WO2008006820A1

WO2008006820A1 - Hair coloring agent

Info

Publication number: WO2008006820A1
Application number: PCT/EP2007/057015
Authority: WO
Inventors: Thomas Döring; Jürgen SCHÖPGENS; Anja Reichert; Kristin Pauli; Britta Bossmann
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2006-07-11
Filing date: 2007-07-10
Publication date: 2008-01-17
Also published as: RU2009104071A; EP2037870A1; DE102006055675A1

Abstract

The invention relates to agents, particularly low-ammonia agents, for coloring keratin-conta

Description

"Hair dye"

The present invention relates to the improvement of the intensity of dyeings on keratin fibers, the enhancement of the fastness properties of these dyeings, as well as scalp feel by using at least one active ingredient selected from at least one N-acylsarcosine derivative or at least one N-acyl taurine derivative, or a mixture from the aforementioned active ingredients.

Human hair is today treated in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role. Apart from the bleaching agents that cause an oxidative lightening of the hair by degradation of the natural hair dyes, so in the field of hair coloring essentially four types of hair dyes of importance:

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such hair dyes usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components. The oxidation dyes are characterized by excellent, long-lasting dyeing results. For naturally acting dyeings but usually a mixture of a larger number of oxidation dye precursors must be used; In many cases, direct dyes are still used for shading.

As developer components are usually primary aromatic amines with another, located in the para or ortho position, free or substituted hydroxy or amino group, Diaminopyridinderivate, heterocyclic hydrazones, 4-aminopyrazolone and 2,4,5,6-tetraaminopyrimidine and its derivatives used , Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-) Diaminophenyl) ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido -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) -diamino-propan-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-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monoethyl 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-5-aminophenol.

For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that grow directly on the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable nuance shift or even a visible "discoloration" occurs much more quickly.

Finally, another dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. Such a process with 5,6-dihydroxyindoline as dye precursor was described in EP-B1-530 229. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The dyeing can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. For use in persons with originally red and especially dark to black hair color, on the other hand, satisfactory results can often only be achieved by the concomitant use of further dye components, in particular special oxidation dye precursors.

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

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

To adjust the pH or to improve the paint lift, the skilled person usually uses ammonia. However, the use of ammonia leads to an undesirable odor during use. Furthermore, the presence of ammonia adversely affects the hair structure. Thus, the skilled artisan has for some time begun to provide low-ammonia color-changing agents.

Although low-ammonia color change agents do not have the aforementioned disadvantages, they lose their tinting strength and color fastness. Therefore, it is a general endeavor to perform the achievable with the known methods dyeings as possible without ammonia and intensify in your color result. A high tinting strength contributes to the profitability of Dyes at. In addition, the dyeings obtained should have a high degree of color fastness, for example against sweat, washing, light or friction and must be compatible with other hair treatment products, in particular in the context of hair care.

It has surprisingly been found that by using at least one representative from the group of N-acylsarcosine derivatives or N-acyltaurine derivatives in color-changing agents, the intensity of hair colorations can be increased and the fastness of the dyeings can be increased. This color intensification offers a general advantage for all color-changing agents, but is particularly surprisingly suitable for low-ammonia color-change agents.

A first subject of the invention is therefore the use of at least one compound of the active ingredients

(a) N-Acyl sarcosine derivatives of the formula (I)

wherein

R ^{1 is} a (C7 to C30) alkyl group, (C7 to C30) alkenyl group or a

(C ₇ to C ₃ o) -hydroxyalkyl group,

R ^{2 is} a (C ₁ to C ₄ ) alkyl group or a (C ₁ to C ₄ ) hydroxyalkyl group, and

M represents a hydrogen atom or one equivalent of a monovalent or polyvalent cation, and / or (b) N-acyltaurine derivatives of the formula (II)

wherein R ^{3 is} a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -

Hydroxyalkyl group stands,

R ^{4 is} a (C ₇ to C ₃ o) alkyl group, (C ₇ to C ₃ o) alkenyl group or a

(C ₇ to C ₃₀ ) hydroxyalkyl group and

M 'represents a hydrogen atom or one equivalent of a mono- or polyvalent cation

In, in particular low-ammonia, color-change agents (i) for intensifying the coloration,

(ii) to increase color fastness, especially wash fastness, (iii) to reduce scalp irritation,

(iv) to relieve sensory discomfort on the scalp, such as stinging or itching.

The intensification of the coloration is reflected in particular on gray hair. Thus, it is possible to dye gray hair satisfactorily. The expert speaks in this context of an improved gray coverage.

As low ammonia in the context of the invention means which contain not more than 0.5 wt .-%, in particular not more than 0.25 wt .-%, of ammonia. The compounds of the formula (I) and / or (II) used according to the invention are preferably used in low-ammonia color-change agents, in particular in ammonia-free color change agents.

The active compounds (a) of the formula (I) and (b) of the formula (II) according to the invention are preferably used in combination, i. at least one compound according to formula (I) together with at least one compound according to formula (II) used.

The compounds of the formula (I) and the compounds of the formula (II), when used together, are more preferably in a weight ratio range of 1: 3 to 3: 1, more preferably 1.5: 1 to 1: 1.5 preferably from 1 to 1, used.

Examples of (C ₁ to C ₄ ) -alkyl groups according to the invention are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl. Examples of (C ₂ to C ₄ ) -hydroxyalkyl groups according to the invention are 2-hydroxyethyl, 3

Hydroxypropyl, 2-hydroxypropyl and 4-hydroxybutyl.

Examples of (C ₇ to C ₃ o) -alkenyl groups are heptadec-8-enyl, heptadeca-8,1 1 -dienyl,

Heptadeca-8,1 1, 14-trienyl, nonadeca-4,7,10,13-tetraenyl, 12-henicosenyl and heptadeca-

7,10,12-trienyl.

The (C ₇ to C ₃₀ ) -alkyl groups according to the invention can be linear or branched.

The radicals R ^{1 of} the formula (I) and R ^{4 of} the formula (II) are preferably, independently of one another, a (C ₉ to C ₂₃ ) -alkyl group, (C ₉ to C ₂₃ ) -alkenyl group or a (C ₉ to C ₂₃ ) Hydroxyalkyl group, particularly preferably independently of one another, a radical selected from the list which is formed from nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, nonadecyl, henicosanyl, 15-methylhexadecyl, heptadec-8-enyl, heptadeca-8, 1 1 -dienyl, nonadeca-4,7,10,13-tetraenyl, heptadeca-8,1 1, 14-trienyl and 1 1-hydroxyheptadecyl.

The radical R ² according to formula (I) preferably represents a radical selected from the group formed from methyl, ethyl, isopropyl, n-propyl and 2-hydroxyethyl. Particularly preferably, said radical R ^{2 is} a methyl group.

The radical R ³ according to formula (II) preferably represents a radical selected from the group consisting of hydrogen atom, methyl, ethyl, isopropyl, n-propyl and 2-hydroxyethyl. R ^{2 of} the formula (I) particularly preferably represents a hydrogen atom or a methyl group.

It is very particularly preferred according to the invention if R ^{2 of} the formula (I) and R ^{3 of} the formula (II) both together represent a (C 1 to C ₄ ) -alkyl group, in particular a methyl group.

When the compounds of the formulas (I) and (II) are present as acid, the radical M or the radical M 'is a hydrogen atom. When the compounds of the formulas (I) or (II) are in the form of a salt, M or M 'represents one equivalent of a monovalent or polyvalent cation. The monovalent or polyvalent cation M ^{z +} or M ' ^{y +} each having a charge number z or y of one or higher is used solely for reasons of electroneutrality to compensate for the single negative charge of the present at salt carboxylate fragment -COO * ^' 'of the formula (I ) or the sulfonate fragment -SO ₃ ^ of the formula (II). The equivalent of the corresponding cation to be used is 1 / z or 1 / y. The fragment -COOM of the formula (I) or the fragment -SO ₃ M of the formula (II) is in the case of salt formation for the group: -COO * ^" '1 / z (M ^{z +} ) or -SO ₃ ^H 1 / y (M' ^{y +} )

In principle, all physiologically compatible cations are suitable as mono- or polyvalent cations M ^{z +} or M ' ^{y +} . In particular, these are metal cations of the physiologically acceptable metals from groups Ia, Ib, IIa, IIb, IIIb, VIa or VIII of the Periodic Table of the Elements, ammonium ions, as well as cationic organic compounds with quaternized nitrogen atom. The latter are formed for example by protonation of primary, secondary or tertiary organic amines with an acid, such as with compounds of formula (I) or formula (II) in their acid form, or by permanent quaternization of said organic amines. Examples of these cationic organic ammonium compounds are 2-ammonioethanol and 2-trimethylammonioethanol. M or M 'in the formulas (I) and (II) is preferably a hydrogen atom, an ammonium ion, an alkali metal ion, half an equivalent of an alkaline earth metal ion or half an equivalent of a zinc ion, particularly preferably a hydrogen atom, an ammonium ion, a sodium ion, a potassium ion,! 4 calcium ion, ^Λ A magnesium ion or ^Λ A zinc ion.

The compounds of formula (I) are preferably selected from at least one member of the group formed from N-lauroyl sarcosine, N-myristoyl sarcosine, N-palmitoyl sarcosine, N-oleyl sarcosine, N-cocoyl sarcosine (here being a group of compounds and cocoyl corresponds to the composition of the fatty acid cut of coconut oil) and N-palm kernel sarcosine (here being a group of compounds and palm kernel corresponds to the fatty acid cut composition of palm kernel oil), as well as the salts of the aforementioned N-acyl sarcosine derivatives.

The compounds of formula (II) are preferably selected from at least one member of the group formed from N-dodecanoyl-N-methyltaurine, N-octadecanoyl-N-methyltaurine, N-hexadecanoyl-N-methyltaurine, N-tetradecanoyl N-methyltaurine, N-oleyl-N-methyltaurine, N-cocoyl-N-methyltaurine (wherein here is a group of compounds and cocoyl corresponds to the composition of the fatty acid cut of coconut oil), N-palm kernel N-methyltaurine (here Group of compounds is present and palm kernel corresponds to the composition of the fatty acid cut of palm kernel oil), as well as from the salts of the aforementioned N-Acyltaurinderivate. The triglycerides of coconut oil have the following fatty acid composition:

45 to 51% lauric acid

16 to 19% tetradecanoic acid

8 to 10% oleic acid

9 to 1 1% palmitic acid 6 to 9% decanoic acid

5 to 8% octanoic acid

The triglycerides of palm kernel oil have the following fatty acid composition:

47 to 52% lauric acid

14 to 16% tetradecanoic acid

10 to 18% oleic acid

6 to 9% palmitic acid 2 to 3% stearic acid

1 to 3% linoleic acid

2 to 5% decanoic acid 1 to 3% octanoic acid

In a preferred embodiment, the agent used, in particular low in ammonia, additionally contains from 0 to 0.5% by weight, in particular from 0 to 0.3% by weight, of at least one anionic surfactant selected from linear or branched C 4 to C 40 -alkyl sulfates, linear or branched alkylsulfates branched C ₈ to C ₄ o-alkyl ether sulfates having at least one ethylene oxide

Unit or propylene oxide unit in the molecule.

Said compounds of the formula (I) and / or (II) are particularly suitable for use according to the invention on keratin-containing fibers, in particular human hair.

Keratin fibers are wool, furs, feathers and especially human hair to understand. The combination of the invention may in principle but also on other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers such. As regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose and synthetic fibers, such as. As polyamide, polyacrylonitrile, polyurethane and polyester fibers are used.

A second subject of the invention is an agent, in particular low in ammonia, for coloring keratin-containing fibers, in particular human hair, containing in a carrier at least one coloring component and additionally at least one compound selected from the group formed

(a) N-Acyl sarcosine derivatives of the formula (I)

wherein

R ^{1 is} a (C ₇ to C ₃₀ ) alkyl group, (C ₇ to C ₃₀ ) alkenyl group or a

(C7 to C30) hydroxyalkyl group means

R ^{2 is} a hydrogen atom, a (C 1 to C ₄ ) -alkyl group or a (C 1 to C ₄ ) -

Hydroxyalkyl group, and

M represents a hydrogen atom or one equivalent of a monovalent or polyvalent cation, and (b) N-acyltaurine derivatives of the formula (II)

wherein

R ^{3 is} a hydrogen atom, a (C 1 to C ₄ ) -alkyl group or a (C 1 to C ₄ ) -

Hydroxyalkyl group stands,

R ^{4 is} a (C ₇ to C ₃₀ ) alkyl group, (C ₇ to C ₃₀ ) alkenyl group or a

(C ₇ to C ₃₀ ) hydroxyalkyl group and M 'represents a hydrogen atom or one equivalent of a mono- or polyvalent cation.

According to the invention, the agent preferably contains a combination of at least one compound according to the abovementioned formula (I) with at least one compound according to the abovementioned formula (II).

As preferred compounds of the formula (I) or of the formula (II) or their preferred mixing ratios apply mutatis mutandis the corresponding embodiments of the first subject of the invention.

The agents according to the invention preferably contain the compounds of the formula (I) and / or of the formula (II) in an amount of from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight, very particularly preferably from 0.5 to each based on the weight of the color changing agent.

The coloring component is preferably selected

(1) at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or

(2) from oxo dye precursors and / or

(3) from at least one direct dye and / or

(4) from at least one precursor of naturally-colored dyes.

It may be preferred according to the invention to select the developer components according to the invention from the group formed from p-phenylenediamine derivatives, binuclear developer components, p-aminophenol and its derivatives, pyrimidine derivatives, pyrazole derivatives and pyrazolopyrimidine derivatives and the physiologically acceptable salts of these compounds. In the following, preferred developer components are mentioned according to the invention.

Particularly preferred according to the invention are p-phenylenediamine derivatives of the formula (E1)

in which

G ¹ represents a hydrogen atom, a Ci to C4 alkyl group, a Cr to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy (C _r to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy ( C _r alkyl to C ₄₎ or a C ₁ - to C ₄ -alkyl, which is substituted with a nitrogenous group;

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

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxy ethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are, in particular, the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ - Dialkylamino, C ₁ - to C ^ Trialkylammoniumgruppen, C ₁ - to C ₄ -Monohydroxy- alkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2 -methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2 Fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N , N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) -p-phenylenediamine, 2- (β-acet ylaminoethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine and 5,8-Diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particular preferred p-phenylenediamine derivatives of the formula (E1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N bis (.beta.-hydroxyethyl) -p-phenylenediamine.

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

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

in which:

Z ¹ and Z ² independently of one another, are a hydroxyl or NH ₂ radical, which is optionally substituted by a Ci _r to C ₄ alkyl, by a C to C ₄ -hydroxyalkyl radical and / or substituted by a Verbrϋckung Y is or where appropriate, is part of a bridging ring system, the bond Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, 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 optionally be substituted by one or more hydroxyl or C ₁ -C ₈ -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bond Y or a C ₁ - to C ₄ -alkyl radical, with the proviso that the compounds of the formula (E2) contain only one bond Y per molecule.

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

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

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1,3-diamino-propan-2-ol, bis - (2-hydroxy-5-amino-phenyl) -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 acceptable salts.

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

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) - alkoxy (C _r C4) alkyl, alkylamino a Ci to C4 aminoalkyl radical, a hydroxy (Ci to C4), a C ₁ - to C ₄ -Hydroxyalkoxyrest, a C ₁ - to C ₄ hydroxyalkyl - (C _r to C ₄ ) -aminoalkyl or a (di-C ₁ - to C ₄ -A ^ yIaImJnO) - (C ₁ - to C ₄ ) -alkyl radical, 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 ) alkoxy (ci- to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a C ₁ - to C ₄ -cyanoalkyl radical,

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

G ¹⁶ is hydrogen or a halogen atom. The substituents used in formula (E3) are defined according to the invention analogously to the above statements.

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-Ami no-2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino 2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethylaminomethyl) -phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) -phenol.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-1-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

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

Preferred pyridine derivatives are, in particular, the compounds described in the 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 selected according to the invention from compounds of the formula (E4),

wherein

G ¹⁷ , G ¹⁸ and G ¹⁹ independently represent a hydrogen atom, a hydroxy group, a (C _r C ₆ ) alkoxy group or an amino group and

20 21 22 21 22

G is a hydroxy group or a group -NG G, in which G and G are each independently hydrogen, a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) -hydroxyalkyl group, with the proviso that at most two the groups G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxy group and at most two of the radicals G, G and G represent a hydrogen atom.

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

Preferred pyrazole derivatives are selected according to the invention from compounds of the formula (E5),

wherein

G ^23, G ^24, G ²⁵ are each independently a hydrogen atom, a Ci to C ₆ - alkyl group, a C ₂ to Ce-monohydroxyalkyl group, a C ₂ to C ₆ - polyhydroxyalkyl group, an optionally substituted aryl group or an optionally substituted aryl C, to C ₆ alkyl group and

G ²⁶ represents a hydrogen atom, a C ₁ to C ₆ alkyl group, a C ₂ to C ₆ -

Monohydroxyalkyl group or a C ₂ to C ₆ polyhydroxyalkyl group. Particularly 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-dimethyl lpyrazol.

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] pyrimidine of the following formula (E6) and its tautomeric forms, provided that a tautomeric equilibrium exists:

G ²⁷ , G ²⁸ , G ²⁹ and G ³⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C _r to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkyl radical is a (C 1 to C ₄ ) -alkoxy (C 1 to C ₄ ) -alkyl radical, a C 1 to C ₄ -aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical, a C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a DK (C ₁ - to C ₄ ) -alkyl] - (C ₁ - to C ₄ ) -aminoalkyl radical, where the dialkyl Radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) - aminoalkyl, the X radicals are each independently a hydrogen atom, a C ₁ - to C ₄ - alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, a n (C ₁ - to C ₄₎ alkylamino (C _r to C ₄₎ - alkyl radical, a di [XC ₁ - to C ₄₎ alkyl] - aminoalkyl to C _4), wherein the dialkyl - (C ₁ radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) -aminoalkyl, an amino group, a C ₁ - to C ₄ -Alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) -amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0, if p + q equals 2, n has the value 0, and the groups NG ²⁷ G ²⁸ and NG ²⁹ G ³⁰ 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 ²⁷ G ²⁸ (or NG ²⁹ G ³⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (E6) are defined according to the invention analogously to the above statements.

When the pyrazolo [1,5-a] pyrimidine of the above formula (E6) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (E6) may be mentioned in particular:

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

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

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

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

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

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

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

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

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

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

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

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

The pyrazolo [1, 5-a] pyrimidines of the above formula (E6) can be prepared as described in the literature by cyclization from an aminopyrazole or from hydrazine.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives and heterocyclic compounds are generally used.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2 6-Dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'- Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4 Dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4-diaminophenoxy-ethanol, 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 , 2 - ({3 - [(2-Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5 methylphenyl} amino) etha nol, 2 - ({3 - [(2-hydroxyethyl) amino] -4,5- dimethylphenyl} amino) ethanol, 2- [3-morpholino-1-phenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

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

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

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

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy 6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or methylenedioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) -amino 3,4-methylenedioxybenzene and their physiologically acceptable salts.

Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically acceptable salts of the aforementioned compounds. The agents according to the invention preferably contain the developer components in an amount of from 0.005 to 10% by weight, preferably from 0.1 to 5% by weight, in each case based on the total agent.

The agents of the invention preferably contain the coupler components in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the total agent.

The composition according to the invention can be used as a coloring component in the form of the oxo dye precursors at least one combination of at least one compound of the component

1 compounds containing a reactive carbonyl group with at least one compound of the component

2 compounds selected from (a) CH-acidic compounds, (b) compounds containing primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component 1) have at least one carbonyl group as reactive group which reacts with the compounds of component 2 to form a chemical bond linking both components. Further, according to the invention, those compounds are also included as component 1 in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to the component 2 is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and their derivatives to form imines or oximes as a condensation compound b) alcohols to form acetals or ketals as a condensation compound c) water to form hydrates as a condensation compound of aldehydes.

Component 1 is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxy acetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3, 4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, A-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, A-imidazolinoacetophenone, 2-hydroxy-5-bromo acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, A-

Hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxybenzophenone 2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9 Fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, A-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, A-hydroxy-2,3 dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, A Hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy -3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4- hydroxy-benzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2- Hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3, 4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2- methoxybenzaldehyde, 4-dimethylaminob enaldehyde, 4-diethylaminobenzaldehyde, A-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2- Methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4- methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino 1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro 4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylaminocinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) -benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine 9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribas Aldehyde)

2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, i-methyl-3-acetylindole, 2- (1 ', 3 ', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine , 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromon-3-aldehyde, 3- (5 ' Nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde, 1, 3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2- Benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) -acetophenone and 2- (3'-pyridoyl) -acetophenone,

Benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4- Diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-benzylidene cyclohexanone, 2- 4'-hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3 (4'-dimethylaminobenzylidene) -1,3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- Benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene) cyclope ntanone, 2- (4'-dimethylaminobenzylidene) cyclopentanone,

5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3, 4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxy- phenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2 , 4-dienal,

6- (4-Dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5 -dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one , 6- (4-Piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) -hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3 , 5-diene-2-one,

5- (4-Dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, A-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy -3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3 nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde , 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro -1 -naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, A-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, S-acetyl -θ-methylcarbazole, 1, 4-dimethyl-3-carbazolaldehyde, 1, 4, 9 trimethyl hyl-3-carbazolaldehyd,

4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1 benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1 -methylpyridinium, 2-acetyl-1-methylpyridinium, A-acetyl-1-methylquinolinium, 5-formyl-i-methylquinolinium, 6-formyl-i-methylquinolinium, 7-formyl-1-methylquinolinium, 8 -Formyl-i-methylquinolinium, 5-formyl-i-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylchinolinium , 6-Formyl-i-benzyl-quinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-i-allyl-quinolinium, 6-formyl-i-allyl-quinolinium, 7-formyl-1 allyl quinolinium and 8-formyl-i-allyl quinolinium, 6-acetyl-1-methylquinolinium, 6-acetyl-1-methylquinolinium, 7-acetyl-1-methyl inolinium, 8-acetyl-i-methylquinolinium, 5-acetyl-1-ethylquinolinium, θ-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl 1-benzylquinolinium, 6-acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5-acetyl-1-allylquinolinium, 6-acetyl-1-allylquinolinium, 7 Acetyl-1-allyl quinolinium and 8-acetyl-1-allyl quinolinium, 9-formyl-10-methyl-acridinium, 4- (2'-formyl-vinyl) -1-methyl-pyridinium, 1, 3-dimethyl-2 ( 4'-formylphenyl) benzimidazolium, 1,3-dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzene zothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium -, 2- (5'-Formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formyl-phenyl) -3 - methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3 , 5-dimethylbenzothiazolium salts, preferably with benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, Tetrachlorozinkat, methyl sulfate, trifluoromethanesulfonate or tetrafluoroborate as counterion, isatin, 1-methyl-isatin, 1-allyl-isatin , 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-methyl-quinisatin, and any mixtures the above connections.

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

The CH-acidic compounds of component 2 are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methylnaphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1, 4-

Dimethylquinolinium iodide, 1, 2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylatoacetate, 2-coumaranone, 5-hydroxybenzoic acid 2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, indan-1, 2-dione, indan-1, 3-dione, indan-1-one, benzoylacetonitrile, 3-dicyanomethylene-indan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1, 2,3-trimethylquinoxaluminum iodide, 3-ethyl 2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium p-toluenesulfonate, 1-ethyl-2-methylquinolinium p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate. Preferred primary or secondary aromatic amines of component B are selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2.5- Dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4- aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5-diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethol, 4-amino-3-methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-2- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethyl) amino) phenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2- hydroxymethylphenol, 2-

(Diethylaminomethyl) ^ -aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) -benzene, 1-hydroxy-2-amino-5-methylbenzene, 1-hydroxy-2-amino-6-methyl benzene, 2-amino-5-acetamidophenol, 1, 3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino) -2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N , N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2- hydroxyethoxy) toluene, 2,4-diamino-5-methylphenol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) -anisole, 2,6-bis (2,6-bis) 2-hydroxyethylamino) -1-methylbenzene, 1, 3-diamino-2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenylacetic acid , 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, amino ^ -hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6 Amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1, 3,5-triaminobenzene, 1, 2,4-triaminobenzene, 1, 2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6- Triaminoresorcinol, 4,5-diaminobrencatechin, 4,6-diaminopyrogallol, 1- (2-hydroxy-5-aminobenzyl) -2-imidazolidinone, 4-amino-2 - ((4 - [(5-amino-2-hydroxyphenyl) methyl] -piperazinyl) methyl) phenol, 3,5-diamino-4-hydroxy-catechol, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4 amino-2- hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, amino groups containing nitro groups, such as 3-amino-6-methylamino-2-nitro-pyridine, picric acid, [8 - [(4-amino-2-nitrophenyl) -azo] -7-hydroxy-naphth-2-yl] -trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) -azo) -7-hydroxy-naphth-2-yl] -trimethylammonium chloride (Basic Brown 17), 1 -Hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2-nitro-4- [bis (2-hydroxyethyl) amino] benzene, 1-amino-2 - [(2-hydroxyethyl) amino] 5-nitrobenzene (HC Yellow No. 5), 1-amino-2-nitro-4 - [(2-hydroxyethyl) amino] -benzene (HC Red No. 7), 2-chloro-5-nitro-N- 2-hydroxyethyl-1, 4-phenylenediamine, 1 - [(2-hydroxyethyl) amino] -2-nitro-4-aminobenzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino 2-nitrophenol, 6-nitro-otoluidine, 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet # 1), 1-amino-2-nitro-4- [(2,3-dihydroxypropyl) amino] -5-chlorobenzene (HC Red # 10), 2- (4-amino-2-nitroanilino) benzoic acid, 6-nitro-2,5-diaminopyridine, 2- amino-6-chl or-4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy 4-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid Disodium salt (gallium), 4-amino-1'-nitrostilbene-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methylazobenzene (Mordant brown 4) '4'-Amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) -benzene, 2- [2 (Diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1 nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, especially nitro group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1,2-diamino-4 nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-Ni tetr-1, 3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro-1-amino-4- [bis- (2-hydroxyethyl) -amino] - benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols with another aromatic radical, as described in the Formula IM are shown

in the

• R ⁷ represents a hydroxy or an amino group substituted with Ci-4 alkyl, Ci- ₄ hydroxyalkyl, C1-4 alkoxy or Ci _-4 alkoxy-Ci- ₄ alkyl groups may be substituted; . • R ^8, R ^9, R ^10, R ¹¹ and R ¹² independently represent a hydrogen atom, a hydroxy or an amino group represented by C _r C ₄ alkyl, C _r C ₄ hydroxyalkyl, C ₁ -C ₄ -Aikoxy, C ₁ -C ₄ - aminoalkyl or C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl groups may be substituted, and

P is a direct bond, a saturated or unsaturated, optionally substituted by hydroxy groups carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group having the formula IV

-Q '- (CH ₂ -Q-CH ₂ -Q ") _O - (IV)

in the

Q signifies a direct bond, a CH ₂ or CHOH group,

Q 'and Q "independently of one another represent an oxygen atom, an NR ¹³ group, in which R ^{13 is} a hydrogen atom, a C 1-6 -alkyl or a hydroxy-C 1-3 -alkyl group, where both groups together with the remaining molecule have a 5-, 6- or 7-Rιng form, the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p -O, wherein p and p 'are 2 or 3, stand and

O is a number from 1 to 4,

such as 4,4'-Dιamιnostιlben and its Hydrochloπd, 4,4'-Dιamιnostιlben-2,2'-dιsul- sulfonic acid mono- or -dι-Na salt, 4-Amιno-4'-dιmethylamιnostιlben and its Hydrochloπd, 4,4'-Dιamιnodιphenylmethan, 4,4'-Dιamιnodιphenylsulfιd, 4,4'-Dιamιnodιphenylsulfoxιd, 4,4'-diaminodiphenylamine, 4,4'-Dιamιnodιphenylamιn-2-sulfonic acid, 4,4'-Dιamιnobenzophenon, 4,4 ' - Diaminodiphenylether, 3,3 ', 4,4'-Tetraamιnodιphenyl, 3,3', 4,4'-Tetraamιno-benzophenone, 1, 3-Bιs- (2,4-dιamιnophenoxy) -propane, 1, 8-Bιs - (2,5-dιamιnophenoxy) -3,6-dιoxaoctan, 1, 3-Bιs- (4-amιnophenylamιno) propane,, 1, 3-Bιs- (4-aminophenylamino) -2-propanol, 1, 3rd -Bιs- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-Bιs- [2- (4-aminophenoxy) ethyl] -methylamιn, N-phenyl-1, 4-phenylenediamine and bis (5-amino-2-hydroxyphenyl) methane.

The abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.

Suitable nitrogen-containing heterocyclic compounds are, for. B. 2-Amιnopyπdιn, 3-Aminopyπdin, 4-Amιnopyπdιn, 2-Amιno-3-hydroxy-pyπdιn, 2,6-Dιamιno-pyπdιn, 2,5-Dιamιno- pyπdin, 2- (Amιnoethylamιno) -5-amιnopyπdιn, 2,3-diamino-pyridine, 2-dimethylamino-5-amino pyridine, 2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino pyridine, 2,6-dihydroxy-3,4-dimethylpyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) -amine, N- [2- (4 -Aminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) -amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5, 6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5 -Diaminopyrimidine, 2-amino-4-methoxy-6-methyl-pyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1,2,4-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1 -PhenyW, 5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-amino-2,3-dimethyl-1-phenyl-3 pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline, 4-aminoquinaldine, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-morpholinoaniline and also indole and indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Furthermore, as heterocyclic compounds, the hydroxypyrimidines disclosed in DE-U1-299 08 573 can be used according to the invention. The aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used.

Suitable aromatic hydroxy compounds are, for. 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3 Dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxy-phenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2,4 , 6-trihydroxybenzoic acid, 2,4,6-trihydroxyace- tophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino-4 -hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

The compounds of component A and the compounds of component B are preferably used in the shading agents according to the invention in each case in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total Nuanciermittels used. The molar ratio of the compound of component A and the compound of component B may range from 0.5 to 2.0, preferably equimolar amounts be used. The actual Nuanciermittel is prepared with separate storage of components A and B immediately before use by mixing.

As precursors of naturally-analogous dyes, preference is given to using, as oxidizing dye precursor of the developer type, indoles and indolines 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. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

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

in the independently of each other

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

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

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

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,

N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline. Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

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

in the independently of each other

R ¹ represents hydrogen, C | -C ₄ alkyl group or a C _r C ₄ hydroxyalkyl group,

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

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

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

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

Preferred substantive dyes which are used in the compositions according to the invention as a coloring component are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those of the HC Yellow 2, HC Yellow 4, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid HC Red 1, HC Red 1, HC Red 1, HC Red 1, 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, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2- Hydro xy-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 1 1 are called.

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

CH ₃ SO ₄ ^"

Cl ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

The cationic substantive dyes sold under the trademark Arianor® are also very particularly preferred cationic substantive dyes according to the invention. The agents according to the invention preferably contain the substantive dyes in an amount of from 0.01 to 20% by weight, based on the ready-to-use agent.

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 compositions according to the invention, due to the production process for the individual dyes, minor amounts of other 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 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.

If the agent according to the invention contains oxidation dye precursors or in particular precursors of a nature-analogous dye based on indole or indoline, the actual oxidative dyeing of the fibers can in principle be carried out with atmospheric oxygen. However, preference is given to using an additional chemical oxidant, preferably in the case of the oxidation dye precursors. When a brightening effect on human hair is desired in addition to coloring with the coloring components, an additional chemical oxidizer is generally used. As a chemical oxidizing agent are persulfates, chlorites and in particular hydrogen peroxide or its addition products of urea, melamine and sodium borate in question.

The compositions according to the invention contain at least one additional chemical oxidizing agent, preferably in an amount of 0.5 to 12.0% by weight, in particular 6 to 12% by weight, in each case based on the weight of the ready-to-use agent. A further embodiment of the agent according to the invention is a coloring agent for keratin-containing fibers, in particular human hair, which is mixed immediately before use of two components, wherein the first component comprises an agent containing in a carrier at least one developer component and optionally at least one

Coupler component and / or at least one substantive dye, the second component is an oxidizing agent composition containing at least one chemical oxidizing agent, in particular hydrogen peroxide, and at least one of the two components comprises at least one compound of the formula (I)

wherein R ¹ , R ² and M are defined as described above, and / or at least one of the two components at least one compound of the formula (II)

wherein R ³ , R ⁴ and M 'are defined as described above. It is preferred according to the invention, when the compounds of formula (I) and / or the formula (II) are both contained in the first component.

Optionally, the agent according to the invention can generally also be applied to the hair together with an oxidation activator which activates the oxidation of the oxidation dye precursors by the oxidizing agent. As mentioned above, the oxidizing agent is atmospheric oxygen or additional chemical oxidizing agents. The oxidation activators are preferably selected from the group consisting of carbonates, hydrogencarbonates, carbamates, carboxylic esters or their salts, aldehydes, in particular aliphatic aldehydes, 1,3-dihydroxyacetone, imidazole and its derivatives, alkali metal and ammonium peroxydisulfates, metal ions, iodides, Quinones and enzymes. The oxidation activators are preferably present in amounts of from 0.01 to 5% by weight, based on the weight of the ready-to-use agent, in the agents according to the invention.

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 in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

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

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

Glucose oxidase and D-glucose,

Glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts,

Alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and 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 (oxidative) hair dye is expediently prepared immediately before use by mixing the oxidizing agent composition with the carrier of the coloring components, preferably in the weight ratio range of 1: 4 to 4: 1, in particular 1: 2 to 2: 1. The effects according to the invention of the compounds of the formulas (I) and (II) or their combination can be increased in a synergistic manner if the agent according to the invention additionally

(c) containing at least one active ingredient selected from at least one member of the group formed from d) protein hydrolysates, c2) silicone derivatives, c3) polyphenols and c4) (pseudo) ceramides.

In this case, again, an active ingredient combination according to the invention is preferred, the (a) at least one N-acylsarcosine derivative of the formula (I) and (b) at least one N-acyl taurine derivative of the formula (II) and (c) at least one member of the above c), c3) or c4).

The protein hydrolysates c1) are product mixtures which are obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins).

According to the invention, protein hydrolysates of both vegetable and animal 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 keratin DEC ^® (Vincience) Dehylan ^® (Cognis), Promois® ^® (Interorgana) Collapuron ^® (Cognis), Nutrilan® ^® (Cognis), Gelita-Sol ^® (German Gelatinefabriken Stoess & Co) distributed Lexein ^® (Inolex) and kerasol tm ^® (Croda).

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

Although the use of the protein hydrolysates is preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also it is possible to use derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are "(Croda) sold, for example, under the names Lamepon® ^® (Cognis), Gluadin® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or crotein ^®.

Preferably, the protein hydrolysates in an amount of 0.05 to 5 wt .-%, particularly preferably from 0.5 to 2.0 wt .-%, each based on the weight of the ready-to-use agent included.

The silicone derivatives c2), when present in the compositions according to the invention, are preferably present in amounts of from 0.05 to 5% by weight, preferably from 0.2 to 5% by weight, based in each case on the ready-to-use agent.

More preferably, the silicones c2) are selected from at least one member of the list formed from:

(i) polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes which are volatile or nonvolatile, straight chain, branched or cyclic, crosslinked or uncrosslinked;

(ii) polysiloxanes containing in their general structure one or more organofunctional groups selected from: a) substituted or unsubstituted aminated groups; b) (per) fluorinated groups; c) thiol groups; d) carboxylate groups; e) hydroxylated groups; f) alkoxylated groups; g) acyloxyalkyl groups; h) amphoteric groups; i) bisulfite groups; j) hydroxyacylamino groups; k) carboxy groups;

I) sulfonic acid groups; and m) sulfate or thiosulfate groups;

(iii) linear polysiloxane (A) - polyoxyalkylene (B) - block copolymers of the type (AB) _n with n>3; (iv) grafted silicone polymers having a non-silicone-containing organic backbone consisting of an organic backbone formed from organic monomers, which contain no silicone to which at least one polysiloxane macromer has been grafted in the chain and optionally on at least one chain end;

(v) grafted polysiloxane backbone silicone polymers having grafted thereto non-silicone-containing organic monomers having a polysiloxane backbone to which at least one organic macromer containing no silicone has been grafted in the chain, and optionally at least at one of its ends , such as the commercial product Abil B 8832 from Degussa marketed under the INCI name Bis-PEG / PPG-20/20 dimethicone;

(vi) or mixtures thereof.

Particularly preferred cosmetic or dermatological preparations according to the invention are characterized in that they contain at least one silicone of the formula (Si-1)

(CH ₃ ) ₃ Si - [O-Si (CH ₃ ) ₂ ] _x -O-Si (CH ₃ ) 3 (Si-1),

in which x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.

The inventively preferred cosmetic or dermatological preparations contain a silicone of the above formula (Si-1). These silicones are referred to as dimethicones according to the INCI nomenclature. It is in the context of the present invention as the silicone of the formula (Si-1), preferably the compounds:

(CHa) ₃ Si-O-Si (CH ₃ ) ₃ (CHa) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si [O- (CH ₃ J ₂ Si] ₂ -O-Si (CHa) ₃ (CHa) ₃ Si [O- (CH ₃ J ₂ Si] J-O-Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si [O- ( CH ₃ J ₂ Si] ₄ T 0-Si (CH ₃ ) ₃ (CH ₃ J ₃ Sh [O- (CH ₃ J ₂ Si) _S -O-Si (CH ₃ J ₃ (CH ₃ ) ₃ Si [ O- (CH ₃ ) ₂ Si] O-Si (CH ₃ ) ₃ (CHa) ₃ Si [O- (CH ₃ ) ₂ Si] τ 0-Si (CH ₃ ) ₃ (CHa) ₃ Si [O- (CH ₃ J ₂ Si) ₁ T 0 -Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si [O- (CH ₃ J ₂ Si) ( _T 0-Si (CH ₃ J ₃ (CHa) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₀ -O-Si (CH ₃ ) ₃ (CHa) ₃ Si [O- (CH ₃ J ₂ Si) HO-Si (CH ₃ J ₃ _(CH3 J ₃ Sh [O- (CH ₃ J ₂ Si] ₁₂ -O-Si (CH ₃₎ ₃ (CH ₃₎ ₃ Si- [O- (CH ₃₎ ₂ Si] ₁₃ -O-Si (CH ₃ ) ₃ (CHa) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₄ -O-Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₅ -O- Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₆ -O-Si (CH ₃ ) ₃ (CHa) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₇ -O-Si (CH ₃ ) ₃ (CHa) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₈ -O-Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₉ -O-Si (CH ₃₎ ₃ (CHa) ₃ Si- [O- (CH ₃₎ ₂ Si] ₂₀ -O-Si (CH ₃₎ ₃

where (CH ₃ ) ₃ Si-O-Si (CH ₃ ) ₃ , (CH ₃ ) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) ₃ and / or (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₂ -O-Si (CH ₃ ) _{3 are} particularly preferred.

Of course, mixtures of o.g. Silicones may be included in the preferred compositions of the invention.

Preferred according to the invention can be used silicones have viscosities at 20 ⁰ C for from 0.2 to 2 mmV ^1, wherein silicones having viscosities of 0.5 to 1 mmV ¹ are particularly preferred.

Particularly preferred agents according to the invention contain one or more amino-functional silicones. Such silicones may e.g. by the formula (Si-2)

M (RaQ _b SiO ₍₄ -a- _{b) / 2)} x (RcSiO _{_(ØC) / 2)} y M (Si-2)

Be described, taking in the above formula

R is a hydrocarbon or a hydrocarbon radical having 1 to about 6

Carbon atoms,

Q is a polar radical of the general formula -R ¹ HZ, in which

R ^{1 is} a divalent linking group bonded to hydrogen and the radical Z composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms, and

Z is an organic, amino-functional group containing at least one amino-functional group; a assumes values in the range of about 0 to about 2, b takes values in the range of about 1 to about 3, a + b is less than or equal to 3, and c is a number in the range of about 1 to about 3, and x a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25; and y is a number ranging from about 20 to about 10,000, preferably from about 125 to about 10,000 and most preferred is from about 150 to about 1000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy.

Non-limiting examples of the groups represented by R in formula (Si-2) include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, as well as sulfur-containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R ¹ include methylene, ethylene, propylene, hexamethylene, decamethylene, - CH ₂ CH (CH ₃ ) CH ₂ -, phenylene, naphthylene, -CH ₂ CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ - , -OCH ₂ CH ₂ -, - OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) C (O) OCH ₂ -, - (CH ₂ ) ₃ CC (O) OCH ₂ CH ₂ - C ₆ H ₄ C ₆ H ₄ -, -C ₆ H 4 CH ₂ C ₆ H ₄ -; and - (CH ₃ C (O) SCH ₂ CH ₂ -.

Z is according to formula (Si-2) an organic, amino-functional radical containing at least one functional amino group. A possible formula for said Z is NH (CH ₂ ) _Z NH ₂ , where z is an integer greater than or equal to 1. Another possible formula for said Z is -NH (CH ₂ ) _Z (CH ₂ ) _ZZ NH, wherein both z and zz independently of one another are an integer greater than or equal to 1, this structure comprising diamino ring structures, such as piperazinyl. Said Z is most preferably an -NHCH ₂ CH ₂ NH ₂ radical. Another possible formula for said Z is -N (CH ₂ ) _Z (CH ₂ ) _ZZ NX ₂ or -NX ₂ , wherein each X of X _{2 is} independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is 0. Q according to formula (Si-2) is most preferably a polar amino-functional radical of formula - CH ₂ CH ₂ CH ₂ NH ₂ CH ₂ CH ₂ NH ₂ .

In the formula (Si-2), α assumes values in the range of 0 to 2, b takes values in the range of 2 to 3, a + b is less than or equal to 3, and c is a number in the range of 1 to 3. The molar ratio of the R _a Q _b SiO ₍₄ _{a a} _{b) / 2} units to the R ₀ SiO ₍₄ _{c) / 2} units in formula (Si-2) is in the range of about 1: From 2 to 1: 65, preferably from about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1: 20. If one or more of the above formula (Si-2) silicones are used then the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.

Preferred cosmetic or dermatological preparations according to the invention contain an amino-functional silicone of the formula (Si-3)

R'aG3-a-Si (OSiG ₂₎ rr (OSiG _b R _'2 - b) mO-SiG _3-a-R'a (Si-3),

where:

G is -H, a phenyl group, -OH, -O-CH ₃ , -CH ₃ , -O-CH ₂ CH ₃ , -CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -O-CH (CH ₃ ) ₂ , -CH (CH ₃ ) ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -O-CH ₂ CH ( CHa) ₂ , -CH ₂ CH (CHa) ₂ , -O-CH (CH ₃ ) CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -O-C (CH ₃ J ₃ , -C ( CH ₃ ), a stands for a number between 0 and 3, in particular 0, b stands for a number between 0 and 1, in particular 1, m and n are numbers, whose sum (m + n) between 1 and 2000, preferably is between 50 and 150, where n preferably assumes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10,

R ^' is a monovalent radical selected from -QN (R ") - CH ₂ -CH ₂ -N (R") ₂

-QN (R ¹¹ J ₂

-QN ⁺ (R ¹ ^ ₃ A ⁾

-QN ⁺ H (R ") ₂ A ^"

-QN ⁺ H ₂ (R ") A ^"

-QN (R ¹ ^ -CH ₂ -CH ₂ -N ⁺ R ¹¹ H ₂ A-, wherein each Q is a chemical bond, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C (CHa) ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, - CH ₂ C (CHa) ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -, R "represents identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ - CH (CH ₃ ) Ph, the C _{1 -20} -Al kylreste, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , - CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , and A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.

Cationic silicone oils, such as the commercially available Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone referred to as amodimethicone), DC 2-2078 (manufactured by Dow Corning, INCI: aminopropyl phenyl trimethicone), DC 5, are suitable according to the invention -71 13 (manufacturer Dow Corning, INCI name: Silicone Quaternium 16), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt;. diquaternary polydimethylsiloxanes, quaternium-80).

Particularly preferred agents according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (Si 3-a)

(CH ₃ ) ₃ Si [O-Si (CH ₃ ) ₂ ] _n [O-Si (CH ₃ )] _m -OSi (CH ₃ ) ₃ (Si-3a),

CH ₂ CH (CH ₃ ) CH ₂ NH (CH ₂ ) ₂ NH ₂

in which m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes.

These silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration and are available, for example, under the name Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone).

Particular preference is also given to compositions according to the invention which contain at least one amino-functional silicone of the formula (Si-3b)

R- [Si (CH ₃₎ ₂ -O] _n1 [Si (R> O] _m - [Si (CH ₃₎ ₂ -O] _n2 SiMe ₂ R (Si-3b),

I (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ contain, in which

R is -OH, an (optionally ethoxylated and / or propoxylated) (Ci to C ₂ o) -

Alkoxy group or a -CH ₃ group,

R 'is -OH, a (C ₁ to C ₂₀ ) alkoxy group or a -CH ₃ group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and Is 150, wherein the sum (n1 + n2) preferably takes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10.

These silicones are according to the INCI declaration as Amodimethicone, or as functionalized Amodimethicone, such as bis (C13-15 alkoxy) PG Amodimethicone (for example, as a commercial product: DC 8500 from Dow Corning available), trideceth-9 PG-amodimethicones (for example as a commercial product Silcare Silicone SEA available from Clariant).

Regardless of which amino-functional silicones are used, preference is given to cosmetic or dermatological preparations according to the invention which contain an amino-functional silicone whose amine number is above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g is. The amine number stands for the milliequivalents of amine per gram of the amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.

Cosmetic or dermatological preparations preferred according to the invention are characterized in that, based on their weight, they contain 0.01 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.25 to 7.5% by weight and in particular from 0.5 to 5% by weight of amino-functional silicone (s).

The cyclic dimethicones designated as cyclomethicones according to INCI are also preferably used according to the invention. Here, cosmetic or dermatological preparations according to the invention are preferred which contain at least one silicone of the formula (Si -4)

in which x is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and especially 0, 1, 2, 3, 4, 5 or 6.

The silicones described above have a backbone composed of -Si-O-Si units. Of course, these Si-O-Si units may also be interrupted by carbon chains. Appropriate molecules are accessible by chain extension reactions and are preferably used in the form of silicone-in-water emulsions.

The silicone-in-water emulsions which can be used according to the invention can be prepared by known processes, as disclosed, for example, in US Pat. No. 5,998,537 and EP 0 874 017 A1.

In summary, this method of preparation comprises the emulsifying mixture of components, one of which contains at least one polysiloxane, the other of which contains at least one organosilicone material which reacts with the polysiloxane in a chain extension reaction, with at least one metal ion-containing catalyst for the chain extension reaction, at least one surfactant and water present are.

Chain extension reactions with polysiloxanes are known and may include, for example, the hydrosilylation reaction in which an Si-H group having an aliphatically unsaturated group in the presence of a platinum / rhodium catalyst to form polysiloxanes having some Si (C) _P- Si bonds (p = 1-6), the polysiloxanes also being referred to as polysiloxane-polysilalkylene copolymers.

The chain extension reaction may also include the reaction of an Si-OH group (e.g., a hydroxy-terminated polysiloxane) with an alkoxy group (e.g., alkoxysilanes, silicates, or alkoxysiloxanes) in the presence of a metal-containing catalyst to form polysiloxanes. The polysiloxanes used in the chain extension reaction comprise a substantially linear polymer of the following structure: R-Si (R ₂ H-OSi (R ₂ H _n -O-SiR ₃

In this structure, each R independently represents a hydrocarbon radical having up to 20 carbon atoms, preferably having 1 to 6 carbon atoms, such as an alkyl group (for example, methyl, ethyl, propyl or butyl), an aryl group (for example, phenyl), or group required for the chain extension reaction ("reactive group", for example, Si-bonded H atoms, aliphatic unsaturated groups such as vinyl, allyl or hexenyl, hydroxy, alkoxy such as methoxy, ethoxy or propoxy, alkoxy-alkoxy, acetoxy, amino, etc.), with the proviso that on average one to two reactive groups are present per polymer, n is a positive number> 1. Preferably, a plurality of the reactive groups, more preferably> 90%, and especially> 98% of the reactive groups, at the terminal Si -Atomen bound in siloxane. Preferably, n is numbers describing polysiloxanes having viscosities between 1 and 1,000,000 mm ² / s, more preferably viscosities between 1,000 and 100,000 mm ² / s.

The polysiloxanes may be branched to a low degree (for example, <2 mol% of the siloxane units), but the polymers are substantially linear, more preferably fully linear. In addition, the substituents R may in turn be substituted, for example with N-containing groups (for example amino groups), epoxy groups, S-containing groups, Si-containing groups, O-containing groups, etc. Preferably, at least 80% of the radicals R are alkyl radicals, especially preferably methyl groups.

The organosilicone material that reacts with the polysiloxane in the chain extension reaction may be either a second polysiloxane or a molecule that acts as a chain extender. When the organosilicone material is a polysiloxane, it has the above-mentioned general structure. In these cases, one polysiloxane in the reaction has (at least) one reactive group, and a second polysiloxane has (at least) a second reactive group that reacts with the first.

If the organosilicone material comprises a chain-extending agent, it may be a material such as a silane, a siloxane (e.g. disiloxane or trisiloxane) or a silazane. Thus, for example, a composition which comprises a polysiloxane according to the above-described general structure which comprises at least one Si-OH group has been chain extended by reacting with an alkoxysilane (for example, a dialkoxysilane or trialkoxysilane) in the presence of tin or titanium-containing catalysts.

The metal-containing catalysts in the chain extension reaction are usually specific for a particular reaction. Such catalysts are known in the art and include, for example, metals such as platinum, rhodium, tin, titanium, copper, lead, etc. In a preferred chain extension reaction, a polysiloxane having at least one aliphatically unsaturated group, preferably an end group, is reacted with an organosilicone material Presence of a hydrosilylation catalyst which is a siloxane or polysiloxane having at least one (preferably terminal) Si-H group. The polysiloxane has at least one aliphatically unsaturated group and satisfies the general formula given above in which R and n are as defined above, with an average of between 1 and 2 groups R having one aliphatically unsaturated group per polymer. Representative aliphatic unsaturated groups are, for example, vinyl, allyl, hexenyl and cyclohexenyl or a group R ² CH = CHR ³ in which R ^{2 is} a divalent aliphatic silicon-bonded chain and R ^{3 is} a hydrogen atom or an alkyl group. The organosilicone material having at least one Si-H group preferably has the above-mentioned structure, wherein R and n are as defined above and wherein, on average, between 1 and 2 groups R is hydrogen and n is 0 or a positive integer.

This material may be a polymer or a low molecular weight material such as a siloxane (for example, a disiloxane or a trisiloxane).

The polysiloxane having at least one aliphatic unsaturated group and the organosilicone material having at least one Si-H group react in the presence of a hydrosilylation catalyst. Such catalysts are known in the art and include, for example, platinum and rhodium-containing materials. The catalysts may take any known form, for example platinum or rhodium coated on support materials (such as silica gel or activated carbon) or other suitable compounds such as platinum chloride, salts of platinum or chloroplatinic acids. Chloroplatinic acid either as a commercially available hexahydrate or in anhydrous form is a preferred catalyst because of good dispersibility in organosilicone systems and low color change.

In another preferred chain extension reaction, a polysiloxane having at least one Si-OH group, preferably an end group, is added with an organosilicone material Reaction having at least one alkoxy group, preferably a siloxane having at least one Si-OR group or an alkoxysilane having at least two alkoxy groups. In this case, the catalyst used is again a metal-containing catalyst.

For the reaction of an Si-OH group with an Si-OR group, there are many catalysts known from the literature, for example organometallic compounds such as organotin salts, titanates or titanium chelates or complexes. Examples include stannous octoate, dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, dibutyltin dimethoxide, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin dineodecanoate, triethyltin tartrate, tin oleate, tin naphthenate, tin butyrate, tin acetate, tin benzoate, tin sebacate, Tin succinate, tetrabutyl titanate, tetraisopropyl titanate, tetraphenyl titanate, tetraoctadecyl titanate, titanium naphthanate, ethyl triethanolamine titanate, titanium diisopropyl diethyl acetoacetate, titanium diisopropoxy diacetyl acetonate and titanium tetra alkoxides in which the alkoxide is butoxy or propoxy.

Agents which are likewise preferred according to the invention are characterized in that they contain at least one silicone of the formula (Si-5)

R _{3 is} -Si- [O-SiR ₂ ] X- (CH ₂ ) H- [O-SiR ₂ Jy-O-SiR ₃ (Si-5),

in which R is identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph, the C ₂₀ -alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , x and y are a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6, and n is a number from 0 to 10, preferably from 1 to 8 and in particular from 2, 3, 4, 5, 6.

The silicones are preferably water-soluble. According to the invention preferred means of Ausfϋhrungsform with a silicone c2) are characterized in that the silicone c2) is water-soluble

Corresponding hydrophilic silicones are selected, for example, from the compounds of the formulas (Si-6) and / or (Si-7). Particularly preferred water-soluble silicone-based surfactants are selected from the group of dimethicone copolyols which are preferably alkoxylated, in particular polyethoxylated or polypropoxylated. Dimethicone copolyols are understood according to the invention as meaning preferably polyoxyalkylene-modified dimethylpolysiloxanes of the general formulas (Si-6) or (Si-7):

O) _b -R (Si-6)

R'-Si- | - [OSi (CH 3) 2] χ- (OC ₂ H ₄ ) _a - (OC ₃ H ₆ ) _b -OR "

(Si-7) wherein R represents a hydrogen atom, an alkyl group having 1 to 12 C atoms, a

Alkoxy group having 1 to 12 carbon atoms or a hydroxyl group, the radicals R 'and R "are alkyl groups having 1 to 12 carbon atoms, x is an integer from 1 to 100, preferably from 20 to 30, y is a integer from 1 to 20, preferably from 2 to 10 and a and b are integers from 0 to 50, preferably from 10 to 30.

Compounds falling within the above formulas are disclosed in the following patent applications, which are incorporated by reference: US-A-4,122,029; US-A-4,265,878; US-A-4,421,769 and GB-A-2,066,659.

Particularly preferred dimethicone copolyols according to the invention are, for example, the products sold commercially under the trade name SILWET (Union Carbide Corporation) and DOW CORNING (Dow).

Dimethicone copolyols particularly preferred according to the invention are Dow Corning 190 and Dow Corning 193 (Dow). Polyphenols c3) are generally compounds containing more than two phenolic (polyol) or phenolic ether groups belonging to different classes of substances. The polyphenols are preferably selected from at least one member of the group formed from: c3- 1) hydroxycinnamic acids, c3-2) 6,7-dihydroxycoumarins, c3-3) hydroxybenzoic acids, c3-4) catechols, c3-5) Leucoanthocyanidins, c3-6) anthocyanidins, c3-7) flavanones and c3-8) flavones and c3-9) flavonols.

In nature, free and etherified polyphenols occur, for example, in flower dyes (anthocyanidins, flavones), in tannins (catechins, tannins), as lichen or fern ingredients (usnic acid, acylpolyphenols), in lignins and as gallic acid derivatives. Preferred polyphenols are flavones, catechins, usnic acid, and as tannins the derivatives of gallic acid, digallic acid and digalloylgallic acid. Particularly preferred polyphenols are the monomeric catechins, ie the derivatives of flavan-3-ols, and leucoanthocyanidins, ie the derivatives of leucoanthocyanidins which preferably carry phenolic hydroxyl groups in the 5,7,3 ', 4', 5 'position, preferably epicatechin and epigallocatechin, as well as the tannins resulting from self-condensation. Such tannins are preferably not used in isolated pure substance, but as extracts of tanning-rich plant parts, eg. Extracts of catechu, quebracho and oak bark and other tree bark, leaves of green tea (camellia sinensis) and mate. Also particularly preferred are the tannins.

The ceramides c4) used are preferably the sphingolipids of the formula (VI),

R ¹ is a linear C ₁₂ - to C ₃₀ -alkyl group or a saturated or unsaturated U) - (C ₁₂ - to C ₂₀ ) -acyloxy- (C ₁₂ -C ₃₀ ) -alkyl group (as preferred tricosanyl, heptadecanyl or ω-

(Octadeca-9,12-dienyloxy) -nonacosanyl) and R ² is a saturated or unsaturated C ₁₅ -alkyl group or a saturated or unsaturated C ₁₅ -hydroxyalkyl group (such as, for example, pentadeca-1 -ene-1-yl, 3 -

Hydroxypentadeca-1 -ene-1-yl, 1-hydroxypentadecanyl).

Preferred compounds according to formula VI according to the invention are the compounds ceramides I, ceramides II, ceramides 1, ceramides 2, ceramides 3, ceramides 5 and ceramides 6 known under the INCI names as active ingredient (W). Mixtures of the compounds of formula (VI) are particularly preferably used, which are obtainable for example under the trade name of SK-Influx ^® and Ceramide III respectively by Degussa Care Specialties, and the commercial product Ceramide TIC-001, sold by the company Takasago International Corporation is marketed. The compounds of the formula (VI) are preferably used in an amount of from 0.01 to 1.0% by weight, based on the weight of the ready-to-use cosmetic product.

In addition, Pseodoceramide, such as in particular the pseudoceramide N- (C. ₈ ₂₂ acyl) -C. ₈ ₂₂ -acyl-hydroxyproline (such as the cetyl-hydroxyproline palmitamides according to the product Sym Repair 153884 from Symrise) according to the invention pseudoceramides c4).

The ready-to-use agent according to the invention should preferably have a pH in the range from pH 5 to pH 12, in particular from pH 7 to pH 11. Particularly preferred is the use of the hair dye in a weakly alkaline medium in a pH range between pH 7 and pH 9.

The agents according to the invention may additionally contain all known and commonly used active ingredients and adjuvants in these fields.

The compounds of the formula (I) and / or of the formula (II) used can completely or partially replace the anionic surfactants customarily used in color-changing agents. Thus, the compounds of formula (I) and / or formula (II) can be used as the sole anionic surfactant in the compositions, or it can be used mixtures with conventional other anionic surfactants. These further anionic surfactants are explained in more detail later. For example, the compounds of formulas (I) and / or (II) and further anionic surfactants in a weight ratio in the range of 1: 0.002 to 3.5: 1, particularly preferably 1: 0.5 to 1: 2, in particular 1: 0.75 to 1: 1, 5 are present.

In particular, it is preferred according to the invention, in a conventional cream base containing alkyl sulfates or alkyl ether sulfates, especially laureth sulfate, as anionic surfactants, the alkyl sulfates or alkyl ether sulfates wholly or partly by the compounds of formula (I) and / or (II) used in the invention replace. In a preferred embodiment, the agent according to the invention, in particular low in ammonia, contains as limited content of these surfactants therefore 0 to 0.5 wt .-%, in particular 0 to 0.3 wt .-% of at least one anionic surfactant selected from linear or branched Cs to C4o alkyl sulfates, linear or branched C ₈ to C ₄₀ alkyl ether sulfates with at least one ethylene oxide

Unit or propylene oxide unit in the molecule.

In agents for the oxidative dyeing of hair, in particular when replacing part or all of the conventional anionic surfactant, such as alkyl sulfates or alkyl ether sulfates, in particular laureth sulfates, by the compounds of the formulas (I) and / or (II) used in the dyeing process and subsequently Investigation of colorations a significantly increased color stability and thus determined color fastness.

In a further embodiment, the agents according to the invention may contain at least one additional surfactant which is different from compounds of the formulas (I) and (II). In principle, both further 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.

Further anionic surfactants suitable in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and Trialkanolammoniumsalze with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 carbon atoms (soaps ) Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or 1 to 16, anionic alkyl oligoglycosides or anionic Alkenyloligoglykosid- Derivatives selected from alkyl and / or alkenyl oligoglycoside carboxylates, sulfates, phosphates and / or isethionates derived from alkyl and / or alkenyl oligoglycosides of general formula (VI), RO- (G) p (VI) with the meaning

RC _6-22 alkyl or C ₆ . ₂₂ alkenyl,

G glycoside unit which is derived from a sugar containing 5 or 6 carbon atoms, p number from 1 to 10, in particular the Laurylglucosidcarboxylat, such as is available as Plantapon ^® LGC from Cognis Germany,

Acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobernsteinsäuremono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 carbon atoms, linear alpha-olefinsulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and Alkylpolyglykolethersulfate the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in the R is a preferably linear alkyl group with 10 bis 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 adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

Preferred additional anionic surfactants are selected from the abovementioned anionic alkyl oligoglycoside or anionic alkenyl oligoglycoside derivatives, 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. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. 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 on

Alkylphenols having 8 to 15 C atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 mol

Ethylene oxide with glycerol,

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

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

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

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

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

Particular preference is given to those alkylpolyglycosides in which R ¹ consists essentially of C ₈ and C 10 -alkyl groups, essentially of C ₁₂ and C ₁₄ -alkyl groups, essentially of C ₈ to C ₁₆ -alkyl groups or essentially of C 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. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO * ^" 'or -SO ₃ '^"'group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, 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 coco acylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, 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 a structural element. Preferred esterquats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium 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. An inventively particularly suitable compound from this group of substances under the name Tegoamid ^® S 18 commercial stearamidopropyl dimethylamine is.

Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

An example of a suitable cationic surfactant quaternary sugar derivative is the commercially available product Glucquat ^® 100 is, 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 usually preferred to use native plant or animal raw materials in the manufacture of these substances, so that one can Substance mixtures with different, depending on the particular raw material alkyl chain lengths obtained.

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

As pH-adjusting agents, the agents according to the invention contain acids and / or alkalizing agents.

As acids according to the invention preferably phosphoric acid or edible acids, such as citric acid, tartaric acid or malic acid, are used.

The alkalizing agents usable in the present invention are preferably selected from the group consisting of ammonia, basic amino acids, alkali hydroxides, alkanolamines, alkali metal metasilicates, urea, morpholine, N-methylglucamine, imidazole, alkali phosphates and alkali hydrogen phosphates. The alkali metal ions used are preferably lithium, sodium, potassium, in particular sodium or potassium. Again, preferably, the alkalizing agents are different from ammonia.

The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from L-arginine, D-arginine, D, L-arginine, L-histidine, D-histidine, D, L-histidine, L-lysine, D-lysine, D, L-lysine, more preferably L-arginine, D-arginine, D, L-arginine used as an alkalizing agent according to the invention.

The usable as the inventive alkalizing alkali metal hydroxides are preferably selected from the group consisting of sodium hydroxide and potassium hydroxide. The alkanolamines which can be used as alkalizing agents according to the invention are preferably selected from primary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1 Aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-1-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol. Very particularly preferred alkanolamines according to the invention are selected from the group consisting of 2-aminoethane-1-ol, 2-amino-2-methylpropan-1-ol and 2-amino-2-methyl-propane-1,3-diol.

The alkalizing agent is particularly preferably selected from at least one compound from the group formed from 2-aminoethanol, 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propane-1,3-diol, Potassium hydroxide, L-arginine, D-arginine, DL-arginine, N-methylglucamine, morpholine, imidazole and urea.

Furthermore, colorants according to the invention may contain further active ingredients, auxiliaries and additives, for example nonionic polymers, for example vinylpyrrolidone / vinyl acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary

Groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as acrylamidopropyl-tri methyl ammonium chloride / acrylate copolymers and octyl acrylamide / methyl methacrylate / tert.

Butylaminoethyl methacrylate ^ -hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids,

Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / 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,

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,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-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,

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

Vitamins, provitamins and vitamin precursors, in particular those of groups A, B3, B5, Be,

C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel,

Hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera,

Spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime,

Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow,

Meadowfoam, Quendel, Yarrow, Thyme, Melissa, Hauhechel, 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,

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

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,

Hydrogencarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

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

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

pigments

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

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

antioxidants contain.

The agent according to the invention contains the ingredients according to the invention in a carrier. Such carriers are for example creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are particularly suitable for use on the hair. But it is also conceivable to integrate the ingredients in a powdered or tablet-like formulation, which is dissolved in water before use. The carriers may in particular be aqueous or aqueous-alcoholic.

An aqueous carrier contains at least 50% by weight of water.

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

The agent according to the invention can be provided in a packaging unit (kit) which contains at least one separately prepared, inventive agent of the second subject of the invention. In addition, the kit may contain at least one separately formulated oxidizer composition, especially if an (oxidative) colorant is to be provided. In addition, the kit may additionally contain optional instructions for use, application aids, mixing bowls or protective gloves.

A third object of the present invention is a method for treating keratin-containing fibers, in which an agent of the second subject of the invention is applied to the fibers and rinsed again after an exposure time. The application temperatures can be in a range between 15 and 40 ⁰ 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, such as a dyeing shampoo was used.

B e i s p e e l e

The following compositions of the following Tables 1, 2, 4 and 5 were prepared according to standard production methods. All quantities are - unless otherwise indicated - weight percent. The following commercial products were used as raw materials:

Hydrenof DC ₁₆ -C ₁₈ -FeHa I kohol (INCI name: Cetearyl alcohol)

(Cognis Germany) Lorol ^® techn. C ₁₂ -C ₁₈ -FeHa I kohol (INCI name: Coconut alcohol)

(Cognis Germany)

Edenor ^® C14 myristic acid (INCI name: Myristic Acid) (Cognis) Dehyton ^® CN, N-dimethyl-N- (C8-18-cocamidopropyl) ammoniumaceto- betaine (30% active substance; INCI name: Aqua (Water) , Cocamidopropyl Betaine) (Cognis)

Eumulgin ^® B 1 Cetylstearylakohol with 12 EO units (EO)

(INCI name: Ceteareth-12) ((Cognis Germany) Eumulgin ^® B2 Cetylstearylalkohol with about 20 EO INCI

Name: Ceteareth-20) (Cognis Germany) Akypo Soft 45 NV ^® 2- (C ₁₂ ₁₄ -fatty alcohol ethoxylate (4.5 EO.)) - acetic acid, sodium salt; 21% active substance in water; INCI name: Sodium Laureth-5 Carboxylate (KAO)

Texapon ^® K 14 S 70 C Laurylmyristylethersulfat sodium salt (ca. 68% to 73% active substance content ^'; INCI name: Sodium Myreth Sulfate) (Cognis) Disponil ^® FES 77 Kokosfettalkoholether (30 EO) sulfate sodium salt (ca 33% active ingredient content, INCI name: Sodium Coceth-30 Sulfate) (Cognis)

Plantacare ^® 1200 UP C-i2-i6-fatty alcohol Glycoside (about 50% active ingredient content in water, INCI name: lauryl glucoside) (Cognis) Polymer W 37194 approx. 20% by weight of active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride / Acrylates Copolymer (Stockhausen)

Protelan ^® MST 35 mixture of sodium N-Myristoylsarcosinate and

Sodium N-methyl-N-cocoyltaurate (40% by weight of active substance, Zschimmer & Schwartz)

Abil ^® B 8832 INCI name: Bis-PEG / PPG-20/20 Dimethicone

(Degussa)

Keratin DEC ^® INCI name: Hydrolysed Keratin (Vincience) Silcare Silicone SEA ^® INCI name: Trideceth-9 PG-Amodimethicone,

Trideceth-12 (Clariant)

Turpinal ^® SL 1-hydroxyethane-1, 1-diphosphonic acid (INCI name: Etidronic Acid, Aqua (Water)) (Solutia) Texapon ^® NSO UP sodium lauryl ether sulfate (27% active substance in water; INCI: Sodium Laureth Sulfate) (manufacturer: Cognis ) Aculyn ^® 33 30 wt .-% of active substance in water (INCI name: Acrylates copolymer) (Rohm & Haas) DOW ^Corning® DB 1 10 A Nonionic Silicone Emulsion (10% by Weight Active Ingredient) (INCI name: Dimethicone) (Dow Corning)

The formulations V1 and V2 of Table 1 are known dyeing creams with conventional surfactant system. The formulations E1 and E2 of Table 1 and all formulations of Table 4 correspond to formulations according to the invention.

Table 1: Dye cream

Table 2: Developer

2. Coloring and determination of color fastness

2.1 Pretreatment of the hair strands:

Hair strands of the company Kerling (80% gray, 15 cm long, about 2 g) were used. The tresses were first treated with Poly Blonde Ultrablondierung for 30 min at 32 ° C, rinsed with lukewarm water and finally dried in air and stored for 24 h. The tresses were measured colorimetrically (device Spectraflash 450, software Colortools) with determination of the Lab values of the initial hair.

2.2 Determination of wash fastness:

Each color cream V1, E1, V2 and E2 of Table 1 was mixed with the developer emulsion according to Table 2 in a weight ratio of 1: 1. The finished mixtures were placed on the pretreated strands and rinsed after a contact time of 30 min at 32 ° C. The strands were dried and measured again colorimetrically. To determine the wash fastness, the hair strands were subjected to a washing procedure that simulates hair washing:

An ultrasonic bath is filled with 1% aqueous solution of sodium laureth sulfate (pH 4 to 5) (adjusted with citric acid) and dissolved on 40 ⁰ C heated. The colored hair strands were dipped into the wash solution and sonicated for 15 minutes. This treatment corresponds to the cleaning performance of six washes. Subsequently, the strands were rinsed thoroughly, dried and measured again colorimetrically. The evaluation of the wash fastness was made on the residual color strength of the hair strands, which is calculated on the basis of the recorded measurement data before and after 15 min ultrasonic treatment according to the following formula:

The ΔE values are determined from the measured quantities via the color difference formula in each case from the bleached starting hair.

Residual color strength [%] = ΔE ( _∞ ioπert) / ΔE ( _as- is) ^' 100

The color retention of the dyeings obtained with the compositions according to the invention is greater than with the noninventive formulations.

Table 3: residual color strength [in%]

Recipe VI El V2 E2

Residual color strength 87 97 76 89

3.0 Example Formulations Table 4: Coloring creams

Table 5: Developer

Before use, each of the color creams E3 to E12 of Table 4 was mixed with the developer emulsion according to Table 5 in a weight ratio of 1: 1.

3.0 open patch test

The open epicutaneous test according to COLIPA (Test Guidelines for the Assessment of Human Skin Tolerance, 1997) is suitable for testing substances and finished products for skin tolerance. Twenty voluntary female and male skin healthy subjects without age limit were included in the test. The creams C1 and C2 of Table 6 were each mixed in a weight ratio of 1 to 1 with the developer EW of Table 6. The above-described mixture of bleaching cream C1 with the developer EW gives an agent according to the invention. The other agent is not according to the invention and was used for comparison.

For each subject, the finished three application mixtures were randomly placed on the forearm inside with a glass rod over a period of 30 minutes every 30 seconds. After the end of the application, the substances were carefully washed off with water from the forearm and the skin areas were dried. The subjects were then checked for redness of the skin. It was also asked if the test subjects feel itching and, if so, on which skin area. The test results are the table 7 and show the number of subjects in percent, who had at least one of the queried skin reactions.

Table 6: Recipes

Table 7: Test results

The mixture according to the invention caused less discomfort on the skin than the mixture of the prior art.

Claims

Patent claims

1. An agent for coloring keratin-containing fibers, in particular human hair, containing in a carrier at least one coloring component and additionally at least one compound selected from the group consisting of (a) N-acylsarcosine derivatives of the formula (I)

wherein

R ^{1 represents} a (C ₇ to C ₃₀ ) -alkyl group, (C ₇ to C ₃₀ ) -alkenyl group or a (C ₇ to C 1) -hydroxyalkyl group,

R ^{2 is} a (C 1 to C ₄ ) -alkyl group or a (C 1 to C ₄ ) -hydroxyalkyl group, and

wherein

R ^{3 is} a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -

Hydroxyalkyl group stands,

R ^{4 is} a (C ₇ to C ₃ o) -alkyl group, (C ₇ to C ₃ o) -alkenyl group or a (C ₇ to C 30) -hydroxyalkyl group and

M 'is a hydrogen atom or one equivalent of a monovalent or polyvalent one Cations means.

2. Composition according to claim 1, characterized in that the coloring component is selected,

(2) from oxo dye precursors and / or

(3) from at least one direct dye and / or

(4) from at least one precursor of naturally-colored dyes.

3. Composition according to one of claims 1 or 2, characterized in that the radicals R ^{1 of} the formula (I) and R ^{4 of} the formula (II) independently of one another for a (Cg to C23) alkyl group, (C ₉ to C ₂₃ ) Alkenyl group or a (C ₉ to C 12) hydroxyalkyl group.

4. Composition according to one of claims 1 to 3, characterized in that the radicals R ^{1 of} the formula (I) and R ^{4 of} the formula (II) independently represent a radical selected from the list which is formed from nonyl , Undecyl, tridecyl, pentadecyl, heptadecyl, nonadecyl, henicosanyl, 15-methylhexadecyl, heptadec-8-enyl, heptadeca-8,1 1 -dienyl, nonadeca-4,7,10,13-tetraenyl, heptadeca-8,1 1 , 14-trienyl and 1 1-hydroxyheptadecyl.

5. Composition according to one of claims 1 to 4, characterized in that the radical R ² according to formula (I) is a radical selected from the group which is formed from methyl, ethyl, isopropyl, n-propyl and 2 hydroxyethyl.

6. A composition according to any one of claims 1 to 5, characterized in that the radical R ³ according to formula (II) is a radical selected from the group formed from hydrogen, methyl, ethyl, isopropyl, n-propyl and 2-hydroxyethyl.

7. Composition according to one of claims 1 to 6, characterized in that the compounds of formula (I) are selected from at least one member selected from the group consisting of N-lauroyl sarcosine, N-myristoyl sarcosine, N-palmitoyl sarcosine, N - Oleylsarcosine, N-cocoylsarcosine and N-palm kernel sarcosine, and from the salts of the aforementioned N-acylsarcosine derivatives.

8. Composition according to one of claims 1 to 7, characterized in that the compounds of formula (II) are selected from at least one member selected from the group consisting of N-dodecanoyl-N-methyltaurine, N-octadecanoyl-N- methyltaurine, N-hexadecanoyl-N-methyltaurine, N-tetradecanoyl-N-methyltaurine, N-oleyl-N-methyltaurine, N-cocoyl-N-methyltaurine, N-palm kernel N-methyltaurine, as well as the salts of the aforementioned N-acyltaurine derivatives.

9. Composition according to one of claims 1 to 8, characterized in that a combination of at least one compound according to formula (I) with at least one compound according to formula (II) is included.

10. Composition according to one of claims 1 to 9, characterized in that it additionally

(c) at least one active ingredient selected from at least one member of the group formed from c1) protein hydrolysates, c2) silicone derivatives, c3) polyphenols and c4) (pseudo) ceramides.

1 1. Composition according to one of claims 1 to 10, characterized in that it is low in ammonia.

12. A method for treating keratin-containing fibers, wherein an agent according to any one of claims 1 to 1 1 is applied to the fibers and rinsed again after an exposure time.

13. Use of at least one compound from the active ingredients (a) N-acylsarcosine derivatives of the formula (I)

wherein

R ^{1 represents} a (C ₇ to C ₃₀ ) -alkyl group, (C ₇ to C ₃₀ ) -alkenyl group or a (C ₇ to C ₃₀ ) -hydroxyalkyl group,

wherein

Hydroxyalkyl group stands,

R ⁴ is a (C ₇ to ₀ C3) alkyl, (C ₇ to C ₃ o) alkenyl group or a

(C ₇ to C ₃ o) -hydroxyalkyl group and

M 'denotes a hydrogen atom or one equivalent of a mono- or polyvalent cation in, in particular low-ammonia, color-changing agents (i) for intensifying the coloration,

(ii) to increase color fastness, in particular wash fastness, (iii) to reduce scalp irritation, (iv) to relieve sensory discomfort on the scalp, in particular

Stinging or itching.