydroxyethylcellulose (INCI name: Hydroxyethylcellulose) (Hercules)

¹⁴ lauryl alcohol 4.5 EO acetic acid sodium salt (at least 21% active ingredient content, INCI name: sodium laureth-6 carboxylates) (Chem-Y)

¹⁵ lauryl myristyl ether sulfate sodium salt (about 68% to 73% active ingredient content, INCI name: Sodium Myreth Sulfate) (Cognis)

¹⁶ Ciz.ie fatty alcohol i ^ glucoside (about 50-53% active ingredient content; INCI name: Lauryl Glucoside, Aqua (Water)) (Cognis)

¹⁷ alkylpolyglucoside monoglyceride mixture (about 65-70% solids; INCI name: Coco-Glucoside, Glyceryl Oleate, Aqua (Water)) (Cognis) ¹⁸ Polymer ^® W 37194ca. 20% by weight of active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen)

¹⁹ Dimethyldiallylammonium chloride Acrylic acid copolymer (about 35 active substance in water, INCI name: Polyquaternium-22) (Ondeo-Nalco)

²⁰ poly (dimethyldiallylammonium chloride) (about 40% solids, INCI name: Polyquaternium-6) (Ondeo Nalco)

²¹ Dimethyldiallylammonium chloride Acrylamide copolymer (about 8.1 -9.1% active substance in water, INCI name: Polyquaternium-7) (Ondeo-Nalco)

²² Crosslinked Acrylate / C ₁₀ to C ₃₀ Alkyl Acrylate Copolymer, White Powder (INCI name: Acrylates (C10-30 Alkyl Acrylate Crosspolymer) (Noveon)

1. Preparation of a hair dye

1.1. color cream

For the preparation of the color cream, the recipe ingredients Nos. 1 to 4 were successively weighed into a beaker, melted at 80 ⁰ C and mixed together. From components A and B, a separate mixture was prepared together with the recipe components No. 7 and No. 8. This mixture was incorporated into the still hot cream. Subsequently, the still missing recipe ingredients Nos. 9 to 13 were added in order, and made up to 100% with distilled water. The batch was stirred cold, forming a homogeneous cream.

1.2. coloring gel

The C, H-acidic compound (component B) was first dissolved with stirring in 20 wt .-% water. With stirring, the Natrosol was added and made up to 100 wt .-% with water. The swelling process was awaited and the resulting gel was stirred well again.

1.3. alkalizing

2. Coloring

2.1 Preparation of the leveling strands

Leveling strands are made by setting off 18 cm strands with 80% gray content (Kerling) in the middle and bleaching in the upper part once with Poly Blonde Ultra (Schwarzkopf & Henkel), in the lower part 2x alternating with Poil Lock normal Welle (Schwarzkopf & Henkel) permed and bleached with Poly Blonde Ultra (Schwarzkopf & Henkel). In this way, different damaged areas are obtained in the hair, which make it possible, equalization, ie the Uniformity of the coloration of different damaged hair parts, to check.

2.2 Coloring of the leveling strands

50.0 g of the color cream was mixed with 50.0 g of the gel component and 5.5 g of the alkalizing agent. The resulting application mixtures had a pH of between 9.3 and 9.5. This ready-to-use hair dye was applied to a leveling bar (liquor ratio gel mixture / hair = 2: 1) and evenly distributed with an applicette. After a contact time of 30 minutes at 32 ⁰ C, the tress was rinsed with lukewarm water and then dried in a stream of warm air.

2.3. Measurement of dE values

After the dyeing process, the leveling strands were measured colorimetrically using a Datacolor Spectraflash 450 colorimeter. On each tress, 6 measurements were made at the top and 6 measurements at the bottom of the tress, and the readings per tress part per tress were averaged. To simulate the washing process, the hair strands were placed for 15 minutes in an ultrasonic bath from Elma (type T 790 / H, level 5), which was filled with a 1% Texapon NSO-UP solution. After drying, a new colorimetric measurement was carried out in the upper and in the lower part of the hair strand.

The dE value used for the assessment of the leveling power results from the L * a ^* b ^* colorimetric values as follows: dE = [(Li-L ₀ ) ² + (a, -a ₀ ) ² + (b, -b ₀ )] ¹ ' ²

L ₀ , a ₀ and b ₀ are the colorimetric values in the upper, hardly damaged part of the

Strand of hair, while L ₁ , a-, and bi are the color readings in the lower, severely damaged

Represent part of the strand of hair.

2.4. Assessment of the leveling ability

The dE value indicates the color difference that exists between the less damaged portion of the hair strand and the severely damaged portion of the hair strand. The leveling power is the worse, the greater the dE value. The dE values were determined both directly after the dyeing process and after 6 hair washes. Dyeing results and dE values are summarized in Table 4.

As components A, B and C, the following substances were used:

Component A

Al 4-formyl-1-methylquinolinium p-toluenesulfonate

Component B

B1, 2-dihydro-1, 3,4,6-tetramethyl-2-oxopyrimidinium hydrogen sulfate

Component C

C1 4-hydroxy-2-methoxybenzaldehyde

Table 4: Staining results

3.0 example colorant

3.1.1 cream component

3.1.2: gel component

The two-component colorants F1 to F9 each consist of a cream component and a gel component. 50.0 g of the cream component was mixed with 50.0 g of the corresponding gel component. This ready-to-use hair dye thus obtained was applied to a strand of human hair with 80% gray content (Kerling) (liquor ratio of colorant / hair = 2: 1) and distributed evenly with an applicette. After a contact time of 30 minutes at 32 ⁰ C, the tress was rinsed with lukewarm water and then dried in a stream of warm air.

3.2.1 cream component

3.2.2 Dispersion component

The two-component colorants F10 to F19 each consist of a cream component and a dispersion component. 50.0 g of the cream component was mixed with 50.0 g of the corresponding dispersion component. This ready-made hair dye thus obtained was applied to a tress Human hair with 80% gray content (Fa Kerling) applied (liquor ratio colorant / hair = 2: 1) and evenly distributed with an Applicette. After a contact time of 30 minutes at 32 ⁰ C, the tress was rinsed with lukewarm water and then dried in a stream of warm air.

Claims

Patent claims

1. An agent for dyeing keratin fibers, in particular human hair, containing in a cosmetic carrier a combination of (A) at least one compound according to formula (I) or its hydrate

wherein R ^{1 is} a (C _r C ₆ ) alkyl group, (C ₂ -C ₆ ) alkenyl group, aryl group, aryl (C _r C ₆ ) alkyl group or heteroaryl (C _r C ₆ ) alkyl group,

R ² and R ³ are each independently a hydrogen atom, a halogen atom, a (Ci-C ₆₎ alkyl group, a (CrC ₆₎ alkoxy, hydroxy (C _r C ₆₎ alkoxy group, hydroxy group, nitro group, aryl group, trifluoromethyl group , Amino group which may be substituted by (C _r C ₆ ) -alkyl groups, or denote (C _r C ₆ ) -acyl group and

A ^{~ means} a physiologically acceptable anion

(B) at least one heterocyclic, CH-acidic compound and (C) at least one aromatic aldehyde derivative other than compounds of formula (I).

2. Composition according to claim 1, characterized in that the formyl group -CHO binds in 2- or 4-position.

3. Composition according to claim 1 or 2, characterized in that in formula (I) R ^{1 is} a (CrC ₆ ) alkyl group.

4. Composition according to one of claims 1 to 3, characterized in that the compound of formula (I) is selected from the group consisting of the benzenesulfonates, p-toluenesulfonates, methanesulfonates,

Trifluoromethanesulfonates, perchlorates, sulfates, chlorides, bromides, iodides and / or tetrachlorozincates of 4-formyl-i-methylquinolinium and 2-formyl-1-methylquinolinium and the hydrates of the aforementioned compounds.

5. Composition according to one of claims 1 to 4, characterized in that the heterocyclic, CH-acidic compound is selected from at least one compound of formula (II) and / or (III) and / or (IV),

wherein

R ⁴ and R ⁵ are independently a linear or cyclic C ₁ - C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl -C ₆ alkyl group, a CVCβ -Hydroxyalkyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl group, a group R ¹ R ¹¹ N- (CH ₂ ) _P -, wherein R ¹ and R "independently represent a hydrogen atom, a C 1 -C ₄ -alkyl group, a C 1 -C ₄ -hydroxyalkyl group or an arylCrC ₆ -alkyl group, where R ¹ and R ¹¹ together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p is a number 2, 3, 4, 5 or 6,

R ⁶ and R ⁷ independently of one another represent a hydrogen atom or a C 1 -C ₆ -alkyl group, where at least one of the radicals R ⁶ or R ⁷ denotes a C 1 -C ₆ -alkyl group,

R ⁸ represents a hydrogen atom, a C _r C ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - Alkoxy group, a Ci-C ₆ -Hydroxyalkoxygruppe, a group R "RI ^V N- (CH ₂ ) _q -, wherein R ¹ " and R ^IV independently represent a hydrogen atom, a CrCβ-alkyl group, a CrC ₆ -Hydroxyalkylgruppe or an arylC _r C ₆ alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ⁸ together with one of the radicals R ⁶ or R ^{7 is} a 5- or 6-membered can form aromatic ring optionally substituted with a halogen atom, a CrC ₆ alkyl group, a C ₁ -C ₆ - hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ - alkoxy group, a -C ₆ -hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _S -, wherein R ^v and R ^vι independently of one another represent a hydrogen atom, a C 1 -C ₆ -alkyl group, a C 1 -C ₆ -hydroxyalkyl group or an arylCrCβ- alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,

Y ¹ represents an oxygen atom, a sulfur atom or a group NR ^V ", in which R ^v " represents a hydrogen atom, an aryl group, a heteroaryl group, a C _r C ₆ -alkyl group or a C _r C ₆ -arylalkyl group,

X "is a physiologically acceptable anion,

Het is an optionally substituted heteroaromatic,

• X ¹ represents a direct bond or a carbonyl group.

• R ⁹ and R ¹⁰ either form together with the nitrogen atom form a saturated or unsaturated 5- or 6-membered ring, or independently represent a (C _{r C6)} alkyl group, a (C ₂ -C ₆₎ - alkenyl group, a Aryl group, an aryl (C _r C ₆ ) alkyl group, a (C ₂ -C ₆ ) hydroxyalkyl group, a (C ₂ -C ₆ ) polyhydroxyalkyl group or a group R'R "N- (CH ₂ ) _m - in which R ¹ and R ¹¹ independently of one another represent a hydrogen atom, a (C _r C ₆ ) -alkyl group, a (C _r C ₆ ) -alkenyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ¹ and R ^{11 are taken} together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and

R ^{11 is} a hydrogen atom, a (C _r C ₆ ) -alkyl group, a (C ₂ -C ₆ ) -alkenyl group, an aryl group, an AryKd-CeJ-alkyl group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a ( C ₂ -C ₆ ) polyhydroxyalkyl group or a group R '' R ^lv N- (CH ₂ ) _n -, wherein R ¹ "and R ^IV independently represent a hydrogen atom, a (CrCβJ-alkyl group, a (CrC ₆ ) -Alkenyl group or an aryl-CrC ₆ alkyl group, wherein R ¹ "and R ^ιv together with the Nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 2, 3, 4, 5 or 6.

6. Composition according to one of claims 1 to 5, characterized in that the heterocyclic, CH-acidic compound is selected from at least one compound of the group consisting of

where X ^"stands for a physiologically acceptable anion.

7. Composition according to one of claims 1 to 6, characterized in that the aromatic aldehyde derivative is selected from compounds of formula (V),

wherein

• R ^{1 *} , R ^{2 *} and R ^{3 *} independently represent a hydrogen atom, a halogen atom, a C _r C ₆ alkyl group, a hydroxy group, a CVC ₆ - alkoxy group, a C _r C ₆ -Dialkylaminogruppe, a di (C ₂ -C ₆ - hydroxyalkyl) amino group, a di (CrC ₆ alkoxy-C ₆ alkyl) aminoguppe, a C _r C ₆ -Hydroxyalkyloxygruppe, a C ₁ -C ₆ -AIkOXy- (C ₂ -C ₆ ) alkyloxy group, sulfonyl group, carboxy group, sulfonic acid group, sulfonamido group, sulfonamide group, carbamoyl group, C ₂ -C ₆ acyl group or nitro group,

Z 'is a direct bond or a vinylene group,

• R ^{4 *} and R ^{5 *} represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

8. Composition according to one of claim 7, characterized in that the radical R ^{1 * is} a hydroxy group.

9. Composition according to one of claims 1 to 8, characterized in that the aromatic aldehyde derivatives are selected from at least one compound from the group consisting of

10. Composition according to one of claims 1 to 9, characterized in that it additionally contains at least one developer component and optionally at least one coupler component as oxidation dye precursors.

11. Composition according to one of claims 1 to 10, characterized in that it additionally contains at least one substantive dye.

12. Composition according to one of claims 1 to 11, characterized in that it additionally contains at least one surfactant.

13. agent, characterized in that it has a pH between 2 and 11, preferably between 8 and 10.

14. A method for dyeing keratin fibers, in particular human hair, characterized in that an agent according to one of claims 1 to 13 applied to the keratin fibers, some time, usually about 15-30 minutes, left on the fiber and then rinsed again or washed out with a shampoo.

15. Use of a composition according to any one of claims 1 to 13 for dyeing keratin fibers, in particular human hair.