DE102004047137B4 - Cationic Cream Base II - Google Patents

Abstract

wobei die Reste R¹ bis R⁴ stehen unabhängig voneinander für eine C₁- bis C₄-Alkylkette oder eine C₁₀- bis C₃₀-Alkylkette, mit der Maßgabe, dass mindestens einer und höchstens zwei der Reste R¹ bis R⁴ für eine C₁₂- bis C₃₀-Alkylkette stehen, und X steht für ein physiologisch verträgliches Anion,
(D) Ammoniumhydrogencarbonat, enthält.Agent for coloring keratin fibers, characterized in that it
(A) at least one dye precursor and/or one direct dye
(B) at least one fatty acid glyceryl ester and
(C) at least one cationic surfactant of formula (I)

where the radicals R ¹ to R ⁴ independently of one another represent a C ₁ to C ₄ alkyl chain or a C ₁₀ to C ₃₀ alkyl chain, with the proviso that at least one and at most two of the radicals R ¹ to R ⁴ represent a C ₁₂ to C ₃₀ alkyl chain, and X represents a physiologically acceptable anion,
(D) ammonium bicarbonate.

Description

The present application relates to colorants for keratinic fibers, containing, in addition to direct dyes and/or dye precursors, at least one fatty acid glyceryl ester and at least one specific cationic surfactant and ammonium bicarbonate.

Today, human hair is treated in a variety of ways with hair cosmetic preparations. These include cleansing the hair with shampoos, conditioning and regenerating it with conditioners and treatments, as well as bleaching, coloring, and shaping the hair with dyes, tints, perming products, and styling products. Products for changing or shading the color of the hair play a prominent role.

Temporary coloring typically involves dyes or tints that contain so-called direct dyes as the coloring component. These are dye molecules that absorb directly into the hair and do not require an oxidative process to develop the color. Examples of such dyes include henna, which has been used since ancient times for coloring body and hair. These dyes are generally much more sensitive to shampooing than oxidative dyes, so an often undesirable shift in shade or even visible "discoloration" occurs much more quickly.

For permanent, intensive dyeings with corresponding fastness properties, so-called oxidation dyes are used. Such dyes typically contain oxidation dye precursors, so-called developer components and coupler components. The developer components, under the influence of oxidizing agents or atmospheric oxygen, form the actual dyes, either with each other or by coupling with one or more coupler components. These oxidation dyes are characterized by excellent, long-lasting dyeing results. For natural-looking dyes, a mixture of a larger number of oxidation dye precursors is usually required; in many cases, direct dyes are still used for shading.

Finally, a new dyeing process has recently attracted considerable attention. In this process, precursors of the natural hair pigment melanin are applied to the hair; these then form natural-analog dyes during oxidative processes in the hair. Such a process, using 5,6-dihydroxyindoline as a dye precursor, has been EP-B1-530 229 described. With the use of products containing 5,6-dihydroxyindoline, especially multiple applications, it is possible to restore the natural hair color to people with graying hair. Coloring can be achieved using atmospheric oxygen as the sole oxidizing agent, eliminating the need for additional oxidizing agents. For people with originally medium-blonde to brown hair, indoline can be used as the sole dye precursor. However, for people with originally red and especially dark to black hair, satisfactory results can often only be achieved with the addition of additional dye components, particularly special oxidation dye precursors.

Hair dyes are typically formulated in the form of aqueous emulsions or dye gels, which may be mixed with an oxidizing agent immediately before use. When formulating hair dyes in the form of emulsions, storage stability problems are often observed due to the sometimes very high salt content of the formulations. The salt content can result, among other things, from the dye precursors, which are often used in the form of more storage-stable salts, as well as salt admixtures that arise from the manufacturing process, particularly in the case of direct dyes.

To improve the condition of the fibers, it has long been common practice to subject the fibers to a special aftercare treatment following the color-changing treatment. This involves treating the hair with special active ingredients, such as quaternary ammonium salts or special polymers, usually in the form of a conditioner. Depending on the formulation, this treatment improves combability, hold, and body of the hair, and reduces split ends.

Recently, so-called combination preparations have also been developed to reduce the complexity of the usual multi-stage procedures, especially when used directly by consumers.

In addition to the usual ingredients, such as those used for coloring hair, these products also contain active ingredients previously reserved for hair aftercare products. This saves the consumer an application step; at the same time, packaging costs are reduced, as one less product is needed.

The active ingredients used in such combination preparations must meet stringent stability requirements, particularly because coloring creams typically have a high pH value and oxidizing agent preparations a low pH value. Furthermore, incompatibilities between the various active ingredients and thus poor storage stability must be avoided.

As part of the registration DE-A-199 14 927 , DE-A-199 14 926 and DE-A-44 08 506 Such combinations of active ingredients have already been proposed for use in oxidative dyes. DE 199 01 886 A1 describes a process for producing a hair dye which is in the form of a stable aqueous emulsion and which contains, among other things, water-soluble surfactants, salts and fat phase components.
US 2004/0019980 A1 concerns hair care compositions with more effective dye formation pathways, which contain a water-soluble peroxide, an oxidation dye, and a water-soluble carbonate. However, even these compositions still leave some room for improvement in terms of their conditioning properties, especially on difficult-to-care fibers such as Japanese hair.

There is therefore still a need for cream bases for the color-changing treatment of fibers with good conditioning properties and good stability even in formulations with a high salt content.

It has now surprisingly been found that dyes which, in addition to the coloring components, contain at least one fatty acid glyceryl ester and at least one special cationic surfactant as well as ammonium bicarbonate, are extremely stable despite high salt contents and also have an excellent care effect.

1. (A) mindestens ein Farbstoffvorprodukt und/oder einen direktziehenden Farbstoff
2. (B) mindestens einen Fettsäureglycerylester und
3. (C) mindestens ein kationisches Tensid der Formel (I)
   
   wobei die Reste R¹ bis R⁴ stehen unabhängig voneinander für eine C₁- bis C₄-Alkylkette oder eine C₁₀- bis C₃₀-Alkylkette, mit der Maßgabe, dass mindestens einer und höchstens zwei der Reste R¹ bis R⁴ für eine C₁₂- bis C₃₀-Alkylkette stehen, und X steht für ein physiologisch verträgliches Anion,
4. (D) Ammoniumhydrogencarbonat,

enthält.A first subject of the present application is therefore an agent for coloring keratin fibers, which

1. (A) at least one dye precursor and/or one direct dye
2. (B) at least one fatty acid glyceryl ester and
3. (C) at least one cationic surfactant of formula (I)
   
   where the radicals R ¹ to R ⁴ independently of one another represent a C ₁ to C ₄ alkyl chain or a C ₁₀ to C ₃₀ alkyl chain, with the proviso that at least one and at most two of the radicals R ¹ to R ⁴ represent a C ₁₂ to C ₃₀ alkyl chain, and X represents a physiologically acceptable anion,
4. (D) Ammonium bicarbonate,

contains.

Although the use of conventional thickeners is not excluded in principle, the cream base according to the invention makes it possible to completely dispense with this class of compounds.

It was further found that the cream base according to the invention enables very good absorption of the dye (precursors) onto the hair, ensures very good length uniformity of the coloring, and the fibers shine after treatment. The use of ammonium bicarbonate results in consistently good color performance of the coloring cream, both over extended storage and application periods.

According to the invention, keratin fibers are understood to mean fur, wool, feathers and, in particular, human hair.

• • Oxidationsfarbstoffvorprodukte vom Entwickler- und/oder Kuppler-Typ, und
• • Vorstufen naturanaloger Farbstoffe, wie Indol- und Indolin-Derivate,

sowie Mischungen von Vertretern dieser Gruppen enthalten.The present invention is not subject to any restrictions with regard to the further dye precursors that can be used in the dyeing agents according to the invention. The dyeing agents according to the invention can be used as dye precursors

• • Oxidation dye precursors of the developer and/or coupler type, and
• • Precursors of natural dyes, such as indole and indoline derivatives,

as well as mixtures of representatives of these groups.

In a first preferred embodiment of the present invention, the agents according to the invention contain at least one dye precursor of the developer and/or coupler type.

The developer components usually used are primary aromatic amines with an additional free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives.

wobei

• - G¹ steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• - G² steht für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest oder einen C₁- bis C₄-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• - G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, lod- oder Fluoratom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Acetylaminoalkoxyrest, einen C₁- bis C₄- Mesylaminoalkoxyrest oder einen C₁- bis C₄-Carbamoylaminoalkoxyrest;
• - G⁴ steht für ein Wasserstoffatom, ein Halogenatom oder einen C₁- bis C₄-Alkylrest oder
• - wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Alkylendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

According to the invention, it may be preferred to use a p-phenylenediamine derivative or one of its physiologically acceptable salts as the developer component. Particular preference is given to p-phenylenediamine derivatives of the formula (E1)

where

• - G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy-(C ₁ to C ₄ ) alkyl radical, a 4'-aminophenyl radical or a C ₁ to C ₄ alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• - G ² represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (C ₁ to C ₄ ) alkoxy-(C ₁ to C ₄ ) alkyl radical or a C ₁ to C ₄ alkyl radical substituted by a nitrogen-containing group;
• - G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ hydroxyalkoxy radical, a C ₁ to C ₄ acetylaminoalkoxy radical, a C ₁ to C ₄ mesylaminoalkoxy radical or a C ₁ to C ₄ carbamoylaminoalkoxy radical;
• - 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 in the ortho position to each other, they can together form a bridging α,ω-alkylenedioxo group, such as 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 - to C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group include a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C ₄ -polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived from the invention. according to the invention deviates from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are, in particular, amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -monohydroxyalkylamino groups, imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-3-methyl-(N,N-diethyl)-aniline, N,N-bis-(β-hydroxyethyl)-p-phenylenediamine, 4-N,N-bis-(β-hydroxyethyl)-amino-2-methylaniline, 4-N,N-bis-(β-hydroxyethyl)-amino-2-chloroaniline, 2-(β-hydroxyethyl)-p-phenylenediamine, 2-(α,β-dihydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylenediamine, N,N-(ethyl,β-hydroxyethyl)-p-phenylenediamine, N-(β,γ-dihydroxypropyl)-p-phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine, 2-(β-hydroxyethyloxy)-p-phenylenediamine, 2-(β-Acetylaminoethyloxy)-p-phenylenediamine, N-(β-Methoxyethyl)-p-phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and their physiologically acceptable salts.

According to the invention, very particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2-(β-hydroxyethyl)-p-phenylenediamine, 2-(α,β-dihydroxyethyl)-p-phenylenediamine and N,N-bis-(β-hydroxyethyl)-p-phenylenediamine.

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

wobei:

• - Z¹ und Z² stehen unabhängig voneinander für einen Hydroxyl- oder NH₂-Rest, der gegebenenfalls durch einen C₁- bis C₄-Alkylrest, durch einen C₁- bis C₄-Hydroxyalkylrest und/oder durch eine Verbrückung Y substituiert ist oder der gegebenenfalls Teil eines verbrückenden Ringsystems ist,
• - die Verbrückung Y steht für eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen, wie beispielsweise eine lineare oder verzweigte Alkylenkette oder einen Alkylenring, die von einer oder mehreren stickstoffhaltigen Gruppen und/oder einem oder mehreren Heteroatomen wie Sauerstoff-, Schwefel- oder Stickstoffatomen unterbrochen oder beendet sein kann und eventuell durch einen oder mehrere Hydroxyl- oder C₁- bis C₈-Alkoxyreste substituiert sein kann, oder eine direkte Bindung,
• - G⁵ und G⁶ stehen unabhängig voneinander für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄- Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest oder eine direkte Verbindung zur Verbrückung Y,
• - G⁷, G⁸, G⁹, G¹⁰, G¹¹ und G¹² stehen unabhängig voneinander für ein Wasserstoffatom, eine direkte Bindung zur Verbrückung Y oder einen C₁- bis C₄-Alkylrest, mit den Maßgaben, dass
• - die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten und
• - die Verbindungen der Formel (E2) mindestens eine Aminogruppe enthalten, die mindestens ein Wasserstoffatom trägt.

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

where:

• - Z ¹ and Z ² independently represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ to C ₄ alkyl radical, by a C ₁ to C ₄ hydroxyalkyl radical and/or by a bridge Y or which is optionally part of a bridging ring system,
• - the bridge Y represents an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which may be interrupted or terminated by one or more nitrogen-containing groups and/or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms and may optionally be substituted by one or more hydroxyl or C ₁ to C ₈ alkoxy radicals, or a direct bond,
• - G ⁵ and G ⁶ independently represent a hydrogen or halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ aminoalkyl radical or a direct connection to the bridge Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ to C ₄ alkyl radical, with the provisos that
• - the compounds of formula (E2) contain only one bridge Y per molecule and
• - the compounds of formula (E2) contain at least one amino group carrying at least one hydrogen atom.

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

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

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

wobei:

• - G¹³ steht für ein Wasserstoffatom, ein Halogenatom, einen C₊- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁-bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, einen Hydroxy-(C₁-bis C₄)-alkylaminorest, einen C₁- bis C₄-Hydroxyalkoxyrest, einen C₁- bis C₄-Hydroxyalkyl-(C₁-bis C₄)-aminoalkylrest oder einen (Di-C₁- bis C₄-Alkylamino)-(C₁- bis C₄)-alkylrest, und
• - G¹⁴ steht für ein Wasserstoff- oder Halogenatom, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest oder einen C₁- bis C₄-Cyanoalkylrest,
• - G¹⁵ steht für Wasserstoff, einen C₁- bis C₄-Alkylrest, einen C₁- bis C₄-Monohydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen Phenylrest oder einen Benzylrest, und
• - G¹⁶ steht für Wasserstoff oder ein Halogenatom.

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

where:

• - G ¹³ represents a hydrogen atom, a halogen atom, a C ₊ 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 ₁ to C ₄ )alkyl radical, a C ₁ to C ₄ aminoalkyl radical, a hydroxy-(C ₁ to C ₄ )alkylamino radical, a C ₁ to C ₄ hydroxyalkoxy radical, a C ₁ to C ₄ hydroxyalkyl-(C ₁ to C ₄ )aminoalkyl radical or a (di-C ₁ to C ₄ alkylamino)-(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-(C ₁ to C ₄ )-alkyl radical, a C ₁ to C ₄ aminoalkyl radical or a C ₁ to C ₄ cyanoalkyl radical,
• - G ¹⁵ represents hydrogen, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ stands for 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-methyl-phenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-(β-hydroxyethoxy)-phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino-2-aminomethylphenol, 4-amino-2-(β-hydroxyethyl-aminomethyl)-phenol, 4-amino-2-(β-dihydroxyethyl)-phenol, 4-amino-2-fluorophenol, 4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2-(diethyl-aminomethyl)-phenol and their physiologically acceptable salts.

Very particularly preferred compounds of 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.

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

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

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

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

Preferred pyrazole derivatives are in particular the compounds described in the 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 are described, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)-pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(β-aminoethyl)-amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-Diamino-4-(β-hydroxyethyl)-amino-1-methylpyrazole.

wobei:

• - G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂-bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁-bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• - die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₊-bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁-bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)-aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)-aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• - i hat den Wert 0, 1, 2 oder 3,
• - p hat den Wert 0 oder 1,
• - q hat den Wert 0 oder 1 und
• - n hat den Wert 0 oder 1,

mit der Maßgabe, dass

• - die Summe aus p + q ungleich 0 ist,
• - wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• - wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

where:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, 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 acetylureide or a sulfonyl radical, a (C ₁ - to C ₄ )-alkylamino-(C ₁ - to C ₄ )-alkyl radical, a di-[(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 radical,
• - the X radicals independently of one another represent a hydrogen atom, a C ₊ to C ₄ alkyl radical, an aryl radical, a C ₁ to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ aminoalkyl radical, a (C ₁ to C ₄ )-alkylamino-(C ₁ to C ₄ )-alkyl radical, a di-[(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 hyd roxyalkyl)-aminoalkyl radical, an amino radical, a C ₁ - to C ₄ -alkyl or di-(C ₁ - to C ₄ -hydroxyalkyl)-amino radical, 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,

provided that

• - the sum of p + q is not equal to 0,
• - if p + q is equal to 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);
• - if p + q is 1, n has the value 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

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

If the pyrazole-[1,5-a]-pyrimidine of the above formula (E4) contains a hydroxy group at one of the positions 2, 5 or 7 of the ring system, a tautomeric equilibrium exists, which is represented, for example, in the following scheme:

• - Pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,5-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - Pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• - 2,7-Dimethyl-pyrazol-[1,5-a]-pyrimidin-3,5-diamin;
• - 3-Aminopyrazol-[1,5-a]-pyrimidin-7-ol;
• - 3-Aminopyrazol-[1,5-a]-pyrimidin-5-ol;
• - 2-(3-Aminopyrazol-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• - 2-(7-Aminopyrazol-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• - 2-[(3-Aminopyrazol-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 2-[(7-Aminopyrazol-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 5,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 2,6-Dimethylpyrazol-[1,5-a]-pyrimidin-3,7-diamin;
• - 3-Amino-7-dimethylamino-2,5-dimethylpyrazol-[1,5-a]-pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.Among the pyrazole-[1,5-a]-pyrimidines of the above formula (E4) one can mention in particular:

• - Pyrazole-[1,5-a]-pyrimidine-3,7-diamine;
• - 2,5-Dimethyl-pyrazole-[1,5-a]-pyrimidine-3,7-diamine;
• - Pyrazole-[1,5-a]-pyrimidine-3,5-diamine;
• - 2,7-Dimethyl-pyrazole-[1,5-a]-pyrimidine-3,5-diamine;
• - 3-aminopyrazole-[1,5-a]-pyrimidin-7-ol;
• - 3-aminopyrazole-[1,5-a]-pyrimidin-5-ol;
• - 2-(3-aminopyrazole-[1,5-a]-pyrimidin-7-ylamino)-ethanol;
• - 2-(7-aminopyrazole-[1,5-a]-pyrimidin-3-ylamino)-ethanol;
• - 2-[(3-aminopyrazole-[1,5-a]-pyrimidin-7-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 2-[(7-aminopyrazole-[1,5-a]-pyrimidin-3-yl)-(2-hydroxy-ethyl)-amino]-ethanol;
• - 5,6-Dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine;
• - 2,6-Dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine;
• - 3-amino-7-dimethylamino-2,5-dimethylpyrazole-[1,5-a]-pyrimidine;

as well as their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium exists.

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

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

As coupler components, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are usually used. Particularly suitable coupling substances are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis-(2',4'-diaminophenoxy)-propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

• - m-Aminophenol und dessen Derivate wie beispielsweise 5-Amino-2-methylphenol, N-Cyclopentyl-3-aminophenol, 3-Amino-2-chlor-6-methylphenol, 2-Hydroxy-4-aminophenoxyethanol, 2,6-Dimethyl-3-aminophenol, 3-Trifluoroacetylamino-2-chlor-6-methylphenol, 5-Amino-4-chlor-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)-benzol, 3-Ethylamino-4-methylphenol und 2,4-Dichlor-3-aminophenol,
• - o-Aminophenol und dessen Derivate,
• - m-Diaminobenzol und dessen Derivate wie beispielsweise 2,4-Diaminophenoxyethanol, 1,3-Bis-(2',4'-diaminophenoxy)-propan, 1-Methoxy-2-amino-4-(2'-hydroxyethylamino)benzol, 1,3-Bis-(2',4'-diaminophenyl)-propan, 2,6-Bis-(2'-hydroxyethylamino)-1-methylbenzol und 1-Amino-3-bis-(2'-hydroxyethyl)-aminobenzol,
• - o-Diaminobenzol und dessen Derivate wie beispielsweise 3,4-Diaminobenzoesäure und 2,3-Diamino-1-methylbenzol,
• - Di- beziehungsweise Trihydroxybenzolderivate wie beispielsweise Resorcin, Resorcinmonomethylether, 2-Methylresorcin, 5-Methylresorcin, 2,5-Dimethylresorcin, 2-Chlorresorcin, 4-Chlorresorcin, Pyrogallol und 1,2,4-Trihydroxybenzol,
• - Pyridinderivate wie beispielsweise 2,6-Dihydroxypyridin, 2-Amino-3-hydroxypyridin, 2-Amino-5-chlor-3-hydroxypyridin, 3-Amino-2-methylamino-6-methoxypyridin, 2,6-Dihydroxy-3,4-dimethylpyridin, 2,6-Dihydroxy-4-methylpyridin, 2,6-Diaminopyridin, 2,3-Diamino-6-methoxypyridin und 3,5-Diamino-2,6-dimethoxypyridin,
• - Naphthalinderivate wie beispielsweise 1-Naphthol, 2-Methyl-1-naphthol, 2-Hydroxymethyl-1-naphthol, 2-Hydroxyethyl-1-naphthol, 1,5-Dihydroxynaphthalin, 1,6-Dihydroxynaphthalin, 1,7-Dihydroxynaphthalin, 1,8-Dihydroxynaphthalin, 2,7-Dihydroxynaphthalin und 2,3-Dihydroxynaphthalin,
• - Morpholinderivate wie beispielsweise 6-Hydroxybenzomorpholin und 6-Aminobenzomorpholin,
• - Chinoxalinderivate wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,
• - Pyrazolderivate wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• - Indolderivate wie beispielsweise 4-Hydroxyindol, 6-Hydroxyindol und 7-Hydroxyindol,
• - Pyrimidinderivate, wie beispielsweise 4,6-Diaminopyrimidin, 4-Amino-2,6-dihydroxypyrimidin, 2,4-Diamino-6-hydroxypyrimidin, 2,4,6-Trihydroxypyrimidin, 2-Amino-4-methylpyrimidin, 2-Amino-4-hydroxy-6-methylpyrimidin und 4,6-Dihydroxy-2-methylpyrimidin, oder
• - Methylendioxybenzolderivate wie beispielsweise 1-Hydroxy-3,4-methylendioxybenzol, 1-Amino-3,4-methylendioxybenzol und 1-(2'-Hydroxyethyl)-amino-3,4-methylendioxybenzol.

Coupler components preferred according to the invention are

• - m-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-Amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-(2'-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol,
• - o-aminophenol and its derivatives,
• - m-Diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis-(2',4'-diaminophenoxy)-propane, 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene, 1,3-bis-(2',4'-diaminophenyl)-propane, 2,6-bis-(2'-hydroxyethylamino)-1-methylbenzene and 1-amino-3-bis-(2'-hydroxyethyl)-aminobenzene,
• - o-Diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• - Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• - Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• - Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• - Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• - Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• - Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• - Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• - Pyrimidine derivatives, such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6-Dihydroxy-2-methylpyrimidine, or
• - Methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1-(2'-hydroxyethyl)-amino-3,4-methylenedioxybenzene.

Coupler components particularly preferred 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.

The colorants according to the invention preferably contain both the developer components and the coupler components in an amount of 0.005 to 20 wt. %, preferably 0.1 to 5 wt. %, based on the total oxidation colorant. Developer components and coupler components are generally used in approximately molar amounts to one another. Although molar use has proven advantageous, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components can be present in a molar ratio of 1:0.5 to 1:3, in particular 1:1 to 1:2.

In a further embodiment of the present invention, the dyes contain at least one precursor of a natural-analogous dye as a dye precursor (FA). Indoles and indolines that have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of natural-analogous dyes. These groups can bear further substituents, e.g., in the form of an etherification or esterification of the hydroxyl group or an alkylation of the amino group. In a second preferred embodiment, the dyes contain at least one indole and/or indoline derivative.

in der unabhängig voneinander

• - R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• - R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• - R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• - R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• - R⁵ steht für eine der unter R⁴ genannten Gruppen, sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

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

in which independently

• - R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group,
• - R ² represents hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically acceptable cation,
• - R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ represents a C ₁ -C ₄ alkyl group, and
• - R ⁵ represents 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 as well as 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-dihydroxyindoline.

in der unabhängig voneinander

• - R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxyalkylgruppe,
• - R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• - R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• - R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• - R⁵ steht für eine der unter R⁴ genannten Gruppen,
• - sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.

Derivatives of 5,6-dihydroxyindole of formula (IIb) are also excellently suited as precursors of natural hair dyes,

in which independently

• - R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ hydroxyalkyl group,
• - R ² represents hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically acceptable cation,
• - R ³ represents hydrogen or a C ₁ -C ₄ alkyl group,
• - R ⁴ represents hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ represents a C ₁ -C ₄ alkyl group, and
• - R ⁵ represents one of the groups mentioned under R ⁴ ,
• - as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

Within this group, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and, in particular, 5,6-dihydroxyindole are worth highlighting.

The indoline and indole derivatives can be used in the dyes according to the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, e.g., the hydrochlorides, sulfates, and hydrobromides. The indole or indoline derivatives are usually present in amounts of 0.05-10 wt.%, preferably 0.2-5 wt.%.

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

The cream base according to the invention has also proven particularly suitable for colorations based on substantive dyes. In addition to or instead of the dye precursors according to the invention, the colorants according to the invention can therefore, in a further preferred embodiment of the present invention, contain one or more substantive dyes. Substantive dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, or indophenols. Preferred direct dyes are those under the international names or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds 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-Hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-Ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

1. (a) kationische Triphenylmethanfarbstoffe, wie beispielsweise Basic Blue 7, Basic Blue 26, Basic Violet 2 und Basic Violet 14,
2. (b) aromatischen Systeme, die mit einer quaternären Stickstoffgruppe substituiert sind, wie beispielsweise Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 und Basic Brown 17, sowie
3. (c) direktziehende Farbstoffe, die einen Heterocyclus enthalten, der mindestens ein quaternäres Stickstoffatom aufweist, wie sie beispielsweise in der EP-A2-998 908 , auf die an dieser Stelle explizit Bezug genommen wird, in den Ansprüchen 6 bis 11 genannt werden.

Furthermore, the agents according to the invention may contain a cationic direct dye. Particularly preferred are

1. (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
2. (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, and
3. (c) direct dyes containing a heterocycle having at least one quaternary nitrogen atom, as described, for example, in EP-A2-998 908 , to which explicit reference is made at this point, are mentioned in claims 6 to 11.

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

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

The cationic direct dyes marketed under the trademark ^Arianor® are also particularly preferred cationic direct dyes according to the invention.

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

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as those found in henna red, henna neutral, henna black, chamomile blossom, sandalwood, black tea, buckthorn bark, sage, logwood, madder root, catechu, sedre and alkanet root.

It is not necessary for the oxidation dye precursors or the direct dyes to each be a single compound. Rather, the hair dyes according to the invention may contain other components in minor amounts, depending on the manufacturing processes for the individual dyes, provided that these do not adversely affect the dyeing result or must be excluded for other reasons, e.g., toxicological ones.

With regard to the dyes that can be used in the hair dyeing and tinting agents according to the invention, express reference is made to the Monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; direct dyes) and Chapter 8, pages 264-267; oxidation dye precursors), published as Volume 7 of the series "Dermatology" (eds.: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of Cosmetic Raw Materials" , published by the European Community, available on diskette from the Federal Association of German Industrial and Trade Companies for Pharmaceuticals, Health Foods and Personal Care Products eV, Mannheim.

As a second component essential to the invention, the colorants contain at least one fatty acid glyceryl ester. Preferred fatty acid glyceryl esters according to the invention are the so-called fatty acid partial glycerides, in particular monoglycerides, diglycerides, and technical mixtures thereof. When using technical products, small amounts of triglycerides may still be present due to the manufacturing process.

in der R¹, R² und R³ unabhängig voneinander für Wasserstoff oder für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22, vorzugsweise 12 bis 18, Kohlenstoffatomen stehen mit der Maßgabe, dass mindestens eine dieser Gruppen für einen Acylrest und mindestens eine dieser Gruppen für Wasserstoff steht. Die Summe (m+n+q) steht für 0 oder Zahlen von 1 bis 100, vorzugsweise für 0 oder 5 bis 25. Ganz besonders bevorzugt sind die Verbindungen der Formel (III), bei denen die Summe (m+n+q) für 0 steht. Besonders bevorzugt sind Verbindungen der Formel (III), bei denen R¹ für einen Acylrest und R² und R³ für Wasserstoff stehen. Typische Beispiele sind Mono- und/oder Diglyceride auf Basis von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Vorzugsweise werden Laurinsäuremonoglyceride, Isostearinsäuremonoglyceride, Behensäuremonoglycerid, Linolsaäuremonoglyceride, Ölsäuremonoglyceride und Stearinsäuremonoglyceride eingesetzt. Ölsäuremonoglyceride und Stearinsäuremonoglyceride sind erfindungsgemäß ganz besonders bevorzugte Fettsäuregylcerylester.Preferred fatty acid glyceryl esters are therefore the compounds of formula (III),

in which R ¹ , R ² and R ³ independently of one another represent hydrogen or a linear or branched, saturated and/or unsaturated acyl radical having 6 to 22, preferably 12 to 18, carbon atoms, with the proviso that at least one of these groups represents an acyl radical and at least one of these groups represents hydrogen. The sum (m+n+q) represents 0 or numbers from 1 to 100, preferably 0 or 5 to 25. Very particular preference is given to the compounds of the formula (III) in which the sum (m+n+q) represents 0. Particular preference is given to compounds of the formula (III) in which R ¹ represents an acyl radical and R ² and R ³ represent hydrogen. Typical examples are mono- and/or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid, and erucic acid, as well as technical mixtures thereof. Lauric acid monoglycerides, isostearic acid monoglycerides, behenic acid monoglyceride, linoleic acid monoglycerides, oleic acid monoglycerides, and stearic acid monoglycerides are preferably used. Oleic acid monoglycerides and stearic acid monoglycerides are particularly preferred fatty acid glyceryl esters according to the invention.

The fatty acid glyceryl esters are preferably contained in the agents according to the invention in amounts of 0.1 to 10 wt.%, in particular 0.3 to 3 wt.%.

wobei die Reste R¹ bis R⁴ stehen unabhängig voneinander für eine C₁- bis C₄-Alkylkette oder eine C₁₀- bis C₃₀-Alkylkette, mit der Maßgabe, dass mindestens einer und höchstens zwei der Reste R¹ bis R⁴ für eine C₁₂- bis C₃₀-Alkylkette stehen, und X steht für ein physiologisch verträgliches Anion.As a third obligatory component, the agents according to the invention contain at least one specific cationic surfactant of formula (I)

where the radicals R ¹ to R ⁴ independently of one another represent a C ₁ to C ₄ alkyl chain or a C ₁₀ to C ₃₀ alkyl chain, with the proviso that at least one and at most two of the radicals R ¹ to R ⁴ represent a C ₁₂ to C ₃₀ alkyl chain, and X represents a physiologically acceptable anion.

Preferred C ₁ to C ₄ alkyl chains in the sense of formula (I) are methyl, ethyl, propyl, isopropyl and butyl groups, the methyl group being particularly preferred according to the invention.

Preferred C ₁₀ to C ₃₀ alkyl chains within the meaning of formula (I) are the capric, cetyl, stearyl, behenyl, and lauryl groups. According to the invention, C ₁₂ to C ₃₀ alkyl chains may be particularly preferred. The cetyl and behenyl groups are very particularly preferred according to the invention.

Preferred physiologically acceptable anions X for the purposes of the present invention are both inorganic anions, such as halides (chloride, bromide, iodide), sulfate, and phosphate, as well as organic anions, such as acetate and lactate. Another anion for the purposes of the present invention is the methosulfate anion. Chloride and bromide are particularly preferred according to the invention, with chloride being most preferred according to the invention.

Preferred compounds of formula (I) are alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, alkyltrimethylammonium bromides, and dialkyldimethylammonium bromides. Particularly preferred compounds of formula (I) are dicaprine dimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, dicetyldimethylammonium chloride, dilauryldimethylammonium chloride, behenyltrimethylammonium chloride, and behenyltrimethylammonium methosulfate. Furthermore, mixtures of the compounds mentioned, in particular naturally occurring mixtures, such as derivatives of tallow fatty alcohol, may also be preferred according to the invention. Ditallowdimethylammonium chloride and monotallowtrimethylammonium chloride are explicitly mentioned as examples here.

The cationic surfactants of formula (I) are preferably present in the compositions used according to the invention in amounts of 0.05 to 10 wt.%, based on the total composition. Amounts of 0.1 to 5 wt.% are particularly preferred.

The colorants contain ammonium bicarbonate as the fourth component essential to the invention.

Ammonium hydrogen carbonate, (NH ₄ )HCO ₃ , (also known as ammonium bicarbonate or ammonium bicarbonate) is commercially available in the form of large, shiny, hard, colorless, almost odorless prisms. Preferred agents according to the invention contain—based on the weight of the agent—0.1 to 10 wt.%, preferably 0.25 to 8 wt.%, particularly preferably 0.5 to 5 wt.%, and in particular 1 to 3 wt.% of ammonium hydrogen carbonate.

In addition, the dyes may contain silica.

In the context of the present application, “silica” is the collective term for compounds of the general formula (SiO ₂ ) _m nH ₂ O. If a silicon halide (e.g. SiCl ₄ ) is reacted with water, the primary product formed is orthosilicic acid (monosilicic acid), H ₄ SiO ₄ , which only releases water continuously and intermolecularly in high dilution. The first condensation product to occur is disilicic acid (pyrosilicic acid, H ₆ Si ₂ O ₇ ). Further condensation leads via cyclic silicic acids and cage-like silicic acids to approximately spherical polysilicic acids. The formal end product of the condensation is polymeric silicon dioxide, (SiO ₂ ) _x , the anhydride of silicic acid. During condensation, chain-elongation, ring-forming, and branching processes occur concurrently, resulting in a disordered (amorphous) polysilicic acid structure. In all silicic acids, the Si atoms are located at the center of irregularly interconnected tetrahedra, at whose four vertices lie O atoms that also belong to the neighboring tetrahedra.

Silicas can be produced from solution ("precipitated silicas") or by pyrolysis of volatile Si compounds ("pyrogenic silicas"). In terms of production volume, precipitated silicas are by far the most important. They are produced from an aqueous alkali silicate solution by precipitation with mineral acids. This process forms colloidal primary particles, which agglomerate as the reaction progresses and eventually coalesce into aggregates. The powdery, voluminous forms have pore volumes of 2.5–15 mL/g and specific surface areas of 30–800 ^m² /g.

The term fumed silica refers to highly dispersed silicas produced by flame hydrolysis. This involves decomposing silicon tetrachloride in an oxyhydrogen flame. Fumed silicas have significantly fewer OH groups on their almost pore-free surface than precipitated silicas. Because of their hydrophilicity, which is caused by the silanol groups, synthetic silicas are often subjected to chemical post-treatment processes in which the OH groups react, for example, with organic chlorosilanes. This creates modified, e.g. hydrophobic surfaces that significantly expand the application properties of the silicas. Both precipitated and fumed silicas can be used in the present invention. Preferably usable silicas have specific surface areas of 25 to 1000 m ² /g, oil absorption values of 30 to 300 g/100 g, primary particle sizes of 5 to 500 nm, densities of 1.9 to 2.2 g/cm ³ , and drying losses of < 7%, preferably < 3%. Commercial products usable in the context of the present invention are marketed, for example, under the trademarks Aerosil ^® , Cab-O-Sil ^® , and HDK.

Preferred agents according to the invention are characterized in that they contain - based on the weight of the agent - 0.05 to 5 wt.%, preferably 0.1 to 3 wt.%, particularly preferably 0.15 to 2 wt.% and in particular 0.2 to 1 wt.% of silica.

In a preferred embodiment of the present invention, the colorants further contain at least one fully or partially hydrogenated vegetable oil. Vegetable oils preferred according to the invention are, for example, soybean oil, coconut oil, hazelnut oil, palm kernel oil, sunflower oil, linseed oil, peanut oil, castor oil, or rapeseed oil.

A particularly preferred hydrogenated vegetable oil according to the invention is the hydrogenated castor oil sold under the trade name ^Cutina® HR (Cognis).

The agents according to the invention preferably contain the fully or partially hydrogenated vegetable oils in amounts of 0.1 to 7% by weight, a range of 0.4 to 1.2% by weight is particularly preferred.

• - Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• - C₁₂-C₂₂-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• - C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga sowie
• - Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl.

In a further preferred embodiment of the present invention, the colorants further contain at least one nonionic surfactant. Nonionic surfactants contain, for example, a polyol group, a polyalkylene glycol ether group, or a combination of polyol and polyglycol ether groups as a hydrophilic group. Such compounds are, for example,

• - Addition products of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide with linear fatty alcohols having 8 to 22 C atoms, with fatty acids having 12 to 22 C atoms and with 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 moles of ethylene oxide with glycerol,
• - C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogues 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 compounds are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and 2-methyl-branched aliphatic radicals are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl, and 1-stearyl. 1-octyl, 1-decyl, 1-lauryl, and 1-myristyl are particularly preferred. 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 usable according to the invention can, for example, contain only one specific alkyl radical R ¹ . However, these compounds are usually prepared from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures depending on the starting compounds or the respective processing of these compounds.

• - im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• - im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• - im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• - im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen besteht.

Particularly preferred are those alkyl polyglycosides in which R ¹

• - consisting essentially of C ₈ and C ₁₀ alkyl groups,
• - consisting essentially of C ₁₂ and C ₁₄ alkyl groups,
• - consisting essentially of C ₈ to C ₁₆ alkyl groups or
• - consists essentially of C ₁₂ to C ₁₆ alkyl groups.

Any mono- or oligosaccharide can be used as the sugar building block Z. Typically, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Examples of such sugars include 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 usable according to the invention contain an average of 1.1 to 5 sugar units. Alkyl polyglycosides with x values of 1.1 to 1.6 are preferred. Alkyl glycosides with x values of 1.1 to 1.4 are particularly preferred.

In addition to their surfactant effect, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. Therefore, the expert will be able to If an effect of the perfume oil on the hair that goes beyond hair treatment is desired, this class of substances is preferably used as a further ingredient in the preparations according to the invention.

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

Nonionic surfactants preferred according to the invention are the addition products of 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of propylene oxide with linear fatty alcohols having 8 to 22 carbon atoms. These surfactants, which are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products, can be products with a "normal" homolog distribution as well as those with a narrow homolog distribution. "Normal" homolog distribution refers to mixtures of homologs obtained from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides, or alkali metal alkoxides as catalysts. Narrow homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides, or alkoxides are used as catalysts. The use of products with a narrow homolog distribution may be preferred. Can we include a list of specific compounds/commercial products here?

According to the invention, it has proven particularly preferable to use two different addition products of ethylene oxide with linear fatty alcohols. This allows the stability and homogeneity of the emulsions to be further improved.

In a first preferred embodiment, at least one adduct of ethylene oxide with a linear fatty alcohol having a chain length of at most 14 carbon atoms and at least one adduct of ethylene oxide with linear fatty alcohols having a chain length of at least 15 carbon atoms are used. A combination of an adduct of ethylene oxide with a linear fatty alcohol having a chain length of 10-14 carbon atoms with an adduct of ethylene oxide with linear fatty alcohols having a chain length of 15-22 carbon atoms may be particularly preferred according to the invention.

In a further preferred embodiment, at least one adduct of ethylene oxide with linear fatty alcohols having an average degree of ethoxylation of at most 25 EO units and at least one adduct of ethylene oxide with linear fatty alcohols having an average degree of ethoxylation of at least 28 EO units are used. A combination of an adduct of ethylene oxide with linear fatty alcohols having an average degree of ethoxylation of 18-25 EO units with an adduct of ethylene oxide with linear fatty alcohols having an average degree of ethoxylation of at least 28-35 EO units may also be particularly preferred according to the invention.

A combination of Laureth-23 and Ceteareth-30 has proven to be particularly preferred according to the invention.

The non-ionic surfactants are preferably used in an amount of 0.05 to 5.0 wt.%, in particular 0.1 to 2.0 wt.%, based on the ready-to-use agent.

In a preferred embodiment of the invention, the effect of the colorant can be further enhanced by fatty substances (D). According to the invention, fatty substances are understood to mean fatty acids, fatty alcohols, natural and synthetic waxes, which can be present both in solid form and in liquid form in aqueous dispersion, as well as natural and synthetic cosmetic oil components.

Linear and/or branched, saturated and/or unsaturated fatty acids with 6 - 30 carbon atoms can be used as fatty acids (D1). Fatty acids with 10 - 22 carbon atoms are preferred. These include, for example, isostearic acids, such as the commercial products Emersol ^® 871 and Emersol ^® 875, and isopalmitic acids such as the commercial product Edenor ^® IP 95, as well as all other fatty acids sold under the trade name Edenor ^® (Cognis). Other typical examples of such fatty acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and eru Fatty acid and their technical mixtures, which are obtained, for example, from the pressure splitting of natural fats and oils, from the oxidation of aldehydes from Roelen's oxosynthesis, or from the dimerization of unsaturated fatty acids. Fatty acid fractions obtainable from coconut oil or palm oil are usually particularly preferred; the use of stearic acid is generally particularly preferred.

The amount used is 0.1–15% by weight, based on the total composition. The amount is preferably 0.5–10% by weight, although amounts of 1–5% by weight can be particularly advantageous.

Fatty alcohols (D2) that can be used are saturated, mono- or polyunsaturated, branched or unbranched fatty alcohols with C ₆ - C ₃₀ , preferably C ₁₀ - C ₃₀ , and very particularly preferably C ₁₂ - C ₂₂ carbon atoms. Examples of fatty alcohols that can be used within the meaning of the invention are decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, erucic alcohol, ricinoleic alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol, and behenyl alcohol, as well as their Guerbet alcohols, whereby this list is intended to be exemplary and non-limiting. However, the fatty alcohols are preferably derived from natural fatty acids, usually derived from the esters of the fatty acids by reduction. Fatty alcohol fractions that are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil, and linseed oil, or fatty acid esters resulting from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols, can also be used according to the invention. Such substances can be purchased, for example, under the names Stenol ^® , e.g. Stenol ^® 1618 or Lanette ^® , e.g. Lanette ^® O or Lorol ^® , e.g. Lorol ^® C8, Lorol ^® C14, Lorol ^® C18, Lorol ^® C8-18, HD-Ocenol ^® , Crodacol ^® , e.g. Crodacol ^® CS, Novol ^® , Eutanol ^® G, Guerbitol ^® 16, Guerbitol ^® 18, Guerbitol ^® 20, Isofol ^® 12, Isofol ^® 16, Isofol ^® 24, Isofol ^® 36, Isocarb ^® 12, Isocarb ^® 16 or Isocarb ^® 24. Of course, wool wax alcohols, such as those commercially available under the names Corona ^® , White Swan ^® , Coronet ^® or Fluilan ^® , can also be used according to the invention.

The fatty alcohols (D2) are used in amounts of 0.1 - 30 wt.%, based on the total preparation, preferably in amounts of 0.1 - 20 wt.%.

According to the invention, natural or synthetic waxes (D3) that can be used include solid paraffins or isoparaffins, carnauba waxes, beeswaxes, candelilla waxes, ozokerites, ceresin, spermaceti, sunflower wax, fruit waxes such as apple wax or citrus wax, and microwaxes made of PE or PP. Such waxes are available, for example, from Kahl & Co., Trittau.

The amount of waxes (D3) used is 0.1 - 50 wt.% based on the total agent, preferably 0.1 - 20 wt.% and particularly preferably 0.1 - 15 wt.% based on the total agent.

• - pflanzliche Öle. Beispiele für solche Öle sind Sonnenblumenöl, Olivenöl, Sojaöl, Rapsöl, Mandelöl, Jojobaöl, Orangenöl, Weizenkeimöl, Pfirsichkernöl und die flüssigen Anteile des Kokosöls. Geeignet sind aber auch andere Triglyceridöle wie die flüssigen Anteile des Rindertalgs sowie synthetische Triglyceridöle.
• - flüssige Paraffinöle, Isoparaffinöle und synthetische Kohlenwasserstoffe sowie Din-alkylether mit insgesamt zwischen 12 bis 36 C-Atomen, insbesondere 12 bis 24 C-Atomen, wie beispielsweise Di-n-octylether, Di-n-decylether, Di-n-nonylether, Di-n-undecylether, Di-n-dodecylether, n-Hexyl-n-octylether, n-Octyl-n-decylether, n-Decyl-n-undecylether, n-Undecyl-n-dodecylether und n-Hexyl-n-Undecylether sowie Di-tert-butylether, Di-iso-pentylether, Di-3-ethyldecylether, tert.-Butyl-n-octylether, iso-Pentyl-n-octylether und 2-Methyl-pentyl-n-octylether. Die als Handelsprodukte erhältlichen Verbindungen 1,3-Di-(2-ethyl-hexyl)-cyclohexan (Cetiol^® S) und Di-n-octylether (Cetiol^® OE) können bevorzugt sein.
• - Esteröle. Unter Esterölen sind zu verstehen die Ester von C₆ - C₃₀ - Fettsäuren mit C₂ - C₃₀ - Fettalkoholen. Bevorzugt sind die Monoester der Fettsäuren mit Alkoholen mit 2 bis 24 C-Atomen. Beispiele für eingesetzte Fettsäurenanteile in den Estern sind Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, die z.B. bei der Druckspaltung von natürlichen Fetten und Ölen, bei der Oxidation von Aldehyden aus der Roelen'schen Oxosynthese oder der Dimerisierung von ungesättigten Fettsäuren anfallen. Beispiele für die Fettalkoholanteile in den Esterölen sind Isopropylalkohol, Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Erfindungsgemäß besonders bevorzugt sind Isopropylmyristat (Rilanit^® IPM), Isononansäure-C16-18-alkylester (Cetiol^® SN), 2-Ethylhexylpalmitat (Cegesoft^® 24), Stearinsäure-2-ethylhexylester (Cetiol^®868), Cetyloleat, Glycerintricaprylat, Kokosfettalkoholcaprinat/-caprylat (Cetiol^® LC), n-Butylstearat, Oleylerucat (Cetiol^® J 600), Isopropylpalmitat (Rilanit^® IPP), Oleyl Oleate (Cetiol^®), Laurinsäurehexylester (Cetiol^® A), Di-n-butyladipat (Cetiol^® B), Myristylmyristat (Cetiol^® MM), Cetearyl Isononanoate (Cetiol^® SN), Ölsäuredecylester (Cetiol^® V).

• - Dicarbonsäureester wie Di-n-butyladipat, Di-(2-ethylhexyl)-adipat, Di-(2-ethylhexyl)-succinat und Di-isotridecylacelaat sowie Diolester wie Ethylenglykoldioleat, Ethylenglykol-di-isotridecanoat, Propylenglykol-di(2-ethylhexanoat), Propylenglykol-di-isostearat, Propylenglykol-di-pelargonat, Butandiol-di-isostearat, Neopentylglykoldicaprylat,
• - symmetrische, unsymmetrische oder cyclische Ester der Kohlensäure mit Fettalkoholen, beispielsweise beschrieben in der DE-OS 197 56 454 , Glycerincarbonat oder Dicaprylylcarbonat (Cetiol^® CC),
• - Trifettsäureester von gesättigten und/oder ungesättigten linearen und/oder verzweigten Fettsäuren mit Glycerin,

The natural and synthetic cosmetic oil bodies (D4) which can enhance the effect of the colorant according to the invention include, for example:

• - Vegetable oils. Examples of such oils include sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, wheat germ oil, peach kernel oil, and the liquid portions of coconut oil. Other triglyceride oils, such as the liquid portions of beef tallow, and synthetic triglyceride oils, are also suitable.
• - liquid paraffin oils, isoparaffin oils and synthetic hydrocarbons as well as di-alkyl ethers with a total of between 12 and 36 C atoms, in particular 12 to 24 C atoms, such as, for example, di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether as well as di-tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2-methylpentyl-n-octyl ether. The compounds 1,3-di-(2-ethyl-hexyl)-cyclohexane (Cetiol ^® S) and di-n-octyl ether (Cetiol ^® OE), which are available as commercial products, may be preferred.
• - Ester oils. Ester oils are esters of _C6 - _C30 fatty acids with _C2 - _C30 fatty alcohols. Monoesters of fatty acids with alcohols containing 2 to 24 carbon atoms are preferred. Examples of fatty acid moieties used in the esters are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid as well as their technical mixtures, which are used, for example, in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from the Len's oxosynthesis or the dimerization of unsaturated fatty acids. Examples of fatty alcohol components in ester oils are isopropyl alcohol, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and brassidyl alcohol, as well as their technical mixtures, which arise, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis, as well as as a monomer fraction in the dimerization of unsaturated fatty alcohols. Particularly preferred according to the invention are isopropyl myristate (Rilanit ^® IPM), isononanoic acid C16-18-alkyl esters (Cetiol ^® SN), 2-ethylhexyl palmitate (Cegesoft ^® 24), 2-ethylhexyl stearate (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprate/caprylate (Cetiol ^® LC), n-butyl stearate, oleyl erucate (Cetiol ^® J 600), isopropyl palmitate (Rilanit ^® IPP), oleyl oleate (Cetiol ^® ), lauric acid hexyl ester (Cetiol ^® A), di-n-butyl adipate (Cetiol ^® B), myristyl myristate (Cetiol ^® MM), cetearyl isononanoate (Cetiol ^® SN), oleic acid decyl ester (Cetiol ^® V).

• - Dicarboxylic acid esters such as di-n-butyl adipate, di-(2-ethylhexyl) adipate, di-(2-ethylhexyl) succinate and di-isotridecyl acylate as well as diol esters such as ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di(2-ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate, neopentyl glycol dicaprylate,
• - symmetrical, asymmetrical or cyclic esters of carbonic acid with fatty alcohols, for example described in DE-OS 197 56 454 , glycerin carbonate or dicaprylyl carbonate (Cetiol ^® CC),
• - Trifatty acid esters of saturated and/or unsaturated linear and/or branched fatty acids with glycerol,

The amount of natural and synthetic cosmetic oil components used in the compositions used according to the invention is usually 0.1 - 30 wt.%, based on the total composition, preferably 0.1 - 20 wt.%, and in particular 0.1 - 15 wt.%.

According to the invention, colorants containing at least one fatty alcohol (D2) are particularly preferred. Furthermore, colorants containing at least one ester oil have proven advantageous. Colorants containing both at least one fatty alcohol (D2) and at least one ester oil may be particularly preferred.

The total amount of oil and fat components in the compositions according to the invention is usually 0.5-75% by weight, based on the total composition. Amounts of 0.5-35% by weight are preferred according to the invention.

It has proven particularly preferred according to the invention if the colorants have a low fat content (less than 20% by weight). Furthermore, it may be particularly preferred according to the invention if the colorants are formulated free of mineral and/or animal-based raw materials.

In a further embodiment of the present invention, it may be preferred if the coloring agents further contain at least one solvent. While some prior art coloring bases react sensitively to the addition of solvents, the cream base according to the invention is characterized by excellent solvent compatibility. Preferred solvents according to the invention are, for example, ethanol, isopropanol, ethylene glycol, propylene glycol, benzyl alcohol, methoxybutanol, ethyl diglycol, glycerin, and diethylene glycol. Particularly preferred solvents are propylene glycol, benzyl alcohol, methoxybutanol, and ethyl diglycol.

The colorants according to the invention preferably contain solvents in amounts of 0.1 to 15% by weight, in particular 2 to 10% by weight.

The colorants according to the invention, especially when the coloring is carried out oxidatively, whether with atmospheric oxygen or other oxidizing agents such as hydrogen peroxide, are usually adjusted to a slightly acidic to alkaline pH, i.e. to a pH in the range of about 5 to 11. For this purpose, the colorants contain alkalizing agents, usually alkali or alkaline earth hydroxides, ammonia or organic amines. Preferred alkalizing agents are monoethanolamine, monoisopropanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylbutanediol. nol and triethanolamine, as well as alkali and alkaline earth metal hydroxides. Monoethanolamine, triethanolamine, 2-amino-2-methylpropanol, and 2-amino-2-methyl-1,3-propanediol are particularly preferred within this group. The use of ω-amino acids such as ω-aminocaproic acid as alkalizing agents is also possible. Ammonia is a particularly preferred alkalizing agent.

Buffer systems, such as diammonium hydrogen phosphate/potassium carbonate, for setting a specific pH value can also be incorporated into the cream base according to the invention without stability problems.

The colorants according to the invention can further contain all active ingredients, additives, and auxiliaries known for such preparations. In many cases, the colorants also contain at least one anionic, zwitterionic, cationic, and/or ampholytic surfactant.

• - lineare Fettsäuren mit 10 bis 22 C-Atomen (Seifen),
• - Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x -CH₂-COOH, in der R eine lineare Alkylgruppe mit 10 bis 22 C-Atomen und x = 0 oder 1 bis 16 ist,
• - Acylsarcoside mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acyltauride mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Acylisethionate mit 10 bis 18 C-Atomen in der Acylgruppe,
• - Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 18 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 18 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• - lineare Alkansulfonate mit 12 bis 18 C-Atomen,
• - lineare Alpha-Olefinsulfonate mit 12 bis 18 C-Atomen,
• - Alpha-Sulfofettsäuremethylester von Fettsäuren mit 12 bis 18 C-Atomen,
• - Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)×-SO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 10 bis 18 C-Atomen und x = 0 oder 1 bis 12 ist,
• - Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030 ,
• - sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354 ,
• - Sulfonate ungesättigter Fettsäuren mit 12 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344 ,
• - Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen.

Suitable anionic surfactants for use on the human body in preparations according to the invention are all anionic surface-active substances. These are characterized by a water-solubilizing anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 10 to 22 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups. Examples of suitable anionic surfactants, each in the form of the sodium, potassium, and ammonium salts, as well as the mono-, di-, and trialkanolammonium salts with 2 or 3 carbon atoms in the alkanol group, are:

• - linear fatty acids with 10 to 22 C atoms (soaps),
• - Ethercarboxylic acids of the formula RO-(CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,
• - Acylsarcosides with 10 to 18 C atoms in the acyl group,
• - Acyltaurides with 10 to 18 C atoms in the acyl group,
• - Acyl isethionates with 10 to 18 C atoms in the acyl group,
• - sulfosuccinic acid mono- and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkylpolyoxyethyl esters with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates with 12 to 18 C atoms,
• - linear alpha-olefin sulfonates with 12 to 18 C atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 12 to 18 C atoms,
• - Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO(CH ₂ -CH ₂ O)×-SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,
• - Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030 ,
• - sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354 ,
• - Sulfonates of unsaturated fatty acids with 12 to 24 C atoms and 1 to 6 double bonds according to DE-A-39 26 344 ,
• - Esters of tartaric acid and citric acid with alcohols, which are addition products of about 2-15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols with 8 to 22 C atoms.

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

Ampholytic surfactants are also particularly suitable as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C ₈ -C ₁₈ alkyl or acyl group, contain at least one free amino group and at least one -COOH- or -SO ₃ H- group in the molecule and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and Alkylaminoacetic acids, each with approximately 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate, and C _12-18 acylsarcosine.

According to the invention, cationic surfactants used are in particular those of the quaternary ammonium compound, esterquat and amidoamine type.

Preferred quaternary ammonium compounds are, for example, the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.

Esterquats are known substances that contain 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, for example, under the trademarks ^Stepantex® , ^Dehyquart® , and ^Armocare® . The products ^Armocare® VGH-70, an N,N-bis(2-palmitoyloxyethyl)dimethylammonium chloride, as well as ^Dehyquart® F-75 and ^Dehyquart® AU-35 are examples of such esterquats.

Alkylamidoamines are typically produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. A particularly suitable compound from this group of substances according to the invention is stearamidopropyldimethylamine, commercially available under the name ^Tegoamid® S 18.

Other cationic surfactants that can be used according to the invention are the quaternized protein hydrolysates.

Other cationic surfactants suitable for use in the invention are the substances known under the INCI names Linoleamidopropyl PG-Dimonium Chloride Phosphate, Cocamidopropyl PG-Dimonium Chloride Phosphate, and Stearamidopropyl PG-Dimonium Chloride Phosphate. These are marketed, for example, by Mona under the trade names Phospholipid EFA ^® , Phospholipid PTC ^® , and Phospholipid SV ^® .

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80).

An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat ^® 100, which according to INCI nomenclature is a “Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride”.

The compounds containing alkyl groups used as surfactants can each be single substances. However, it is generally preferred to start with native plant or animal raw materials when producing these substances, resulting in mixtures of substances with different alkyl chain lengths, depending on the respective raw material.

For surfactants that are addition products of ethylene 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. "Normal" homolog distribution refers to mixtures of homologs obtained from the reaction of fatty alcohols and alkylene oxide using alkali metals, alkali metal hydroxides, or alkali metal alkoxides as catalysts. Narrow homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides, or alkoxides are used as catalysts. The use of products with a narrow homolog distribution may be preferred.

However, it has proven particularly advantageous according to the invention if the colorants are formulated free of anionic, zwitterionic and/or ampholytic surfactants.

• - nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• - kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallylammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylaminoethylmethacrylat-Vinylpyrrolidon-Copolymere, Vinylpyrrolidon-Imidazoliniummethochlorid-Copolymere und quaternierter Polyvinylalkohol,
• - zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere,
• - anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-tert.Butyl-acrylamid-Terpolymere,
• - Verdickungsmittel wie Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z.B. Polyvinylalkohol,
• - Strukturanten wie Maleinsäure und Milchsäure,
• - haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline,
• - Proteinhydrolysate, insbesondere Elastin-, Kollagen-, Keratin-, Milcheiweiß-, Sojaprotein- und Weizenproteinhydrolysate, deren Kondensationsprodukte mit Fettsäuren sowie quaternisierte Proteinhydrolysate,
• - Parfümöle, Dimethylisosorbid und Cyclodextrine,
• - faserstrukturverbessernde Wirkstoffe, insbesondere Mono-, Di- und Oligosaccharide wie beispielsweise Glucose, Galactose, Fructose, Fruchtzucker und Lactose,
• - quaternierte Amine wie Methyl-1-alkylamidoethyl-2-alkylimidazolinium-methosulfat
• - Entschäumer wie Silikone,
• - Farbstoffe zum Anfärben des Mittels,
• - Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• - Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• - Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genußsäuren und Basen,
• - Wirkstoffe wie Allantoin, Pyrrolidoncarbonsäuren und deren Salze sowie Bisabolol,
• - Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• - Pflanzenextrakte wie die Extrakte aus Grünem Tee, Eichenrinde, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Weißdorn, Lindenblüten, Mandel, Aloe Vera, Fichtennadel, Roßkastanie, Sandelholz, Wacholder, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Malve, Wiesenschaumkraut, Quendel, Schafgarbe, Thymian, Melisse, Hauhechel, Huflattich, Eibisch, Meristem, Ginseng und Ingwerwurzel,.
• - Cholesterin,
• - Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• - Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• - Fettsäurealkanolamide,
• - Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• - Quell- und Penetrationsstoffe wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• - Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere
• - Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• - Pigmente,
• - Stabilisierungsmittel für Wassserstoffperoxid und andere Oxidationsmittel,
• - Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• - Antioxidantien,

enthalten.Furthermore, the colorants according to the invention may contain further active ingredients, auxiliaries and additives, such as

• - non-ionic polymers such as vinylpyrrolidone/vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone/vinyl acetate copolymers and polysiloxanes,
• - cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate-quaternized dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• - zwitterionic and amphoteric polymers such as acrylamidopropyl trimethylammonium chloride/acrylate copolymers and octylacrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers,
• - anionic polymers such as polyacrylic acids, cross-linked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers,
• - Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives such as methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol,
• - Structurants such as maleic acid and lactic acid,
• - hair conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins,
• - Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• - Perfume oils, dimethylisosorbide and cyclodextrins,
• - fiber-improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose,
• - quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - Defoamers such as silicones,
• - Dyes to color the product,
• - Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - Sunscreens, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• - Substances for adjusting the pH value, such as common acids, especially food acids and bases,
• - Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts as well as bisabolol,
• - Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as extracts from green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden blossom, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, wild thyme, yarrow, thyme, lemon balm, restharrow, coltsfoot, marshmallow, meristem, ginseng and ginger root.
• - cholesterol,
• - Thickeners such as sugar esters, polyol esters or polyol alkyl ethers,
• - Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• - Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating agents such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas as well as primary, secondary and tertiary phosphates,
• - Opaqueants such as latex, styrene/PVP and styrene/acrylamide copolymers
• - Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• - Pigments,
• - Stabilizers for hydrogen peroxide and other oxidizing agents,
• - Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - Antioxidants,

contain.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. Kh. Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

1. (A) mindestens ein Farbstoffvorprodukt und/oder einen direktziehenden Farbstoff
2. (B) mindestens einen Fettsäureglycerylester und
3. (C) mindestens ein kationisches Tensid der Formel (I)
   
   wobei die Reste R¹ bis R⁴ stehen unabhängig voneinander für eine C₁- bis C₄-Alkylkette oder eine C₁₀- bis C₃₀-Alkylkette, mit der Maßgabe, dass mindestens einer und höchstens zwei der Reste R¹ bis R⁴ für eine C₁₂- bis C₃₀-Alkylkette stehen, und X steht für ein physiologisch verträgliches Anion, und
4. (D) Ammoniumhydrogencarbonat,

und einer zweiten Zubereitung, enthaltend mindestens ein Oxidationsmittel, bestehen.A second subject of the present invention are two-component agents for coloring keratin fibers, which consist of a first preparation containing

1. (A) at least one dye precursor and/or one direct dye
2. (B) at least one fatty acid glyceryl ester and
3. (C) at least one cationic surfactant of formula (I)
   
   where the radicals R ¹ to R ⁴ independently of one another represent a C ₁ to C ₄ alkyl chain or a C ₁₀ to C ₃₀ alkyl chain, with the proviso that at least one and at most two of the radicals R ¹ to R ⁴ represent a C ₁₂ to C ₃₀ alkyl chain, and X represents a physiologically acceptable anion, and
4. (D) Ammonium bicarbonate,

and a second preparation containing at least one oxidizing agent.

In a preferred embodiment of this inventive article, the second preparation contains at least one anionic or at least one cationic surfactant. Regarding the anionic or cationic surfactants preferred according to the invention, reference is made to the above statements. The colorants according to the invention in this embodiment are characterized by the excellent viscosity of the resulting application preparation. The viscosity is such that the agents can be easily distributed on the hair without subsequently dripping.

The two-component agents according to the invention are characterized by good miscibility, ease of manufacture and exceptional long-term stability.

If the actual coloring takes place within the framework of an oxidative process, conventional oxidizing agents such as, in particular, hydrogen peroxide or its adducts with urea, melamine or sodium borate can be used. Oxidation with atmospheric oxygen as the sole oxidizing agent may, however, be preferred. However, a chemical oxidizing agent is preferably used, especially if, in addition to coloring, a lightening effect on human hair is desired. Suitable oxidizing agents are persulfates, chlorites and, in particular, hydrogen peroxide or its adducts with urea, melamine and sodium borate. According to the invention, however, the oxidation coloring The product can also be applied to the hair together with a catalyst that activates the oxidation of the dye precursors, e.g., by atmospheric oxygen. Such catalysts include metal ions, iodides, quinones, or certain enzymes.

Suitable metal ions include Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , _Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Zn ²⁺ , Cu ²⁺ and Mn ²⁺ are particularly suitable. 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 acetates, sulfates, halides, lactates and tartrates. By using these metal salts, the formation of the color can be accelerated and the color nuance can be specifically influenced.

• - Pyranose-Oxidase und z.B. D-Glucose oder Galactose,
• - Glucose-Oxidase und D-Glucose,
• - Glycerin-Oxidase und Glycerin,
• - Pyruvat-Oxidase und Benztraubensäure oder deren Salze,
• - Alkohol-Oxidase und Alkohol (MeOH, EtOH),
• - Lactat-Oxidase und Milchsäure und deren Salze,
• - Tyrosinase-Oxidase und Tyrosin,
• - Uricase und Harnsäure oder deren Salze,
• - Cholinoxidase und Cholin,
• - Aminosäure-Oxidase und Aminosäuren.

Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, enzymes suitable according to the invention are those that directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as laccases, or that 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 glycerol,
• - Pyruvate oxidase and benzoic acid or their 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 dye is advantageously prepared immediately before use by mixing the oxidizing agent preparation with the preparation containing the dye precursors. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 5 to 14, in particular 7 to 12. It is particularly preferred to use the hair dye in a slightly alkaline environment. Application temperatures can be in a range between 15 and 40°C. After a contact time of 5 to 45 minutes, the hair dye is removed from the hair to be dyed by rinsing. Subsequent shampooing is not necessary if a carrier with a high surfactant content, e.g., a dye shampoo, was used.

Particularly in the case of hair that is difficult to dye, the preparation containing the dye precursors can also be applied to the hair without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes - optionally after an intermediate rinse - the oxidation component is then applied. After a further exposure time of 10 to 20 minutes, the hair is then rinsed and, if desired, shampooed. In this embodiment, according to a first variant, in which the prior application of the dye precursors is intended to improve penetration into the hair, the corresponding agent is adjusted to a pH of approximately 4 to 7. According to a second variant, air oxidation is initially desired, with the applied agent preferably having a pH of 7 to 10. For the subsequent accelerated post-oxidation, the use of acidic peroxydisulfate solutions as oxidizing agents may be preferred.

A third subject of the present invention is therefore a method for coloring keratin fibers, in which one of the agents according to the invention is mixed with an oxidizing agent preparation, the application preparation is applied to the fibers and rinsed off again after a contact time.

Particularly preferred is a method for coloring keratin fibers in which a two-component agent according to the invention is mixed to form an application preparation, which is applied to the fibers and rinsed off again after a contact time.

The following examples are intended to illustrate the subject matter of the present invention without limiting it.

Examples

The quantities used in the following examples are in percent by weight unless otherwise stated.

The following dyes were produced: Raw material Coloring Cream 1 Coloring Cream 2 Coloring Cream 3 Glycerin 5.0 5.0 5.0 Tetrasodium EDTA 0.3 0.3 0.3 Ascorbic acid 0.1 0.1 0.1 Sodium sulfite 0.3 0.3 0.3 perfume 0.5 0.5 0.5 Ammonia 25% 5.6 5.6 5.6 Ammonium bicarbonate 2.0 2.0 2.0 Myristyl alcohol 0.9 0.9 0.9 Cetyl alcohol 6.6 6.6 6.6 Hydrogenated Castor Oil 0.7 0.7 0.7 Glyceryl Stearate 1.2 1.2 1.2 Laureth-23 0.3 0.3 0.3 Ceteareth-30 0.9 0.9 0.9 Stearyl trimethyl ammonium chloride 3.6 3.6 3.6 Isopropyl palmitate 2.6 2.6 2.6 Silica 0.13 0.13 0.13 p-Toluenediamine sulfate 1.84 - 5.2 m-Aminophenol 0.24 0.36 0.36 Resorcin 0.66 - 1.76 2-Amino-4-(2-hydroxyethyl)aminoanisole sulfate 0.04 - 0.18 1-(2-Hydroxyethyl)-4,5-diaminopyrazole - 1.35 - 4-Amino-3-methylphenol - 0.14 - 5-Amino-2-methylphenol - 0.41 - KOH, aqueous to pH 10.3 to pH 10.6 to pH 10.0 demineralized water to 100 to 100 to 100 Shade of color Light brown Fire-red Black Raw material Coloring Cream 4 Coloring Cream 5 Coloring Cream 6 1,2-propylene glycol 5.0 5.0 5.0 Tetrasodium EDTA 0.3 0.3 0.3 Ascorbic acid 0.1 0.1 0.1 Sodium sulfite 0.3 0.3 0.3 perfume 0.5 0.5 0.5 Ammonia 25% 5.6 5.6 5.6 Ammonium bicarbonate 2.0 2.0 2.0 Myristyl alcohol 0.9 0.9 0.9 Cetyl alcohol 6.6 6.6 6.6 Hydrogenated Castor Oil 0.7 0.7 0.7 Glyceryl Stearate 1.2 1.2 1.2 Laureth-23 0.3 0.3 0.3 Ceteareth-30 0.9 0.9 0.9 Stearyl trimethyl ammonium chloride 3.6 3.6 3.6 Isopropyl palmitate 2.6 2.6 2.6 p-Toluenediamine sulfate 1.84 - 5.2 m-Aminophenol 0.24 0.36 0.36 Resorcin 0.66 - 1.76 2-Amino-4-(2-hydroxyethyl)aminoanisole sulfate 0.04 - 0.18 1-(2-Hydroxyethyl)-4,5-diaminopyrazole - 1.35 - 4-Amino-3-methylphenol - 0.14 - 5-Amino-2-methylphenol - 0.41 - KOH, aqueous to pH 10.3 to pH 10.6 to pH 10.0 demineralized water to 100 to 100 to 100 Shade of color Light brown Fire-red Black Raw material Coloring Cream 7 Coloring Cream 8 Coloring Cream 9 Glycerin 5.0 5.0 5.0 Tetrasodium EDTA 0.3 0.3 0.3 Ascorbic acid 0.1 0.1 0.1 Sodium sulfite 0.3 0.3 0.3 perfume 0.5 0.5 0.5 Ammonia 25% 5.6 5.6 5.6 Myristyl alcohol 0.9 0.9 0.9 Cetyl alcohol 6.6 6.6 6.6 Hydrogenated Castor Oil 0.7 0.7 0.7 Glyceryl Stearate 1.2 1.2 1.2 Laureth-23 0.3 0.3 0.3 Ceteareth-30 0.9 0.9 0.9 Stearyl trimethyl ammonium chloride 3.6 3.6 3.6 Isopropyl palmitate 2.6 2.6 2.6 Silica 0.13 0.13 0.13 p-Toluenediamine sulfate 1.84 - 5.2 m-Aminophenol 0.24 0.36 0.36 Resorcin 0.66 - 1.76 2-Amino-4-(2-hydroxyethyl)aminoanisole sulfate 0.04 - 0.18 1-(2-Hydroxyethyl)-4,5-diaminopyrazole - 1.35 - 4-Amino-3-methylphenol - 0.14 - 5-Amino-2-methylphenol - 0.41 - KOH, aqueous to pH 10.3 to pH 10.6 to pH 10.0 demineralized water to 100 to 100 to 100 Shade of color Light brown Fire-red Black

10 ml of each of the inventive coloring creams 1 to 3 were mixed with 10 ml of the oxidizing agent preparation. The resulting application preparation was applied to buffalo belly hair fibers with a brush, left at room temperature for 30 minutes, and then thoroughly rinsed with clean water. The fibers were dried with a hairdryer and subsequently colorimetrically measured. The following colorations were obtained: L-value (brightness) a-value (red/green component) b-value (yellow/blue component) Coloring Cream 1 21.3 2.1 2.9 Coloring Cream 2 33.1 40.6 22.4 Coloring Cream 3 18.2 -0.2 -2.8 Coloring Cream 4 21.3 2.1 2.9 Coloring Cream 5 33.1 40.6 22.4 Coloring Cream 6 18.2 -0.2 -2.8 Coloring Cream 7 21.3 2.1 2.9 Coloring Cream 8 33.1 40.6 22.4 Coloring Cream 9 18.2 -0.2 -2.8

The use of ammonium bicarbonate and/or silica does not affect the color result (the coloring), but leads to improved color performance of the coloring creams.

Claims (14)

Agent for coloring keratin fibers, characterized in that it contains (A) at least one dye precursor and/or a direct dye (B) at least one fatty acid glyceryl ester and (C) at least one cationic surfactant of the formula (I)

where the radicals R ¹ to R ⁴ independently of one another represent a C ₁ to C ₄ alkyl chain or a C ₁₀ to C ₃₀ alkyl chain, with the proviso that at least one and at most two of the radicals R ¹ to R ⁴ represent a C ₁₂ to C ₃₀ alkyl chain, and X stands for a physiologically acceptable anion, (D) ammonium bicarbonate. Means according to Claim 1 , characterized in that at least one developer or coupler component is contained as dye precursor. Remedy according to one of the Claims 1 or 2 , characterized in that at least one indole and/or indoline derivative is contained as dye precursor. Remedy according to one of the Claims 1 until 3 , characterized in that it contains oleic acid monoglycerides and/or stearic acid monoglycerides as fatty acid glyceryl esters. Remedy according to one of the Claims 1 until 4 , characterized in that the compound of formula (I) is selected from alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides, alkyltrimethylammonium bromides and dialkyldimethylammonium bromides. Remedy according to one of the Claims 1 until 5 , characterized in that the compound of formula (I) is selected from dicaprin dimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, dicetyldimethylammonium chloride, dilauryldimethylammonium chloride, behenyltrimethylammonium chloride and behenyltrimethylammonium methosulfate. Remedy according to one of the Claims 1 until 6 , characterized in that it further contains at least one fully or partially hydrogenated vegetable oil. Means according to Claim 7 , characterized in that the fully or partially hydrogenated vegetable oil is selected from soybean oil, coconut oil, hazelnut oil, palm kernel oil, sunflower oil, linseed oil, peanut oil, castor oil or rapeseed oil. Remedy according to one of the Claims 1 until 8 , characterized in that it contains - based on the weight of the agent - 0.1 to 10 wt.% ammonium bicarbonate. Remedy according to one of the Claims 1 until 9 , characterized in that it contains - based on the weight of the agent - 0.05 to 5 wt.% of silica. Two-component agent for coloring keratin fibers, characterized in that it contains a first preparation according to one of the Claims 1 until 10 and a second preparation containing at least one oxidizing agent. Two-component agent according to Claim 11 , characterized in that the second preparation contains at least one anionic or cationic surfactant. Process for coloring keratin fibers, characterized in that an agent according to one of the Claims 1 until 10 is mixed with an oxidizing agent preparation, the application preparation is applied to the fibers and rinsed off again after a certain exposure time. Process for coloring keratin fibers, characterized in that a two-component agent according to one of the Claims 11 or 12 is mixed into an application preparation, which is applied to the fibers and rinsed off after a certain exposure time.