WO2006029712A1 - Polyalkoxylated diaminobenzenes for use as developers - Google Patents

Abstract

The invention relates to products for dyeing keratin fibers, especially human hair, which comprise at least one diaminobenzene derivative of the general formula (I), wherein R<SUP>1</SUP> represents, for example, H, C<SUB>1-6</SUB> alkyl, C<SUB>1-6</SUB> hydroxyalkyl, C<SUB>3-12</SUB> alkoxyalkyl, R<SUP>2</SUP>, R<SUP>3</SUP> represent, for example, H, p is 0, 1 or 2, and q, r are, for example, 2, in a cosmetically acceptable carrier as the dye precursor.

Description

Polyalkoxylated diaminobenzenes as a developer

The present invention relates to agents for coloring keratinic fibers containing specific polyalkoxylated diaminobenzenes as developers, a process for dyeing hair with these agents, and these polyalkoxylated diaminobenzenes themselves and synthetic intermediates.

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

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

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

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

DE-A-27 41 762 and US 4,311,478 relate to p-phenylenediamine derivatives and colorants for keratin fibers. Developers of oxidation dyes for hair coloring are described. In the examples, among others 2,5-diaminophenyl-3-methoxyethyl ether dihydrochloride is listed. In addition, 2,5-diaminophenoxyethanol dihydrochloride is listed. In addition, it is generally stated that the phenyl nucleus may have an alkoxyalkyl-O radical.

Dimer phenylenediamine compounds which have a polyether bridge are described, for example, in DE-A-43 14 317 and DE-A-41 02 907. The compounds are used to dye hair.

Good oxidation dye precursors should form the desired color shades in sufficient intensity and fastness in the oxidative coupling. They should also have a good Aufziehvermögen on the fiber, in particular in human hair no significant differences between strained and freshly regrown hair should exist (leveling). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, eg permanent wave 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 The coloring achieved by bleaching can easily be removed from the hair if it does not meet the individual wishes of the individual and should be reversed.

But with a developer component or coupler component or a special coupler / developer combination, it is generally not possible to obtain a color shade that has a natural effect on the hair. In practice, therefore, combinations of different developer and / or coupler components are usually used. There is therefore a constant need for new, improved dye components which exhibit the above property profile and which are also unproblematic in terms of toxicology and dermatology.

The object of the present invention was therefore to develop new dye precursors or oxidation dye precursors, in particular developer components, which meet the requirements imposed on oxidation dye precursors, also with regard to the toxicological and dermatological properties, and allow dyeings in a broad color spectrum with good fastness properties.

It has been found according to the invention that special polyalkoxylated diaminobenzenes satisfy the requirements imposed on oxidation dye precursors, in particular on developer components, to a high degree. They allow in particular high color intensities, a good leveling and good (light) fastnesses.

A first subject of the invention are therefore agents for coloring keratinic fibers, in particular human hair, containing in a cosmetically acceptable carrier as dye precursor at least one diaminobenzene derivative of the general formula (I)

(I)

with the meaning

R ^1, R ² are independently H, C _1-6 alkyl, Ci _-6 hydroxyalkyl, C _2-6 - polyhydroxyalkyl, C _7- i ₂ arylalkyl, C _3-12 alkoxyalkyl, C _1-6 aminoalkyl , C _2-10 -alkylaminoalkyl, C _3-12 -dialkylaminoalkyl, C _2-6 -alkenyl, acetyl,

R ³ independently of one another H, OH, halogen, NH ₂ , C _1-6 -alkylamino, C ₂ -I ₂ -

Dialkylamino, NO _2, COOH, CN, C _1-6 alkyl, Ci _-6 hydroxyalkyl, C _2-6 -

Polyhydroxyalkyl, C _7-I2 - arylalkyl, C _2-6 alkoxyalkyl, _{Ci-6-aminoalkyl,} C _2-10 - alkylaminoalkyl, C ₃ -] ₂ dialkylaminoalkyl, C _1-6 alkoxy, C _2-6 - alkenyl .

p 0, 1 or 2,

q integer from 2 to 6

r integer from 2 to 6

or a salt of it.

The invention particularly relates to agents for the oxidative dyeing of keratinic fibers which contain at least one dye precursor of the general formula (I). According to the invention, keratinic fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the oxidation dyes according to the invention are primarily suitable for dyeing keratin fibers, in principle, there is nothing to prevent their use in other fields, in particular in color photography.

The dye precursors of the general formula (I) are characterized by a polyether radical and two radicals derived from amino groups, which are covalently bound to a benzene nucleus. An amino group is present in the o-position to the polyether group. These are developer components used in oxidative hair dyeing.

Each of the radicals indicated, for example R ³ , can have a different meaning in each of the given positions. However, it is also possible that the radicals have the same meanings. In the compounds of the general formula (I), there are preferably zero, one or two radicals R ³ other than hydrogen. Particularly preferably, there is no radical R ³ different from hydrogen.

Since the derivatives according to the invention are amino compounds, the known acid addition salts can be prepared therefrom in the customary manner. The invention therefore relates both to the compounds present in free form and to their water-soluble, physiologically tolerated salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred.

Examples of the C ₁ -C ₆ -alkyl groups which are mentioned as substituents in the compounds according to the invention, preferably C ₁ -C ₄ -alkyl groups which may be linear or branched, are the groups methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl. Ethyl and methyl are preferred alkyl groups. As a preferred C ₁ to C ₆ (mono) hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. C _3-12 Alkoxyalkylreste have a total of 3 to 12 carbon atoms, which are distributed over the alkoxy and the alkyl radical. It can thus be present in the alkoxy or alkyl radical in each case up to 11 carbon atoms. It is preferably a C i _-6- alkoxy-C _2-6 - alkyl radical, more preferably C _1-2 alkoxy-C _2-3 - alkyl radical. Both the alkoxy and the alkyl moiety may be linear or branched. They are preferably linear and thus correspond to the formula H ₃ C- (CH ₂ ) _n -O- (CH ₂ ) _m - with n integer from 0 to 5, preferably 0 or 1, m integer from 2 to 6, preferably 2 or 3. Ci- ₆ -Aminoalkylreste, preferably Ci _-4 -Aminoalkylreste, C _2- I ₀ - Alkylaminoalkylreste, preferably C _2-6 -Alkylaminoalkylreste and C ₃ -I2 - Dialkylaminoalkyl radicals, preferably C _3-9 -dialkylaminoalkyl radicals, can each have linear or branched alkyl radicals. Each individual alkyl group preferably has 1 to 3 carbon atoms. The alkyl radicals present in the respective groups are preferably as defined above for the pure alkyl radicals. Arylalkyl radicals are preferably phenyl-C 1-4 -alkyl radicals. Dihydroxyalkyl radicals preferably have OH groups on non-adjacent C atoms.

Halogen is preferably fluorine, chlorine or bromine, in particular chlorine. C _1-6 - alkylamino is particularly preferably Ci _-4 alkylamino, especially methylamino or ethylamino. C ₂ i ₂ dialkylamino preferably di-Ci- ₄ alkylamino, especially dimethylamino or diethylamino.

Particularly preferably, a derivative of general formula (I) has a total of at most two OH groups, preferably at most one OH group. There are preferably in the derivative of the general formula (I) preferably a maximum of four nitrogen atoms, more preferably two nitrogen atoms. Overall, apart from the hydroxyl groups, in the derivative of the general formula (I) a maximum of five further oxygen atoms, preferably a maximum of four further oxygen atoms, in particular a maximum of three further oxygen atoms.

Preferred meanings of the radicals are listed below.

Preferably, R ^{1 is} H, C _1-6 alkyl, C _2-6 alkenyl or alkoxyalkyl of the formula H ₃ C- (CH ₂ ) _n -O- (CH ₂ ) _m - with n integer from 0 to 5 and m integer from 2 to 6.

Preferably, R ² is H, Ci _-6 alkyl, Ci _-6 hydroxyalkyl, C _2-6 polyhydroxyalkyl or acetyl.

Preferably R ³ is independently H, Ci _-6 alkyl, _C2-6 alkenyl, Ci _-6 - hydroxyalkyl, C _2-6 polyhydroxyalkyl radical, OH, Ci _-6 alkoxy or halogen. Preferably q is 2 or 3 and r or 2 or 3. In the derivative of general formula (I), R ¹ particularly preferably denotes H, C _1-4 -alkyl or H ₃ C- (CH ₂ ) _n -O- (CH ₂ ) _m - where n is 0 or 1 and m is 2 or 3 , R ² is H, C _M alkyl or Ci _-4 - hydroxyalkyl, R ³ is H, q and r is 2 or 3, and p is zero.

In particular, R ^{1 is} H, CH ₃ or CH ₃ -O-CH ₂ -CH ₂ -, R ^{2 is} H and R ^{3 is} H, q is 2 or 3, r 2 and p is zero.

Furthermore, R ² is particularly preferably H, methyl and 2-hydroxyethyl.

When R ^{2 is} other than hydrogen, the following compounds are most preferred:

TV- {4-amino-2- [2- (2-methoxyethoxy) phenyl} -7 V -methylamine,

2- ({4-amino-2- [2-methoxyethoxy) ethoxy] phenyl} amino) ethanol,

2- [2- [5-amino-2- (methylamino) phenoxy] ethoxy} ethanol and

2- ({4-amino-2- [2- (2-hydroxyethoxy) ethoxy] phenyl} amino) ethanol.

Particularly preferred compounds according to the invention are 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine, 2- {2- [2- (2-methoxyethoxy) ethoxy] ethoxy} benzene-1, 4- diamine, 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol, 2- [3- (2-methoxyethoxy) propoxy] benzene-1,4-diamine.

Most preferably, the two compounds are 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 2- [2- (2,5-)

Diaminophenoxy) ethoxy] ethanol.

The composition of the invention may contain one or more, for example at least two different derivatives of the general formula (I). The derivatives of the formula (I) can be prepared by conventional organic methods, for. B. according to DE-A-2741762 and US 4,311,478. For example, reference is made at this point to the experimental procedures in the context of the embodiments.

The compositions according to the invention for, in particular oxidative, dyeing of keratinic fibers preferably contain at least one derivative of the general formula (I) in an amount of 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, more preferably 0, 1 to 3 wt .-%, based on the finished agent.

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

A general composition is given below:

Developer 0.05 - 5%

Coupler 0.05 - 5%

Surfactants, emulsifiers 0.1 - 20% fatty alcohols and other emulsifiers 0.5 - 20%

Complexing agent 0.05 - 10%

Buffering agent 0.1 - 1.0%

Solubilizer + solvent 0.5 - 15% pH adjuster as needed

Perfume oils 0.1 - 0.6%

Polymers 0.1 - 5%

Water 50 - 98% Suitable colorant compositions are described, for example, in DE-Ul-2 99 11 819, DE-A-1 025 451, DE-Ul-201 11 036, Kosmetik, ed. W. Umbach, 2nd ed. 1995, G. Thieme Verlag Stuttgart , New York.

In addition to the derivatives of the formula (I), the colorants according to the invention may further comprise at least one further developer component.

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

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

in which

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

G ² represents a hydrogen atom, a Ci to C ₄ alkyl radical, a Ci to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (Ci -C ₄₎ - alkoxy- (Ci to C ₄ ) alkyl or C 1 to C ₄ alkyl substituted with a nitrogen containing group; G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a Ci to C ₄ alkyl, C) - to C ₄ -

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

Hydroxyalkoxy, a Ci- to C ₄ -acetylaminoalkoxy, a Ci- to C ₄ -

Mesylaminoalkoxy radical or a Cr to C ₄ carbamoylaminoalkoxy radical;

G ⁴ represents a hydrogen atom, a halogen atom or a Cr to C ₄ -

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

To form ethylenedioxy group.

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

Particularly preferred p-phenylenediamines of the formula (III) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, 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 ₅ N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-

Hydroxyethyloxy) -p-phenylenediamine, 2- (β-acetylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H -imidazol-1-yl) propyl] amine, and phenyl or C _1-6 -alkylphenyl may also generally be present instead of 3-methylphenyl and 5,8-diaminobenzo-l, 4-dioxane and their physiologically tolerated salts.

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

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

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

in which:

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

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

Alkylene ring containing one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or

Nitrogen atoms may be interrupted or terminated and may be substituted by one or more hydroxyl or Ci to C ₈ alkoxy, or a direct bond,

G ⁵ and G ⁶ are each independently a hydrogen or halogen atom, a Ci to C ₄ alkyl radical, a Ci to C ₄ monohydroxyalkyl radical, a C ₂ - to

C ₄ - Polyhydroxyalkylrest, a Ci to C ₄ -Aminoalkylrest or a direct

Connection to the bridge Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² are each independently

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

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

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

Very particularly preferred 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, 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-tetraoxadecane or one of its physiologically tolerable salts.

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

in which: G ¹³ represents a hydrogen atom, a halogen atom, a Ci to C ₄ alkyl radical, a Ci to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy , alkyl (Ci to C ₄₎ a Ci to C ₄ aminoalkyl radical, a hydroxy (Ci to _C4) alkylamino group, a Ci to C ₄ -Hydroxyalkoxyrest, a Ci to C ₄ hydroxyalkyl (Ci-bis C ₄ ) -aminoalkylrest or a (di-Ci- bis

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

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

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

(C ₁ - to C ₄₎ alkyl alkoxy- (Ci to _C4), a Ci to C ₄ -aminoalkyl radical or a Ci to C ₄ -Cyanoalkylrest,

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 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-Dichlθφhenol, 4-amino-2- (diethyl-aminomethyl) -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 additional 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 additional 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-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German patent DE 2 359 399, Japanese laid-open specification JP 02019576 A2 or in published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- 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-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 the pyrazolo [1,5-a] pyrimidine of the following formula (E4) and their tautomeric forms, if a tautomeric equilibrium exists:

in which:

G, G, G and G are independently a hydrogen atom, a Ci to C ₄ alkyl radical, an aryl radical, a Ci to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ polyhydroxyalkyl radical a (CJ to C ₄₎ alkoxy (Ci -C ₄₎ - alkyl group, a Ci to C ₄ -aminoalkyl radical, which may be optionally protected by an acetyl ureide or a sulfonyl residue, a (Ci to C ₄ Alkylamino- (Ci- to C ₄ ) -alkyl radical, a di - [(Ci- to C ₄ ) -alkyl] - (Ci- to C ₄ ) -aminoalkyl radical, wherein the dialkyl radicals optionally have a carbon cycle or a heterocycle form a C to C ₄ - hydroxyalkyl or a di- (Cr to C ₄ ) - [hydroxyalkyl] - (Cr 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 (C , i- alkyl to C ₄₎ a di - [(C _r to C ₄₎ alkyl] - (Ci to C ₄₎ - aminoalkyl, wherein the dialkyl residues optionally form a carbocycle or a heterocycle with 5 or 6 chain links a Ci to C ₄ - hydroxyalkyl or a di- (Ci to C ₄ hydroxyalkyl) aminoalkyl group, a Amino, a C 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 (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

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

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

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

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

Pyrazole [l, 5-a] pyrimidine-3,5-diamine;

2,7-dimethyl-pyrazolo [1,5-a] -pyrimidine-3,5-diamine; 3-aminopyrazole [l, 5-a] pyrimidin-7-ol;

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

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

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

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

2 - [(7-aminopyrazole [l, 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 [l, 5-a] -pyrimidines of the above formula (E4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.

In a further preferred embodiment, the colorants according to the invention contain at least one coupler component.

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

Coupler components which are preferred according to the invention are m-aminophenol and derivatives thereof, 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-diarninobenzene and its derivatives such as 2,4-

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

2,6-Bis- (2'-hydroxyethylamino) -1-methylbenzene and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -2 -methoxy-5-methylphenyl} amino) ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 2- ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - [(3-morpholin-4-yl-phenyl) -amino] -ethanol, 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-dimethoxy,

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,

Moφholinderivate such as 6-hydroxybenzomorpholine and 6-amino benzomoφholin,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Pyrazole derivatives such as, for example, 1-phenyl-3-methylpyrazol-5-one, Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-

Trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-aminobenzene 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, 2,6-dihydroxy-3,4-dimethylpyridine, 2- ({3 - [(2 -Hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol and 2 - [(3 Morpholine-4-ylphenyl) amino] ethanol.

Particularly preferred combinations of compounds of the general formula (I) according to the invention are

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and resorcinol 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 2-methylresorcinol 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 4-chlororesorcinol 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and resorcinol monomethyl ether 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and and m-aminophenol

2- [2- (2,5-Diaminophenoxy) ethoxy] ethanol and and 5-amino-2-methylphenol

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 5- (2'-hydroxyethyl) amino-2-methylphenol

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 5- (3'-hydroxypropyl) amino-2-methylphenol

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 3-amino-2-chloro-6-methylphenol

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 2,4-dichloro-3-aminophenol

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 5-amino-4-chloro-2-methylphenol

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 2-amino-3-hydroxypyridine 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 3-ammo-2-methylamino-6-methoxy - pyridine

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 1-naphthol 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 2-methyl-1-naphthol 2- [2- (2, 5-diaminophenoxy) ethoxy] ethanol and 2,7-dihydroxynaphthalene

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and 1,3-bis (2 ', 4'-diaminophenoxy) propane

2- [2- (2,5-diaminophenoxy) ethoxy] ethanol and

1-Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene

2- [2- (2-Methoxyethoxy) ethoxy] benzene-1,4-diamine and resorcinol 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 2-methylresorcinol 2- [2- (2- 2-methoxyethoxy) ethoxy] benzene-1, 4-diamine and 4-chlororesorcinol 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and resorcinol monomethyl ether 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and and m-aminophenol

2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 5-amino-2-methylphenol

2- [2- (2-methoxyethoxy) ethoxy] benzene-1, 4-diamine and

5 - (2'-hydroxyethyl) amino-2-methylphenol

2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and

5- (3'-hydroxypropyl) amino-2-methylphenol

2- [2- (2-Methoxyethoxy) ethoxy] benzene-1,4-diamine and 3-amino-2-chloro-6-methylphenol

2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 2,4-dichloro-3-aminophenol

2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 5-amino-4-chloro-2-methylphenol

2- [2- (2-Methoxyethoxy) ethoxy] benzene-1,4-diamine and 2-amino-3-hydroxypyridine 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 3-amino 2-methylamino-6-methoxypyridine

2- [2- (2-Methoxyethoxy) ethoxy] benzene-1,4-diamine and 1-naphthol 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 2-methyl-1-naphththol 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 2,7-dihydroxynaphthalene

2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine and 1,3-bis (2 ', 4'-diaminophenoxy) propane 2- [2- (2-methoxyethoxy) ethoxy] benzene 1,4-diamine and 1-methoxy-2-amino-4- (2'-hydroxyethylamino) benzene

In a further embodiment of the present invention, the colorants may contain at least one precursor of a naturally-analogous dye. As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. 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 precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (IIa),

in the independently of each other

- R ¹ represents hydrogen, a dC ₄ alkyl group or a C ₁ -C ₄ -Hy droxy-alkyl group,

R ² is hydrogen or a -COOH group, where the -COOH group may also be in the form of a salt with a physiologically compatible cation, R ³ is hydrogen or a Q-G 1 -alkyl group,

R ⁴ is hydrogen, a C rG _t -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a QQ-alkyl group, and R ⁵ is one of the groups mentioned under R ⁴ , and physiologically acceptable salts thereof Compounds with an organic or inorganic acid.

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

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxy-indoline and in particular the 5,6-Dihydroxyindolin.

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

in the independently of each other

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

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

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

R ⁴ is hydrogen, a QQ-alkyl group or a -CO-R ⁶ group in which

R ⁶ is a Ci-C ₄ alkyl group, and

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

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

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

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with anorga¬ African or organic acids, eg. 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.

In addition to the derivatives of the formula (I) according to the invention, in a further preferred embodiment of the present invention, the colorants according to the invention may contain one or more substantive dyes for shading. Direct dyes are usually 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 (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2 - (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5- chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid acid, 6-nitro-l, 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 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, to which reference is explicitly made at this point in claims 6 to 11 are called.

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

CH ₃ SO ₄ ^'

Cl ^"

(DZ3)

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

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

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

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

With regard to the dyes which can be used in the hair-dyeing and tinting compositions according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the European Inventory of Cosmetic Raw Materials ", published by the European Community, available in disk form from the Bundesverband Deutscher Industrial and commercial enterprise for medicaments, reform goods and Körperpflegemit tel eV, Mannheim, taken reference.

The compositions according to the invention preferably comprise at least one care substance selected from cationic surfactants, polymers, UV filters, vitamins, provitamins, their precursors and derivatives, plant extracts, carboxylic acids, protein hydrolysates or their derivatives, ecotin or ecotin derivatives, allantoin, taurine, bisabolol, amino acids, mono and oligosaccharides, silicone oils, silicone gums, lipids, oily bodies, enzymes and mixtures thereof.

Within the scope of a preferred embodiment, the agent according to the invention contains at least one cationic surfactant as a care substance.

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

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex®, Dehyquart® and Armocare®. The products Armocare® VGH-70, an N, N-bis (2-palmitoyloxy) ethyl) dimethylammonium chloride, as well as Dehyquart® F-75, Dehyquart® C-4046, Dehyquart® L80 and Dehyquart® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A compound of this group of substances which is particularly suitable according to the invention is stearamidopropyl-dimethylamine, which is commercially available under the name Tegoamid® S 18.

The nourishing cationic surfactants are contained in the compositions according to the invention preferably in amounts of from 0.05 to 10% by weight, based on the total application preparation. Amounts of 0.1 to 5 wt .-% are particularly preferred.

In the context of a further preferred embodiment of the present invention, the agents contain as care substance at least one nourishing polymer.

A first group of caring polymers are the cationic polymers. Cationic polymers are polymers according to the invention which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group are bound via a Ci _-4 hydrocarbon group to a synthesized from acrylic acid, methacrylic acid or derivatives thereof, polymer backbone have been found to be particularly suitable. Homopolymers of the general formula (GI-I),

R ¹

- [CH ₂ -CJ _n X ^" (Gl-I)

CO-O- (CH ₂ ) H ₁ -N ⁺ R ² R ³ R '

R ¹ = -H or -CH _3, R ^2, R ³ and R ⁴ are independently selected from Ci _-4 alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X- is a physiologically acceptable organic or inorganic anion, as well as copolymers consisting essentially of the monomer units listed in formula (GI-I) and nonionic monomer units, are particularly preferred cationic polymers. In the context of these polymers, those are preferred according to the invention for which at least one of the following conditions applies: R ¹ is a methyl group R ² , R ³ and R ⁴ are methyl groups m has the value 2.

Suitable physiologically tolerated counterions X ^" are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions, preference being given to halide ions, in particular chloride.

A particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. The crosslinking can, if desired, be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent. The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such Polymer¬ are dispersions under the names Salcare ^® SC 95 (about 50% polymer content, wei¬ tere components: mineral oil (INCI name: Mineral Oil) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI name: PPG l trideceth-6)) and Salcare ^® SC 96 (about 50% polymer content, additional components: polyoxypropylene tridecyl propylene glycol Dicaprylate / Dicaprate) and: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name polyoxyethylene ether (INCI name: PPG-l-trideceth-6)) are commercially available.

Copolymers containing monomer units according to formula (Gl-I) as non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid-Ci _-4 alkyl ester and methacrylic acid-Ci _-4 alkyl ester. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

Further preferred cationic polymers are, for example

- Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® are commercially available. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives

cationic alkyl polyglycosides according to DE-PS 44 13 686,

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

- cationic guar derivatives, such as in particular the products sold under the trade names Cosme- dia ^® Guar and Jaguar ^®,

Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized Trimethylsilylamodi- methicone), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone) , SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® Quat 3270 and 3272 (manufacturer: Th. Goldschmidt), diquaternary polydimethylsiloxanes, quaternium-80), polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers,

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially - vinylpyrrolidone vinylimidazoliummethochloride copolymers as among the Be¬ drawings Luviquat.RTM ^® FC 370, FC 550, FC 905 and HM offered 552, quaternized polyvinyl alcohol, and the polymers known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 with quaternary nitrogen atoms in the polymer main chain.

It is likewise possible to use as nourishing cationic polymers those known under the names Polyquaternium-24 (commercial product eg Quatrisoft® LM 200). Also usable in accordance with the invention are the copolymers of vinylpyrrolidone, such as available as commercial products Copolymer 845 (manufacturer: ISP), Gaffix® VC 713 (manufacturer: ISP), Gafquat®ASCP 1011, Gafquat®HS 110, Luviquat® 8155 and Luviquat® MS 370 are.

Other nourishing cationic polymers according to the invention are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as a quaternary ammonium group and thus cationically. Preference is given, for example, to chitosan and its derivatives, as are freely available commercially, for example, under the trade names Hydagen® CMF, Hydagen® HCMF, Kytamer® PC and Chitolam® NB / 101. Nursing cationic polymers preferred according to the invention are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer® JR 400, Hydagen® HCMF and Kytamer® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat® 50, cationic Alkylpolyglycodside according to DE-PS 44 13 686 and polymers of the type Polyquaternium-37.

Furthermore, cationized protein hydrolyzates are to be counted among the cationic polymers, wherein the underlying protein hydrolyzate from the animal, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, soy or almonds, marine life forms, for example from fish collagen or algae, or biotechnologically derived protein hydrolysates. The protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons up to several thousand daltons. Preference is given to those cationic protein hydrolyzates whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolyzates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationic protein hydrolysates and derivatives according to the invention, those mentioned under the INCI names in the "International Cosmetic Ingredient Dictionary and Handbook", (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 ^th Street, NW, Suite 300 Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimopnium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyl Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Lauridimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lau Ryldimonium Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

Very particular preference is given to the cationic protein hydrolysates and derivatives based on plants.

Further care polymers which can be used according to the invention are the amphoteric compounds mentioned in British Offenlegungsschrift 2,104,091, European Offenlegungsschrift 47,714, European Offenlegungsschrift 217,274, European Offenlegungsschrift 283,817 and German Offenlegungsschrift 28 17 369. Preferred amphoteric polymers are those polymers which are composed essentially of one another

(a) monomers having quaternary ammonium groups of the general formula (II), R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ³ R ⁴ R ⁵ A ^w (II) in the R ¹ and R ² independently of one another represent hydrogen or a methyl group and R ³ , R ⁴ and R ⁵ independently of one another represent alkyl groups having 1 to 4 carbon atoms, Z an NH group or an oxygen atom, n an integer from 2 to 5 and

A is the anion of an organic or inorganic acid, and

(B) monomeric carboxylic acids of general formula (III), R ⁶ -CH = CR ⁷ -COOH (III) in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention. With regard to the details of the preparation of these polymers, reference is expressly made to the content of German Offenlegungsschrift 39 29 973. Very particular preference is given to those polymers in which monomers of the type (a) are used in which R ³ , R ⁴ and R ^{5 are} methyl groups, Z is an NH group and A is a halide, methoxysulfate or ethoxysulfate ion ; Acrylamido-propyl-trimethyl-ammonium chloride is a particularly preferred monomer (a). Acrylic acid is preferably used as monomer (b) for the stated polymers. The compositions according to the invention preferably contain the nourishing cationic polymers in an amount of 0.01 to 5% by weight, in particular in an amount of 0.1 to 2% by weight, in each case based on the total application preparation.

Within the scope of a further preferred embodiment, the compositions according to the invention contain as care substance at least one UV filter. The UV filters suitable according to the invention are not subject to any general restrictions with regard to their structure and their physical properties. On the contrary, all UV filters which can be used in the cosmetics sector and whose absorption maximum lies in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (<280 nm) range are suitable. UV- Filters having an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

The UV filters preferred according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters.

Examples of UV filters which can be used according to the invention are 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline-methyl sulfate, 3,3,5-trimethylcyclohexylsilicylate (homosalates ), 2-hydroxy-4-methoxy-benzophenone (benzophenone-3; Uvinul ^® M 40, Uvasorb MET ^{®, ®} Neo Heliopan BB, Eusolex ^® 4360), 2-Phenylbenzimida- zol-5-sulfonic acid and potassium, sodium - and triethanolamine (Phenylbenzimi- dazole sulfonic acid; Parsol ^® HS; Neo Heliopan Hydro ^®), 3,3 '- (l, 4-phenylenedimethylene) - bis (7,7-dimethyl-2-oxo-bicyclo [2.2. 1] hept-l-yl-methane-sulfonic acid) and salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1, 3-dione (butyl methoxydibenzoyl- methane; Parsol ^® 1789 Eusolex ^® 9020), α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul ^® P 25), 4-Dimethylaminobenzoesäure- 2-ethylhexyl (octyl dimethyl PABA; Uvasorb ^® DMO, Escalol ^® 507, Eusolex ^® 6007), Salicylsäur e-2-ethylhexyl ester (octyl salicylate; Esca lol ^® 587, Neo Heliopan OS ^®, Uvinul ^® 018), 4-methoxycinnamic acid isopentyl (isoamyl p-methoxycinnamate; Neo Heliopan E 1000 ^®), 4-methoxycinnamic acid 2-ethylhexyl ester (Octyl Methoxycinnamate; Parsol ^® MCX , Escalol ^® 557, Neo Heliopan AV ^®), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (Benzophenone-4; Uvinul ^® MS 40; Uvasorb S 5 ^®), 3- (4'-methylbenzylidene) - D, L-camphor (4-Methylbenzyli- dene camphor; Parsol ^® 5000, Eusolex ^® 6300), 3-benzylidene camphor (3-benzylidene camphor), 4-isopropylbenzyl, 2,4,6-trianilino- (p -carbo-2'-ethylhexyl-1'-oxi) -l, 3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N- {(2 and 4) - [2-oxoborn -3-ylidenemethyl] benzyl} -acrylamids, 2,4-dihydroxybenzophenone (none benzophenone-1; Uvasorb ^® 20 H, Uvinul ^® 400), l, l'-Diphenylacrylonitrilsäure-2-ethylhexyl ester (Octocrylene; Eusolex ^® OCR , Neo Heliopan ^® Type 303, Uvinul ^® N 539 SG), o-aminobenzoic benzoic acid menthyl (menthyl Anth ranilate; Neo Heliopan MA ^®), 2,2 ', 4,4'-tetrahydropyran droxybenzophenon (benzophenone-2; Uvinul ^® D-50), 2,2'-dihydroxy-4,4'-dimethoxy- Jo

benzophenone (benzophenone-6), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-natrium sulfonate and 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester. Preference is given to 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline-methyl sulfate, 3, 3, 5-trimethyl cyclohexyl salicylate, 2-hydroxy-4-methoxy-benzophenone , 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3'- (1,4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo-bicyclo- [2.2. 1] hept-1-yl-methanesulfonic acid) and salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione, α- (2- Oxoborn-3-ylidene) -toluene-4-sulfonic acid and its salts, ethoxylated 4-aminobenzoic acid ethyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl salicylate, isopentyl 4-methoxycinnamate, 4-methoxycinnamic acid 2 ethylhexyl ester, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3- (4'-methylbenzylidene) -D, L-camphor, 3-benzylidene-camphor, 4-isopropylbenzylsalicylate, 2,4,6 Trianilino (p-carbo-2'-ethylhexyl-r-oxi) -l, 3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of the N- {(2 and 4) - [2-oxoborn-3-ylidenemethyl] benzyl} -acrylamide. Very particularly preferred according to the invention are 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 1- (4-tert-butylphenyl) -3- ( 4-methoxyphenyl) -propane-1,3-dione, 4-methoxycinnamic acid 2-ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor.

Preference is given to those UV filters whose molar extinction coefficient at the absorption maximum is above 15,000, in particular above 20,000.

Furthermore, it has been found that, in structurally similar UV filters, the water-insoluble compound in the context of the teaching according to the invention has the higher effect than those water-soluble compounds which differ from it by one or more additional ionic groups. In the context of the invention, water-insoluble UV filters are to be understood which dissolve at 20 ° C. to not more than 1% by weight, in particular not more than 0.1% by weight, in water. Furthermore, these compounds should be soluble in the usual cosmetic oil components at room temperature to at least 0.1, in particular at least 1 wt .-%). The use of water-insoluble UV filters can therefore be preferred according to the invention. According to a further embodiment of the invention, preference is given to UV filters which have a cationic group, in particular a quaternary ammonium group.

These UV filters have the general structure U - Q.

The structural part U stands for a UV-absorbing group. In principle, this group can be derived from the known UV filters which can be used in the cosmetics sector and in which a group, generally a hydrogen atom, of the UV filter is replaced by a cationic group Q, in particular with a quaternary amino group. function, is replaced.

Compounds from which the structural part U can be derived are, for example, substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters,

Salicylic acid ester,

Benzimidazoles and

o-aminobenzoic acid ester.

Structural parts U, which are derived from cinnamic acid amide or from N, N-dimethylaminobenzoic acid amide, are preferred according to the invention.

The structural parts U can in principle be chosen such that the absorption maximum of the UV filters can be in both the UVA (315-400 nm) and in the UVB (280-315 nm) or in the UVC (<280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

Furthermore, the structural part U, also as a function of structural part Q, is preferably selected so that the molar extinction coefficient of the UV filter at the absorption maximum is above 15,000, in particular above 20,000. The structural part Q preferably contains a quaternary ammonium group as the cationic group. This quaternary ammonium group can in principle be connected directly to the structural part U, so that the structural part U represents one of the four substituents of the positively charged nitrogen atom. Preferably, however, one of the four substituents on the positively charged nitrogen atom is a group, especially an alkylene group of 2 to 6 carbon atoms, which functions as a compound between the structural portion U and the positively charged nitrogen atom.

Advantageously, the group Q has the general structure - (CH ₂ ) _X -N ⁺ R ¹ R ² R ³ X ^' , in which x is an integer from 1 to 4, R ¹ and R ^{2 are} independently of one another ₄ alkyl groups, R ³ is a Ci _-22- alkyl group or a benzyl group and X ^'is a physiologically acceptable anion. In the context of this general structure, x preferably represents the number 3, R ¹ and R ² each represent a methyl group and R ^{3 represents} either a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain having 8 to 22, in particular 10 to 18, carbon atoms.

Physiologically acceptable anions are, for example, inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions and also organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.

Two preferred UV filters with cationic groups are the compounds keeps handy er¬ as commercial products cinnamic acid-trimethylammonium chloride (quat Incro- ^® UV-283) and dodecyl tosylate (Escalol ^® HP 610).

Of course, the teaching of the invention also includes the use of a combination of several UV filters. In the context of this embodiment, the combination of at least one water-insoluble UV filter with at least one UV filter with a cationic group is preferred. The UV filters are contained in the compositions of the invention usually in amounts of 0.01-5 wt .-%, based on the total application preparation. Amounts of 0.1-2.5% by weight are preferred.

Within the scope of a further preferred embodiment, the compositions according to the invention contain as care substance at least one vitamin, one provitamin, one vitamin precursor and one of their derivatives.

According to the invention, such vitamins, pro-vitamins and vitamin precursors are preferred, which are usually assigned to groups A, B, C, E, F and H.

The group of substances called vitamin A includes retinol (vitamin Ai) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of the Re¬ tinols. As vitamin A component according to the invention, for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as the palmitate and the acetate into consideration. The preparations used according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the total application preparation.

The vitamin B group or the vitamin B complex include u. a.

- Vitamin Bi (thiamine)

- Vitamin B ₂ (riboflavin)

- Vitamin B ₃ . Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. Preferred according to the invention is the nicotinic acid amide, which is preferably present in the compositions according to the invention in amounts of from 0.05 to 1% by weight, based on the total application preparation.

- Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Panthenol and / or pantolactone are preferably used in the context of this group. According to the invention ein¬ settable derivatives of panthenol are in particular the esters and ethers of panthenol and cationically derivatized panthenols. Individual representatives are, for example, the panthenol triacetate, the panthenol monoethyl ether and its monoacetate and the cationic disclosed in WO 92/13829 Panthenol. The said compounds of the vitamin B ₅ type are preferably present in the agents according to the invention in amounts of 0.05-10% by weight, based on the total application preparation. Amounts of 0.1-5 wt .-% are particularly preferred.

Vitamin B ₆ (pyridoxine and pyridoxamine and pyridoxal). The compounds of the vitamin B ₆ type mentioned are preferably present in the agents according to the invention in amounts of from 0.01 to 5% by weight, based on the total application preparation. Levels of 0.05-1 wt% are particularly preferred.

Vitamin C (ascorbic acid). Vitamin C is used in the compositions according to the invention preferably in amounts of 0.1 to 3 wt .-%, based on the total application preparation. Use in the form of palmitic acid ester, glucosides or phosphates may be preferred. The use in combination with tocopherols may also be preferred.

Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, which include in particular the esters such as acetate, nicotinate, phosphate and succinate, are preferably present in the compositions according to the invention in amounts of 0.05-1% by weight, based on the total application preparation.

Vitamin F. The term "vitamin F" is usually understood as meaning essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

Vitamin H. Vitamin H is the compound (3aS, 4S, 6ai?) - 2-oxohexahydrothienol [3,4 - (/] - imidazole-4-valeric acid, for which, however, the trivial name biotin has become established. Biotin is preferably present in the compositions according to the invention in amounts of from 0.0001 to 1.0% by weight, in particular in amounts of from 0.001 to 0.01% by weight, in each case based on the total application preparation.

The agents according to the invention preferably contain vitamins, provitamins and vitamin precursors from groups A, B, C, E and H. Panthenol, pantolactone, pyridoxine and its derivatives as well as nicotinic acid amide and biotin are particularly preferred.

Within the scope of a further preferred embodiment, the agents according to the invention contain at least one plant extract.

Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.

With regard to the plant extracts preferred according to the invention, particular reference is made to the extracts listed in the table beginning on page 44 of the 3rd edition of the guideline for the ingredient declaration of cosmetic products, published by the Industrial Association for Personal Care and Detergent e.V. (IKW), Frankfurt.

The extracts of green tea, oak bark, stinging nettle, witch hazel, hops, henna, camomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot , Lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root.

Particularly preferred are the extracts of green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, lime blossom, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, Rosemary, birch, meadowfoam, quenelle, yarrow, toadstool, meristem, ginseng and ginger root.

Especially suitable are the extracts of green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon. As extracting agent for the preparation of said plant extracts, water, Al¬ alcohols and mixtures thereof can be used. Among the alcohols, lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as the sole extractant and in admixture with water, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

The plant extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80% by weight of active substance and, as solvent, the extractant or extractant mixture used in their extraction.

Furthermore, it may be preferred to use in the compositions according to the invention mixtures of several, especially two, different plant extracts.

In a further embodiment, the compositions according to the invention contain as care substance at least one carboxylic acid.

In the context of the invention, short-chain carboxylic acids may in particular be advantageous. Short-chain carboxylic acids and their derivatives in the context of the invention are understood to mean carboxylic acids which may be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750. For the purposes of the invention, preference may be given to saturated or unsaturated straight-chain or branched carboxylic acids having a chain length of from 1 to 16 C atoms in the chain, very particular preference being given to those having a chain length of from 1 to 12 C atoms in the chain.

The short-chain carboxylic acids according to the invention may have one, two, three or more carboxy groups. Preferred within the meaning of the invention are carboxylic acids having a plurality of carboxy groups, in particular di- and tricarboxylic acids. The carboxy groups can be used, in whole or in part, as ester, acid anhydride, lactone, amide, imidic acid, lactam, Lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, amido-dim, nitrile, phosphonic or phosphate ester. The carboxylic acids according to the invention may, of course, be substituted along the carbon chain or the ring skeleton. The substituents of the carboxylic acids according to the invention are, for example, Q-Cg-alkyl, C ₂ -C ₈ -alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C ₂ -C ₈ -hydroxyalkyl-, C C ₂ -C ₈ hydroxyalkenyl, aminomethyl, C ₂ -C ₈ aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups. Preferred substituents are CrQ alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Particular preference is given to substituents in the α position. Very particularly preferred substituents are hydroxyl, alkoxy and amino groups, where the amino function may optionally be further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals. Furthermore, preferred carboxylic acid derivatives are also the phosphonic and phosphate esters.

Examples of carboxylic acids according to the invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, propiolic acid , Crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoic acid, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, bicarbamic acid, 4,4 '-Dicyano-6,6'-binicotinic acid, 8-

Carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalene pentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propane tricarboxylic acid, a dicarboxylic acid selected from the group consisting of is formed by compounds of general formula (NI),

(NI) in the Z is a linear or branched alkyl or alkenyl group having 4 to 12 carbon atoms, n is a number from 4 to 12 and one of the two groups X and Y is a COOH group and the other is hydrogen or a Methyl or ethyl radical, dicarboxylic acids of the general formula (NI), which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids from the dicarboxylic according to formula (NI) formally by addition of a molecule of water to the double bond in Cyclohexene ring arise.

Dicarboxylic acids of the formula (N-I) are known in the literature. For example, US Pat. No. 3,753,968 discloses a production process.

The dicarboxylic acids of the formula (N-I) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization. Usually one will assume a polyunsaturated fatty acid as the dicarboxylic acid component. Preferred is the linoleic acid obtainable from natural fats and oils. As the monocarboxylic acid component, in particular, acrylic acid, but also e.g. Methacrylic acid and crotonic acid are preferred. Normally, in the case of reactions according to Diels-Alder, mixtures of isomers are formed in which one component is present in excess. These isomer mixtures can be used according to the invention as well as the pure compounds.

In addition to the preferred dicarboxylic acids according to formula (NI), those dicarboxylic acids which differ from the compounds according to formula (NI) by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring or can be used according to the invention from these compounds formally formed by addition of one molecule of water to the double formation of the cyclohexene ring.

The dicarboxylic acid (mixture), which is obtained by reacting linoleic acid with acrylic acid, has proved to be particularly effective according to the invention. It is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid. Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ^{® ®} 1595 (manufacturer: Westvaco).

In addition to the short-chain carboxylic acids of the invention listed above by way of example, their physiologically tolerable salts can also be used according to the invention. Examples of such salts are the alkali metal salts, alkaline earth metal salts, zinc salts and ammonium salts, which in the context of the present application also includes the mono-, di- and trimethyl-, -ethyl- and -hydroxyethyl ammonium salts. However, in the context of the invention, neutralized acids can very particularly preferably be used with alkaline-reacting amino acids, such as, for example, arginine, lysine, ornithine and histidine. Furthermore, it may be preferred for formulation reasons to select the carboxylic acid from the water-soluble representatives, in particular the water-soluble salts.

Furthermore, it is inventively preferred to use 2-pyrrolidinone-5-carboxylic acid and derivatives thereof as the carboxylic acid. Particularly preferred are the sodium, potassium, calcium, magnesium or ammonium salts in which the ammonium ion in addition to hydrogen carries one to three C ₁ - to C ₄ alkyl groups. The sodium salt is most preferred. The amounts used in the inventive compositions are 0.05 to 10 wt.%, Based on the total application preparation, particularly preferably 0.1 to 5, and in particular 0.1 to 3 wt.%.

Furthermore, it is preferred according to the invention to use hydroxycarboxylic acids and here again in particular the dihydroxy, trihydroxy and polyhydroxycarboxylic acids as well as the dihydroxy, trihydroxy and polyhydroxy di-, tri- and polycarboxylic acids. It has been shown that in addition to the hydroxycarboxylic also the Hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be particularly preferred be¬ preferred. Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Further basic hydroxycarboxylic acid esters which are suitable are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols having 8-22 C atoms, ie, for example, fatty alcohols or synthetic fatty alcohols. The esters of Ci ₂ -Ci ₅ fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ^® EniChem, Augusta Industriale. Particularly preferred polyhydroxypolycarboxylic acids are polylactic acid and polyuric acid and their esters.

Within the scope of a further preferred embodiment, the compositions according to the invention contain as care substance at least one protein hydrolyzate and one of its derivatives.

Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, the term protein hydrolyzates also means total hydrolyzates as well as individual amino acids and their derivatives as well as mixtures of different amino acids. Furthermore, according to the invention, polymers made up of amino acids and amino acid derivatives are understood by the term protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc. Further examples of compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-methylsulfonium chloride. Of course, according to the invention, β-amino acids and their derivatives such as β-alanine, anthranilic acid or hippuric acid can also be used. The molecular weight of the protein hydrolysates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons. According to the invention, protein hydrolysates of both vegetable and animal or marine or synthetic origin can be used.

Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois® ^® (Interorgana) Collapuron ^® (Cognis), Nutrilan® ^® (Cognis), Gelita-Sol ^® (German Gelatinefabriken Stoess & Co), Lexein ^® (Inolex) sericin (Pentapharm) and kerasol tm ^® (Croda) sold.

Preferred according to the invention is the use of protein hydrolysates of plant origin, eg. Soybean, almond, pea, potato and wheat protein hydrolysates. Such products are, for example, under the trademarks Gluadin ^® (Cognis), diamine ^® (Diamalt) ^® (Inolex), Hydrosoy ^® (Croda), hydro Lupine ^® (Croda), hydro Sesame ^® (Croda), Hydro tritium ^® (Croda) and Crotein ^® (Croda) available.

Although the use of the protein hydrolysates is preferred as such, amino acid mixtures otherwise obtained may be used in their place, if appropriate. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda), Crosilk ^® (Croda) or Crotein ^® (Croda).

Of course, the teaching according to the invention encompasses all isomeric forms, such as eis - trans - isomers, diastereomers and chiral isomers.

According to the invention it is also possible to use a mixture of several protein hydrolysates.

The protein hydrolysates are present in the compositions according to the invention in concentrations of 0.01% by weight up to 20% by weight, preferably from 0.05% by weight up to 15% by weight and completely particularly preferably in amounts of 0.05% by weight up to 5% by weight, in each case based on the total application preparation.

Within the scope of a further preferred embodiment, the compositions according to the invention contain as care substance ectoin or ectoine derivatives, allantoin, taurine, bisabolol and amino acids.

According to the invention, the term "ectoine and ectoine derivatives" means compounds of the formula (IV)

and / or their physiologically acceptable salt and / or an isomeric or stereoisomeric form, wherein

R ¹⁰ is a hydrogen atom, a branched or unbranched Ci - C ₄ -

Alkyl radical or a C ₂ -C ₄ -hydroxyalkyl radical,

R ¹¹ represents a hydrogen atom, a grouping -COOR ¹⁴ or a grouping -

CO (NH) R ¹⁴ , where R ^{14 is} a hydrogen atom, a C 1 -C ₄ -alkyl radical, a

Amino acid residue, a dipeptide or a tripeptide residue,

R ¹² and R ¹³ are each independently a hydrogen atom, a Ci - C ₄ -

Alkyl radical or one of the two radicals represents a hydroxy group and n represents an integer from 1 to 3.

Suitable physiologically tolerable salts of the general compounds of the formula (IVa) or (IVb) are, for example, the alkali metal, alkaline earth metal, ammonium, triethylamine or tris (2-hydroxyethyl) amine salts and also those resulting from the reaction of compounds according to the formula (IVa) or (FVb) with inorganic and organic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, branched or unbranched, substituted or unsubstituted (for example by one or multiple hydroxy groups) C ₁ -C ₄ -mono- or dicarboxylic acids, aromatic carboxylic acids and sulfonic acids such as acetic acid, citric acid, benzoic acid, maleic acid, fumaric acid, tartaric acid and p-toluenesulfonic acid. Examples of particularly preferred physiologically acceptable salts are the Na, K, Mg and Ca and ammonium salts of the compounds of the formula (IVa) or (IVb), and the salts which are obtained by reacting compounds of the formula (IVa ) or (IVb) with hydrochloric acid, acetic acid, citric acid and benzoic acid.

Isomeric or stereoisomeric forms of the compounds of the formula (IVa) or (IVb) are understood according to the invention to mean all occurring optical isomers, diastereomers, racemates, zwitterions, cations or mixtures thereof.

By the term amino acid, the stereoisomeric forms, e.g. D and L

Forms, the following compounds understood:

Asparagine, arginine, aspartic acid, glutamine, glutamic acid, ß-alanine, γ-

Aminobutyrate, N _e -acetyllysine, Ng-acetylornitine, N _γ -acetyldiaminobutyrate, N _α -

Acetyldiaminobutyrate, histidine, isoleucine, leucine, methionine, phenylalanine, serine,

Threonine and tyrosine.

L-amino acids are preferred. Amino acid residues are derived from the corresponding

Amino acids. The following amino acid residues are preferred:

Gly, Ala, Ser, Thr, VaI, β-Ala, γ-aminobutyrate, Asp, Glu, Asn, AIn, N _ε- acetyllysine, Ng-

Acetylornithine, N _γ -acetyldiaminobutyrate, N _α -acetyldiaminobutyrate.

The short notation of the amino acids was carried out according to the generally customary Schreib¬. The di- or tripeptide radicals are acid amides in their chemical nature and decompose on hydrolysis in 2 or 3 amino acids. The amino acids in the di- or tripeptide moiety are linked together by amide bonds.

With regard to the preparation of the di- and tripeptide radicals, reference is expressly made to EP 0 671 161 A1 of Marbert. Examples of di- and tripeptide radicals can also be found in the disclosure of EP 0 671 161 A1. Examples of C ₁ -C ₄ -alkyl groups in the compounds according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Preferred alkyl groups are methyl and ethyl, methyl is a particularly preferred alkyl group. Preferred C ₂ -C ₄ -hydroxyalkyl groups are the groups 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; 2-hydroxyethyl is a particularly preferred hydroxyalkyl group.

The agents according to the invention preferably contain these active ingredients in amounts of from 0.001 to 2, in particular from 0.01 to 0.5,% by weight, based in each case on the total application preparation.

In the context of a further preferred embodiment, the agent contains as care substance at least one mono- or oligosaccharide.

Both monosaccharides and oligosaccharides, such as cane sugar, lactose and Raffϊnose be used. The use of monosaccharides is preferred according to the invention. Among the monosaccharides, in turn, those compounds which contain 5 or 6 carbon atoms are preferred.

Suitable pentoses and hexoses are, for example, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fucose and fructose. Arabinose, glucose, galactose and fructose are preferably used carbohydrates; Very particular preference is given to using glucose which is suitable both in the D (+) or L (-) configuration or as a racemate.

Furthermore, derivatives of these pentoses and hexoses, such as the corresponding on- and uronic acids (sugar acids), sugar alcohols and glycosides, can also be used according to the invention. Preferred sugars are gluconic acid, glucuronic acid, sugar acid, mannose and mucic acid. Preferred sugar alcohols are sorbitol, mannitol and dulcitol. Preferred glycosides are the methylglucosides. Since the mono- or oligosaccharides used are usually obtained from natural raw materials such as starch, they usually have the configurations corresponding to these raw materials (eg D-glucose, D-fructose and D-galactose).

The mono- or oligosaccharides are preferably present in the hair-treatment compositions according to the invention in an amount of from 0.1 to 8% by weight, in particular from 1 to 5% by weight, based on the total application preparation.

In the context of a further embodiment, the agent according to the invention contains as care substance at least one silicone oil and / or one silicone gum.

Silicones or silicone gums which are suitable according to the invention are in particular dialkyl and alkylaryl siloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated, quaternized or else anionic derivatives.

Examples of such silicones are:

Oligomeric polydimethylcyclosiloxanes (INCI name: cyclomethicone), in particular the tetrameric and the pentameric compound, which are sold as commercial products DC 344 or DC 345 by Dow Corning,

Hexamethyldisiloxane (INCI name: hexamethyldisiloxane), eg. B. the product sold under the name Abil ^® K 520,

Polydimethylsiloxane polymers (INCI name: Dimethicone), z. For example, the products sold under the name DC 200 by Dow Corning,

- Polyphenylmethylsiloxane (INCI name: Phenyl Trimethicone), z. B. the commercial product DC 556 fluid from Dow Corning,

Silicone glycol copolymers (INCI name: Dimethicone Copolyol), z. The commercial products DC 190 and DC 193 from Dow Coming,

Esters and partial esters of silicone glycol copolymers, such as, for example, by the company Fanning under the trade name LIM Fancorsil ^®: marketed, (INCI name dimethicone copolyol Meadowfoamate)

- Dimethylsiloxanes with hydroxy end groups (INCI name: Dimethiconol), z. The commercial products DC 1401 and Q2-1403 from Dow Corning, amino-functional polydimethylsiloxanes and hydroxylamine-modified silicones (INCI name: amodimethicone and quaternium-80, inter alia), such as the commercial products XF42-B1989 (manufacturer GE Toshiba Silicones) Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 939 emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: the General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt),

- anionic silicone oils, such as the product Dow Corning ^® 1784 amino-modified organosilicones, such as the product Abil Soft A843 (manufactured by Osi Specialties).

According to a preferred embodiment, the preparations according to the invention contain a combination of a volatile and a nonvolatile silicone. Volatile in the context of the invention are those silicones which have a volatility which is equal to or greater than the volatility of the cyclic, pentameric dimethylsiloxane. Such combinations are also available as commercial products (eg, Dow ^Corning® 1401, Dow ^Corning® 1403, and Dow ^Corning® 1501, each containing mixtures of a cyclomethicone and a dimethiconol).

According to a particularly preferred embodiment, a dialkylpolysiloxane or one of its derivatives is used. The alkyl groups are preferably methyl, ethyl, i-propyl and n-propyl. Dimethylpolysiloxane or one of its derivatives is particularly preferably used. Preferred are the derivatives of dimethylsiloxane which are amino-functional. A most preferred derivative is commercially available under the INCI name amodimethicones.

The preparations according to the invention preferably contain the silicones in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 5% by weight, based on the total application preparation. Within the scope of a further embodiment, the agent according to the invention contains at least one lipid as a care substance.

Lipids which are suitable according to the invention are phospholipids, for example soya lecithin, egg lecithin and cephalins, and the substances known by the INCI names linoleic amidopropyl PG-dimonium chlorides phosphates, cocamidopropyl PG-dimonium chlorides phosphates and stearamidopropyl PG-dimonium chlorides phosphates. These are sold, for example, by the company Mona under the trade names Phospholipid EF ^A® , Phospholipid ^PTC® and Phospholipid ^SV® .

The preparations according to the invention preferably contain the lipids in amounts of 0.01-10% by weight, in particular 0.1-5% by weight, based on the total application preparation.

In a further embodiment, the agent contains at least one oil body as a care substance.

The natural and synthetic cosmetic oil bodies include, for example:

- vegetable oils. Examples of such oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil and the liquid portions of coconut oil. Also suitable, however, are other triglyceride oils such as the liquid portions of beef tallow as well as synthetic triglyceride oils. liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons and di-n-alkyl ethers having a total of from 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether , Di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether and n-hexyl-n Undecyl ether and di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds are available as commercial products l, 3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol ^® S), and di-n-octyl ether (Cetiol ^® OE) may be preferred. JO

Esteröle. Ester oils are to be understood as meaning the esters of C ₆ - C ₃₀ fatty acids with C ₂ - C ₃ o fatty alcohols. The monoesters of the fatty acids with alcohols having 2 to 24 carbon atoms are preferred. Examples of fatty acid components used in the esters are caproic, caprylic, 2-ethylhexanoic, capric, lauric, isotridecanoic, myristic, palmitic, palmitoleic, stearic, isostearic, oleic, elaidic, petroselic, linoleic, linolenic Behenic acid and erucic acid and their technical mixtures which are obtained, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids. Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, caproic alcohol, capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol, erucyl alcohol and Brassdylalkohol and their technical mixtures, for example, in the Hochdruckhy¬ drierung of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred , According to the invention particularly preferably isopropyl myristate (IPM Rilanit ^®), isononanoic acid C16-18 alkyl ester (Cetiol ^® SN), 2-ethylhexyl palmitate (Cegesoft ^® 24), stearic acid-2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate, Kokosfettalkohol- caprate / caprylate (Cetiol ^® LC), n-butyl stearate, oleyl erucate (Cetiol ^® J 600), isopropyl palmitate (IPP Rilanit ^®), oleyl Oleate (Cetiol ^®), hexyl laurate (Cetiol ^® A), di-n-butyl adipate (Cetiol ^® B), myristyl myristate (Cetiol ^® MM), cetearyl isononanoate (Cetiol ^® SN), oleic acid decyl ester (Cetiol ^® V).

Dicarboxylic acid esters such as di-n-butyl adipate, di (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelaat, and diol esters such as ethylene glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2 ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate, Get symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454, glycerol carbonate or dicaprylyl carbonate (Cetiol ^® CC),

Trifatty acid esters of saturated and / or unsaturated linear and / or branched fatty acids with glycerol,

Fatty acid partial glycerides, ie monoglycerides, diglycerides and their technical mixtures. With the use of technical products production reasons may still contain small amounts of triglycerides. The partial glycerides preferably follow the formula (D4-I),

CH ₂ O (CH ₂ CH ₂ O) ₁₁₁ R ¹

CHO (CH ₂ CH ₂ O) _n R ² (D4-I)

CH ₂ O (CH ₂ CH ₂ O) _q R ³

in which R ¹ , R ² and R ³ independently of one another represent hydrogen or a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups is an acyl radical and at least one of these groups is hydrogen. The sum (m + n + q) is O or numbers from 1 to 100, preferably 0 or 5 to 25. Preferably, R ^{1 is} an acyl radical and R and R ^{3 are} hydrogen and the sum (m + n + q ) is 0. Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, Elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Preferably, oleic acid monoglycerides are used. Jo

The amount used of the natural and synthetic cosmetic oil body in the inventive compositions is usually 0.1 to 30 wt.%, Based on the total application preparation, preferably 0.1 to 20 wt .-%, and in particular 0.1 to 15 wt .-%.

In a further embodiment, the agent contains an enzyme as a care substance. Enzymes which are particularly preferred according to the invention are selected from a group which is formed from proteases, lipases, transglutaminase, oxidases and peroxidases.

Although each of the care substances mentioned in the various embodiments alone already gives a satisfactory result, in the context of the present invention, all embodiments are also included in which the agent (B) contains a plurality of care substances also from different groups.

The colorants according to the invention may furthermore contain all active ingredients, additives and auxiliaries known for such preparations, some of which may be identical to the conditioners. 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 Natri¬ um-, potassium and ammonium and mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (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 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the acyl group Alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 carbon atoms, linear alpha-olefin sulfonates having 12 to 18 carbon atoms, alpha sulfo fatty acid methyl esters of fatty acids with 12 to 18 C atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,

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

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

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

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

Nonionic surfactants contain as hydrophilic group z. B. a polyol group, a polyalkylenglykolethergruppe or a combination of polyol and Polyglykolether- group. Such compounds are, for example Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

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

C ₈ -C ₂₂ -AlkVImOnO- and -oligoglycoside and their ethoxylated analogs and

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

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

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

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

And C _O alkyl groups, mainly of C ₂ - - and C ₄ alkyl groups, essentially of C ₈ - to C ₆ -alkyl or substantially from Ci alkyl polyglycosides are those in which R ¹ consists essentially of C ₈ are particularly preferred ₂ - to Ci ₆ alkyl groups. As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

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

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an effect of the 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. As zwitterionic surfactants, surface-active compounds are described which carry in the molecule at least one quaternary ammonium group and at least one -COO ⁽⁾ or -SO ^ group. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyldimethylammoniumglycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the cocoacylamino ethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Under am- pholytischen surfactants are surface-active compounds which, apart from a C ₈ -C ₈ alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO ₃ H group and to form internal Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₂ 1 ₈ - sarcosine.

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

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

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

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A Erfin dung particularly suitable according to compound from this group is that available under the brand Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

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, quaternium-80.).

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

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained. In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, it is possible to use both products having a "normal" homolog distribution and those having a narrowed homolog distribution. By "normal" homolog distribution are meant mixtures of homologs which are 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 may be preferred.

Furthermore, the inventive colorants, other active ingredients, adjuvants and additives, such as nonionic polymers such as vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and

Polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylamino-ethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone copolymers.

Imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate

Copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans,

Cellulose derivatives, e.g. Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and

Dextrins, clays such as Bentonite or fully synthetic hydrocolloids such as e.g.

polyvinyl alcohol,

Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein,

Soy protein and wheat protein hydrolysates, their condensation products with

Fatty acids and quaternized protein hydrolysates,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, in particular mono-, di- and

Oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-l-alkylamidoethyl-2-alkylimidazolinium methosulfate

Defoamers like silicones,

Dyes for staining the agent,

Anti-dandruff agents 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

bisabolol,

Vitamins, provitamins and vitamin precursors, in particular those of groups A,

B ₃ , B ₅ , B ₆ , C, E, F and H, Plant extracts such as extracts of green tea, oak bark, nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat , Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,. Cholesterol,

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

Complexing agents such as EDTA, NTA, β-alaninediacetic acid and 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 erfϊndungsgemäßen means contain the dye precursors preferably in a suitable aqueous, alcoholic or aqueous-alcoholic or aqueous-organic solvent carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, O

such as shampoos, foam aerosols or other preparations that are suitable for use on the hair. But it is also conceivable to integrate the dye precursors in a powdered or tablet-shaped 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 according to the invention may additionally or instead of the C 1 -C ₄ -alcohol contain (further) organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. In this case, preference is given to all water-soluble or water-miscible organic solvents whose proportion in the water / organic solvent mixture can correspondingly be 3 to 70% by weight.

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

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

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

In particular, in the case of hair which is difficult to dye, the preparation with the dye precursors can also be applied to the hair without pre-mixing with the oxidation component Hair will be applied. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes, the product is then rinsed and, if desired, shampooed again. In this embodiment, according to a first variant, in which the previous application of the dye precursors is intended to bring about 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 derivatives according to the invention - in particular as a developer - for the dyeing of keratinic fibers.

A third object of the present invention is a process for coloring keratinic fibers, in which a hair colorant according to the invention is applied to the fibers and rinsed off again after a contact time.

A fourth subject of the present invention is a diaminobenzene derivative of the general formula (I) as described above.

A fifth subject of the present invention is a synthetic intermediate selected from the group consisting of N- {2- [2- (2-methoxyethoxy) ethoxy] -4-nitrophenyl} acetamide and 2- [2- (2-methoxyethoxy) ethoxy ] -4-nitroaniline. The invention is further illustrated by the following examples.

Examples

1 Synthesis examples

1.1 Preparation of 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine, dihydrochloride

The substance can be prepared starting from the potassium salt of 3-nitro-6-acetylaminophenol according to the following scheme via a three-step synthetic route.

1.1.1 Preparation of N- {2- [2- (2-methoxyethoxy) ethoxy] -4-nitrophenyl} acetamide

48.2 g (0.206 mol) of the potassium salt of 3-nitro-6-acetylaminophenol were dissolved in 250 ml of dimethylformamide. Subsequently, 50.0 g (0.246 mol) of 1-bromo-2- (2-methoxyethoxy) ethane was added and the reaction mixture was heated at 100 ^° C. for 8 hours. After cooling, the reaction mixture was poured into ice-water. After some time, a beige solid precipitated, which was dried in vacuo.

Yield: 40%

IH-NMR (400 MHz, DMSO-d6): δ = 2.12 (s, 3H); 3.31 (s, 3H); 3.46 (t, 2H), 3.60 (t, 2H);

3.84 (t, 2H); 4.35 (t, 2H); 7.87 (d, IH); 7.92 (s, IH); 8.39 (d, IH); 9.38 (br, IH) 1.1.2 Preparation of 2- [2- (2-methoxyethoxy) ethoxy] -4-nitroaniline

There were 12.3 g (0.041 mol) of N- {2- [2- (2-methoxyethoxy) ethoxy] -4-nitrophenyl} acetamide from step 1 in 50 g of 7% aqueous sodium hydroxide solution for 6 hours at 85 ° C heated , After cooling, a yellow-brown oil separated, which was separated and washed thoroughly with water. After drying, the oil could be used in the next step without further purification. Yield: 65%

IH-NMR (400 MHz, DMSO-d6): δ = 3.28 (s, 3H); 3.49 (t, 2H), 3.63 (t, 2H); 3.81 (t, 2H); 4.24 (t, 2H); 6.41 (br, 2H); 6.70 (d, IH), 7.67 (s, IH); 7.78 (d, IH)

1.1.3 Preparation of 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine (dihydrochloride)

There were 8.0 g (0.031 mol) of 2- [2- (2-methoxyethoxy) ethoxy] -4-nitroaniline from step 2 dissolved in 400 ml of ethanol and hydrogenated after addition of PdVC under atmospheric pressure. After complete hydrogen absorption, the reaction mixture was filtered from the catalyst and poured onto a 1: 1 mixture of concentrated hydrochloric acid and ethanol. The product was completely concentrated on a rotary evaporator and dried. Yield: 98%

IH-NMR (400 MHz, D2O): δ = 3.37 (s, 3H); 3.64 (t, 2H), 3.72 (t, 2H); 3.91 (t, 2H); 4.36 (t, 2H); 6.62 (d, IH), 6.73 (s, IH); 7.09 (d, IH)

1.2 Preparation of 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol (dihydrochloride)

The substance can be prepared starting from the potassium salt of 3-nitro-6-acetylaminophenol according to the following scheme via a three-step synthetic route.

Preparation of N- {2- [2- (2-hydroxyethoxy) ethoxy] -4-nitrophenyl} acetamide 13.0 g (0.056 mol) of the potassium salt of 3-nitro-6-acetylaminophenol were dissolved in 670 ml of dimethylformamide. Subsequently, 8.4 g (0.067 mol) of 2- (2-chloroethoxy) ethanol were added and the reaction mixture was heated to 100 ° C. for 8 hours. After cooling, the reaction mixture was poured into ice-water. A brown solid precipitated, which was dried in vacuo. Yield: 13.8 g (87%) m.p .: 125 ° C

¹ H-NMR (400 MHz, DMSOd ₆ ): δ = 2.12 (s, 3H); 3.51 (t, 2H), 3.60 (t, 2H); 3.92 (t, 2H); 4.38 (t, 2H); 7.89 (d, IH); 7.93 (s, IH); 8.32 (d, IH)

1.2.2 Preparation of 2- [2- (2-amino-5-nitrophenoxy) ethoxy] ethanol

There were 7.7 g (0.029 mol) of N- {2- [2- (2-methoxyethoxy) ethoxy] -4-nitrophenyl} acetamide from stage 1 in 28 g of 7% aqueous sodium hydroxide solution for 7 hours at 80 ° C heated , After cooling, a brown oil separated, which crystallized after some time.

The resulting solid was washed thoroughly with water several times. After this

Drying the solid could be used without further purification in the next stage.

Yield: 5.2 g (80%)

¹ H-NMR (400 MHz, DMSOd ₆ ): δ = 3.78 (t, 2H), 3.82 (t, 2H); 4.28 (t, 2H); 4.62 (t, 2H);

6.65 (d, IH), 7.61 (s, IH); 7.73 (d, IH) 1.2.3 Preparation of 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol (dihydrochloride)

There were 9.2 g (0.038 mol) of 2- [2- (2-amino-5-nitrophenoxy) ethoxy] ethanol from stage 2 dissolved in 400 ml of ethanol and hydrogenated after addition of Pd / C as a catalyst under atmospheric pressure. After complete hydrogen uptake, the reaction mixture from

Catalyst and filtered to a 1: 1 mixture of concentrated hydrochloric acid and

Poured ethanol. The product was completely concentrated on a rotary evaporator and dried.

Yield: 9.7 g (90%)

¹ H-NMR (400 MHz ₅ D ₂ O): δ = 3.49 (t, 2H), 3.52 (t, 2H); 3.82 (t, 2H); 4.25 (t, 2H); 6.94

(d, IH), 7, 17 (s, IH); 7.48 (d, IH)

2 floats

2.1 Experimental procedure

For the preparation of the dye cream 50g of a cream base in a 250ml

Weigh the beaker and melt at 80 ° C. The cream base used had the following composition:

Hydrenol ^® D ¹ 17.0 wt .-%

Lorol® ^® tech. ² 4.0% by weight

Texapon ^® NSO ³ 40.0% wt .-

Dehyton ^® K ⁴ 25.0 wt .-%

Eumulgin ^® B2 ⁵ 1.5% wt .-

Water 12.5% by weight

¹ Ci _ö - ₁₈ fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)

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

³ lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)

⁴ N, N-dimethyl-N- (C _8- i ₈ -cocoamidopropyl) ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)

⁵ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

In each case 1/400 mol of the developer or coupler component were suspended separately in distilled water or dissolved by heating. Then ammonia (<1 ml, 25% ammonia solution) was added until the pH was between 9 and 10.

The dissolved dye precursors were incorporated successively into the hot cream. It was then made up to 97 g with distilled water and adjusted to a pH of 9.5 with ammonia. After filling with distilled water to 100 g, the mixture was stirred cold (<3O ⁰ C), resulting in a homogeneous cream. For the dyeings, 25 g of dyeing cream were mixed with 25 g of the following oxidizing agent preparation (unless stated otherwise).

Dipicolinic acid 0.1% by weight

Sodium pyrophosphate 0.03% by weight

Turpinal SL ^{® 6} 1.50% wt .-

Texapon ^® N28 ⁷ 2.00% wt .-

Acrysol ^® 22 ⁸ 0.60 wt .-%

Hydrogen peroxide, 50% 12.0% by weight

Sodium hydroxide, 45% 0.80% by weight

Water ad 100

⁶ l-Hydroxyethane-l, l-diphosphonic acid (about 58 - 61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

⁷ lauryl ether sulfate sodium salt (at least 26.5% active ingredient content, INCI name: Sodium Laureth Sulfate) (Cognis)

⁸ acrylic polymer (about 29.5 - 30.5% solids in water, INCI name: Acrylates / Steareth-20 Methacrylate Copolyme)

One strand of hair (80% gray, 330 mg to 370 mg heavy) was added to each of the mixtures thus obtained. Subsequently, the mixtures and the hair strands were placed on a watch glass and the hair strands well embedded in the dyeing creams. After 30 minutes (± 1 minute) Reaction time at 32 ° C were removed and the strands of hair so washed many times, until the color was removed with an aqueous excess Texapon EVR ^® solution. ⁹ The strands of hair were air-dried and their color was determined and noted under the daylight lamp (color tester HE240A) (Taschenlexikon der Farben, A. Kornerup and JH Wanscher, 3rd unchanged edition 1981, MUSTER-SCHMIDT Verlag, Zurich, Göttingen) ,

⁹ Lauryl ether sulfate sodium salt with special additives (about 34 to 37% active ingredient content, INCI name: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate,

Laureth-10) (Cognis)

The results obtained in the staining tests are shown in the tables below.

2.2 colorations with 2- [2- (2-methoxyethoxy) ethoxy] benzene-1,4-diamine, dihydrochloride (El)

2.3. Colorations with 2- [2- (2,5-diaminophenoxy) ethoxy] ethanol (dihydrochloride) (E2)

Claims

claims

1. An agent for coloring keratinic fibers, in particular human hair, comprising in a cosmetically acceptable carrier as a dye precursor at least one diaminobenzene derivative of the general formula (I)

with the meaning

R ^1, R ² are independently H, C _1-6 alkyl, C _1-6 hydroxyalkyl, C _2-6 polyhydroxyalkyl radical, a C _7-12 arylalkyl, C _3-12 alkoxyalkyl, _{Ci-6-aminoalkyl,} C _2-10 alkylaminoalkyl, C _3-12 -

Dialkylaminoalkyl, C _2-6 alkenyl, acetyl,

R ^ό are independently H, OH, halogen, _NH2, Ci _-6 - alkylamino, C ₂ i ₂ dialkylamino, NO _2, COOH, CN, Ci _-6 - alkyl, _{Ci-6-hydroxyalkyl,} C _2-6 polyhydroxyalkyl, C _7-I2 - arylalkyl, C _2-6 alkoxyalkyl, _{Ci-6-aminoalkyl,} C _2-I0 - alkylaminoalkyl, C ₃ i ₂ dialkylaminoalkyl, Ci _-6 alkoxy, C _{2- 6} alkenyl .

O, 1 or 2,

integer from 2 to 6 r integer from 2 to 6

or a salt of it.

2. Composition according to claim 1, characterized in that in the derivative of the general formula (I) R ¹ H Ci _-6 alkyl, C _2-6 alkenyl or alkoxyalkyl of the formula H ₃ C- (CH ₂ ) _n - O- (CH ₂ ) _m - where n is an integer from 0 to 5 and m is an integer from 2 to 6.

3. A composition according to claim 2, characterized in that in the derivative of the general F Foorrmmeell ((I) R ^{2 is} H, Ci _-6- alkyl, Ci _-6- hydroxyalkyl, C _2-6 -polyhydroxyalkyl or acetyl.

4. Composition according to one of claims 1 to 3, characterized in that in the derivative of the general formula (I) R ^{3 is} independently H, Ci _-6 alkyl, C _2-6 alkenyl, Ci _-6- hydroxyalkyl, C _{2 -6} -polyhydroxyalkyl, OH, C _1-6 -alkoxy or halogen.

5. Composition according to one of claims 1 to 4, characterized in that in the derivative of the general formula (I) q is 2 or 3 and r is 2 or 3.

6. Composition according to one of claims 1 to 5, characterized in that in the derivative of the general formula (I) R ^{1 is} H, C, _-4- alkyl or H ₃ C- (CH ₂ ) _n -O- (CH ₂ ) _m - is 3 or n is O or 1 and m is 2 or 3, R ² is H, Ci _-4 alkyl or C _1-4 hydroxyalkyl, R ³ is H, q and r are 2 and p represents the 0th

7. Composition according to claim 6, characterized in that in the derivative of the general formula (I) R ¹ H, CH ₃ or CH ₃ -O-CH ₂ -CH ₂ -, R ² H and R ³ H, q is 2 or 3 , r 2 and p O mean.

8. Composition according to one of claims 1 to 7, characterized in that it contains at least one further developer component.

9. Composition according to one of claims 1 to 8, characterized in that it contains at least one coupler component.

10. Composition according to one of claims 1 to 9, characterized in that it further contains at least one substantive dye.

11. A composition according to claim 10, characterized in that the substantive dye is cationic.

12. Composition according to one of claims 1 to 11, characterized in that it additionally contains at least one care substance selected from cationic surfactants, polymers, UV filters, vitamins, provitamins, their precursors and derivatives, plant extracts, carboxylic acids, protein hydrolysates or their derivatives, Ecotin or ecotin derivatives, allantoin, taurine, bisabolol, amino acids, mono- and oligosaccharides, silicone oils, silicone gums, lipids, oil bodies, enzymes and mixtures thereof.

13. Composition according to one of claims 1 to 12, characterized in that it is present in an aqueous, alcoholic or aqueous-alcoholic or aqueous-organic solvent carrier.

14. A method for coloring keratinous fibers, wherein an agent according to any one of claims 1 to 13 is applied to the fibers and rinsed again after a contact time.

15. Use of diaminobenzene derivatives of the general formula (I) as defined in any one of claims 1 to 7 for the coloring of keratinous fibers, in particular human hair.

16. Diaminobenzene derivative of the general formula (I) as defined in any one of claims 1 to 7. 7. Synthetic intermediate selected from the group consisting of N- {2- [2- (2-methoxyethoxy) ethoxy] -4-nitrophenyl} acetamide, N- {2- [2- (2-

Hydroxyethoxy) ethoxy] -4-nitrophenyl} acetamide, 2- [2- (2-methoxyethoxy) ethoxy] -4-nitroaniline and 2- [2- (2-amino-5-nitrophenoxy) ethoxy] ethanol.