WO2007141163A1 - Appliqué device for the use of an appliqué fluid on keratinaceous fibers - Google Patents

Abstract

This invention relates to an appliqué device (1) for the use of an appliqué fluid on keratinaceous fibers with at least one container (2) to hold the appliqué fluid, with an appliqué head (3) connected to the at least one container (2) and a porous application body (31) for applying the appliqué fluid by coating the fibers, wherein the appliqué fluid contains at least one oxidation dye precursor and is mixed with an oxidizing agent composition immediately before use.

Description

"Application device for applying an application liquid to keratinic fibers"

The present invention relates to a special application device for applying an application liquid to keratinic fibers, in particular a liquid dyeing preparation, based on oxidation dye precursors.

Human hair as an example of a keratin fiber is treated today in many ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role.

For temporary dyeings usually dyeing or tinting agents are used which contain as coloring component so-called substantive dyes. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the paint. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are usually prone to shampooing, so that sometimes after a few washes an undesirable nuance shift or even a visible "discoloration" occurs.

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

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

Usually, the colorants of the three categories described in the form of creams, gels or solutions are usually applied to the fibers with the aid of a brush. Also available on the market are dyes that are applied to the fibers as a shampoo formulation or conditioner formulation.

In addition to these more conventional application methods, application devices have also been developed in the past for temporary colorants based on substantive dyes and partially also for colorants based on oxidation dye precursors, with the aid of which the compositions can be applied to the keratinic fibers or to specific areas of the fibers. However, the known from the prior art application devices for oxidative colorants have the disadvantage that they are very complicated in design, since the preparation containing the dye precursors, must be made up separately from the oxidant preparation until immediately before use. Furthermore, the application devices known hitherto could not fully convince with regard to the uniformity of the application of paint and the simple operability by the consumer. An important aspect of ease of use is the "cleanliness" of the application, that is, neither the mixing of the colorant components nor the actual dyeing process contaminates the user's environment.

Specifically, DE 199 22 092 A1 describes, for example, a cap-like application device for dyeing hair strands, which is placed on an associated container with hair dye. This application device comprises a plurality of outlet openings for applying the hair dye and adjacent thereto guide prongs, which are drawn during use with combing movements through the hair. In addition, bristles are arranged around the outlet opening in order to achieve a more uniform application of the hair dye. Nevertheless, the outlet openings with the bristles do not allow a sufficiently metered application of the hair dye. In particular, an excessive leakage of the hair dye and thus also an unwanted wetting of the scalp can not be effectively excluded. It was therefore an object of the present invention to develop a dyeing system which makes it possible to prepare dyeing agents based on oxidation dye precursors until they are used separately and still allows easy handling by the consumer. In addition, the dyeing properties of the application device should also convince.

After extensive research it has now surprisingly been found that a special application device with a special oxidative dye overcomes the disadvantages of the prior art. With the aid of the application device according to the invention, it is now possible to dye gray areas of hair, in particular on the temples, the contours and the apex, in a targeted manner and without much effort ("clean" application).

A first subject of the present invention is therefore an application device for applying an application liquid to keratinic fibers, in particular hair, with at least one container for receiving the application liquid, with an application head which is connected to the at least one container and has a porous application body for applying the Application liquid by sweeping the fibers, wherein the application liquid contains the application liquid at least one oxidation dye precursor and is mixed with an oxidizing agent preparation immediately before use.

A first parameter essential to the invention is the use of at least one oxidation dye precursor in the application liquid. The term oxidation dye precursor summarizes according to the invention developer and Kupperkomponenten. As a rule, the application liquids according to the invention contain at least one developer component and at least one coupler component. Accordingly, it has proved to be preferred if the application fluid contains at least one developer component.

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

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

in which

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

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

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

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

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are in particular the 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, N- ( 4-amino-3-methylphenyl) -N- [3- (1 H -imidazol-1-yl) propyl] amine and 5,8-diaminobenzo-1,4-dioxane, see above like their physiologically acceptable salts.

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

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

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

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ -ReSt which is optionally substituted by a C 1 -C ₄ -alkyl radical, by a C 1 -C ₄ -hydroxyalkyl radical and / or by a bridging Y or which optionally part of a bridging ring system, the bridging Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, 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 of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl radical or a direct compound for bridging Y,

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

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

Preferred binuclear developer components of the formula (E2) are in particular: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis 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, 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 its physiologically acceptable salts.

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

in which:

G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkyl group - (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a hydroxy- (C 1 -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 or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ to C ₄ ) -alkyl, and

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

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

G ¹⁶ is hydrogen or a halogen atom.

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

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.

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

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol. Further, the developer component may be selected from heterocyclic developer components such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

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

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

Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 Diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4.5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole , 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3 methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5- Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

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

in which:

G 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 - Polyhydroxyalkylrest a (C ₁ - to C ₄ ^ AIkOXy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ - aminoalkyl radical which may optionally be protected by an acetyl-ureide or a sulfonyl radical , a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl radical, a di - [(C ₁ - to C ₄ ) -alkyl] - (C 1 -C ₄ ) -aminoalkyl radical where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 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 ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkylrest, a C ₁ - to C ₄ -Aminoalkylre st, a (C ₁ - to C ₄ ) -alkylamino- (C 1 -C ₄ ) -alkyl radical, a di - [(C 1 -C ₄ ) -alkyl] - (C ₁ - to C ₄ ) aminoalkyl radical, wherein 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) aminoalkyl radical, an amino radical , a C ₁ - to C ₄ -alkyl or di (C ₁ - to C ₄ -hydroxyalkyl) -amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1, q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0, if p + q equals 2, n has the value 0 , and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); wweennnn pp ++ qq gglleeiicchh 11 iisstt, nn ddtwhen WWeerrtt 11 hhaatt, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

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

When the pyrazolo [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium shown, for example, in the following scheme:

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are in particular 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3 methyl pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chloro-resorcinol, 2-chloro 6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methyl resorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol. Coupler components preferred according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-

Cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5- Amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-

Hydroxyethyl) -amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol,

1, 3-Dihydroxy-5- (methylamino) benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as 2,4 -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, 2 - ({3 - [(2-

Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -

2-methoxy-5-methylphenyl} amino) ethanol, 2- ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} -amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino ] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino-3-bis (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3

Diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol,

Resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-

Chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,

Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4 dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

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

Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-

dihydroxynaphthalene,

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

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

Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,

Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,

Pyrimidine derivatives such as 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 and their physiologically acceptable salts. Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

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

A second essential constituent of the application liquid according to the invention is at least one oxidizing agent preparation which is mixed with the dye precursor-containing preparation only immediately before use.

According to the invention, the term "immediately before use" preferably means a period of at most 45 minutes before the application liquid is applied to the fibers It is particularly preferred according to the invention to combine the preparations, to thoroughly mix them and directly to the application of the resulting To start application liquid.

According to the invention, the preferred oxidizing agents are persulfates, chlorites and, in particular, hydrogen peroxide or its addition products, for example, urea, alkali metal carbonates, melamine and alkali metal borates.

The oxidizing agent preparation preferably contains the oxidizing agent (s) in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purposes of the present invention, such carriers are, for example, creams, emulsions, gels or else other preparations which are suitable for mixing with the dye preparation and the subsequent use on the hair.

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

In a preferred embodiment, the oxidant preparation is formulated as a powder or as a tablet. The term tablets are also to be understood as meaning pressed powders according to the invention. In the context of this embodiment, percarbamide, percarbonate and perborate are particularly preferred oxidizing agents.

In the event that the oxidizing agent preparation is formulated as a tablet, it has proven to be particularly preferred if it further contains at least one dissolution accelerator. The term dissolution accelerator includes gas-evolving components, preformed and trapped gases, disintegrants and mixtures thereof.

In one embodiment of the present invention, gas-developing components are used as the dissolution accelerator. Upon contact with water, these components react with each other to form gases in-situ, which create a pressure in the tablet that disintegrates the tablet into smaller particles. An example of such a system are specific combinations of suitable acids with bases. Preference is given to mono-, di- or trihydric acids having a pK _{a of from} 1.0 to 6.9. Preferred acids are citric, malic, maleic, malonic, itaconic, tartaric, oxalic, glutaric, glutamic, lactic, fumaric, glycolic and mixtures thereof. Particularly preferred is citric acid. It may be very particularly preferable to use the citric acid in particulate form, the particles having a diameter of less than 1000 μm, in particular less than 700 μm, very particularly preferably less than 400 μm. Other alternative suitable acids are the homopolymers or copolymers of acrylic acid, maleic acid, methacrylic acid or itaconic acid having a molecular weight of 2,000 to 200,000. Particularly preferred are homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid. According to the invention, preferred bases are alkali metal silicates, carbonates, bicarbonates and mixtures thereof. Metasilicates, bicarbonates and carbonates are particularly preferred, bicarbonates are most preferred. Particular preference is given to particulate hydrogencarbonates having a particle diameter of less than 1000 μm, in particular less than 700 μm, very particularly preferably less than 400 μm. Sodium or potassium salts of the above bases are particularly preferred. These gas-evolving components are preferably contained in the tablets according to the invention in an amount of at least 10% by weight, in particular of at least 20% by weight.

In a further embodiment of the present invention, the gas is preformed or trapped so that upon onset of dissolution of the molded article, gas evolution begins and the further resolution accelerates. Examples of suitable gases are air, carbon dioxide, N ₂ O, oxygen and / or other non-toxic, non-combustible gases.

In a third, particularly preferred embodiment of the present invention, disintegration auxiliaries, so-called shaped body disintegrants, are incorporated into the moldings as dissolution accelerators in order to shorten the disintegration times. According to Römpp (9th edition, Vol. 6, page 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, pp. 182-184), the term "disintegration agent" or "disintegration accelerator" is understood as meaning excipients which are suitable for rapid disintegration of moldings in water or gastric juice and for the release of the pharmaceuticals in resorbable form.

These substances, which are also referred to as "explosives" due to their action, increase their volume upon swelling (swelling) Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives , Alginates or casein derivatives.

Disintegrating agents based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred tablets comprise such cellulose-based disintegrants in amounts of from 0.5 to 50% by weight, preferably from 3 to 30% by weight, based on the total tablet contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _H and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used as the sole cellulosic disintegrating agent but are used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives. The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The disintegration auxiliaries according to the invention are available commercially for example under the name of Arbocel ^® from Rettenmaier. A preferred disintegration assistants, for example, Arbocel ^® TF-30-HG.

As a further disintegrating agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm. Suitable microcrystalline cellulose is available commercially for example under the trade name Avicel ^®.

The accelerated dissolution of the moldings can also be achieved according to the invention by pre-granulation of the further constituents of the tablet.

A third essential aspect of the present invention is the nature of the application device.

An advantageous design of the actual application device provides that the porous applicator has continuous pores to achieve capillary action. The capillary properties of the application body, which is in contact with the application liquid in a wick-like manner, ensure reliable transport of the application liquid out of the at least one container and metered application of the application liquid by sweeping it over the fibers. According to a further developed variant of the application device, the application body preferably has a fibrous, sponge, foam, felt or sintered material-like material structure. This material structure causes the desired capillary action of the application body, so that, for example, an unwanted leakage or dripping of the application liquid from the application body is omitted, but at the same time a reliable fluid delivery is ensured by means of the application body.

As an alternative to a substantially block-shaped design of the porous application body, it can also have a plurality of pin-shaped projections. This increases the effective surface area of the application body and thus improves the order of the application liquid. Accordingly, by means of the coating movement of the applicator body over the keratinic fibers, in particular the hair, a better dyeing result is guaranteed both quantitatively and qualitatively.

Another useful embodiment of the application device is achieved in that the application head has a plurality of possibly detachably arranged, comb teeth. These comb teeth are arranged in particular adjacent to the application body. The brushing motion of the entire application head during the application initially provides, by means of the comb teeth, for a disentanglement of the fibers or the hair and thus, above all, for a uniform application of the application liquid. Basically, the detachable arrangement of the comb teeth on the application head allows a more versatile use of the application device. It also proves to be advantageous for such an arrangement when the comb teeth protrude from the porous applicator body. A preferred embodiment of the application device is to arrange the comb teeth of the application head in a circle around the application body. Regardless of the respective coating movement direction, the fibers or hair are first unraveled during use in each case before the actual application of the application liquid takes place.

Furthermore, it is essential to the invention that the actual application liquid is prepared only immediately before use by mixing the preparation of the oxidizing agent with the preparation containing the dye precursors. In particular, as a result of often insufficient storage stability of the mixture, correspondingly designed storage and mixing containers are required in the context of the overall device. The suitably designed storage and mixing containers guarantee on the one hand prior to use sufficient storage stability for the individual components of the application liquid and on the other hand ensure appropriate handling of the overall device during use. For this purpose, different variants of the application device are possible. These different variants have in common that immediately before the application, the already mixed preparation of the application liquid is in the container of the device according to the invention. The container is connected to the application head. For the container, a variety of design options is conceivable. For example, this container can be ergonomically adapted in its shape to the application process in order to facilitate the handling of the application device for the user.

The container can be designed both as a separate application container, in which the ready-mixed preparation of the application liquid is filled before starting the application. Similarly, it is also conceivable that the container serves both as an application container, as well as before application as a mixing container. Mixing container and application container are identical in this variant and form the container. For both design variants is Below a variety of ways described to design such mixing container constructive.

In order to prepare a mixture of the preparation of the oxidizing agent with the preparation containing the dye products, there are a variety of possibilities, some of which are to be enumerated here by way of example.

Thus, it is possible to provide the user with three or more containers in a first embodiment of the present invention. The first container contains the oxidizing agent, the second container the dye composition and the third container serves as a mixing container. Further additional storage containers are possible. To prepare the mixture, the desired amount is added from the two storage containers in the mixing container, this closed and, for example, by subsequent shaking of the mixing container, the two components are mixed together. The mixing process can be accelerated by the fact that internals in the mixing vessel when shaking produce a turbulent flow (high Reynolds numbers) and thus improve and accelerate the mixing process. In the case where one or both components are particulate or granular components, it may be advantageous to provide internals in the mixing container in such a way that a mechanical action is aimed at destruction or faster solubility of the granules or component pieces. This is achieved, for example, by projecting into the mixing container tips or barb-like elements. Also internals in the form of stirrers achieve a similar result.

Another embodiment within the scope of the present invention is to provide one or more of the liquid soluble material reservoirs. These soluble storage containers are placed in the mixing container and there dissolved by the respective solvent, preferably a component of the mixture to be prepared. This embodiment has the advantage for the user of never coming into contact with individual components packed in the storage containers during the preparation of the overall preparation. In order to accelerate the dissolution process in addition, it may be advantageous to use mechanical installations here, too, which achieve a comminution of the reservoirs described and an associated increase in the speed of the dissolution process. Advantageously, such soluble storage containers are designed as a foil bag.

A further variant for producing mixtures according to the invention is the provision of at least two separate containers for storing the respective component, wherein at least one of the containers simultaneously acts as a mixing container. For such embodiments, all the above examples of the variant with at least three containers are also conceivable within the scope of the present invention. Both in two storage containers, one of which additionally serves as a mixing container and in the variant with at least three containers (ie a separate mixing container), it may be advantageous to provide Umfüllhilfen, which ensure that when transferring from the storage containers in the mixing container / combined Vorratsmischbehälter no single component is spilled. Such Umfüllhilfen are, for example, extended Ausgießrohre that allow the nesting of reservoir and mixing container and means for fixing the reservoir to the mixing container during Umfüllvorgangs. Such fixing means are for example snap-locking connections, screw or bayonet.

In order to further accelerate transfer, it may be advantageous to provide means which provide pressure equalization between the two containers during the transfer operation. Such means are, for example, arranged within the opening of a reservoir tubes, which can act as a snorkel. Also, one-way valves in the reservoir for pressure equalization are conceivable for such functionalities.

It is also helpful for the user if the storage containers are provided with a closure which only opens upon a triggering command. Thus, the user can ensure that the transfer process does not start until the reservoir and mixing container are in the correct position for the mixing process. One possible embodiment of such closures is, for example, a tear-open film which tears open due to an increased internal pressure in the storage container and thus starts the transfer process. The internal pressure in the reservoir can be increased for example by pumping means or by simply squeezing.

Also mechanical destruction of such films by mechanical aids, such as thorns, or by the contained component itself, for example in tablets, is conceivable.

For example, it is also conceivable to carry out the storage container for granules, powder or lumpy goods as a blister pack and additionally to provide auxiliaries which allow these blisters to be placed above the opening of the mixing container. The user of such mixing systems simply presses the component contained in the blister through the sealing film into the mixing container.

In addition to the variants with three or more containers, or two or more containers, it is also conceivable to provide only a single container, which serves both as a storage container and as a mixing container. Such containers must be equipped due to the lack of storage stability of the individual components in mixture with a possibility for separation of the two components during storage. Such a separation can be generated for example by a partition, through which a container with two separate chambers is formed. The mixture in such a system is created by the destruction of the partition or by the arrangement of a valve in this partition. For destructible partitions, it may be useful to achieve this destructibility either by increasing the internal pressure or by mechanical means that are directly or indirectly operable from outside the container. An embodiment of such mixing containers can be, for example, a storage container whose destructible dividing wall can be destroyed by mechanical means mounted on the applicator head and projecting into the container. The destruction takes place in such a case by screwing or placing the applicator head in the application position. Separate devices for destroying the partition are of course conceivable within the scope of the present invention.

In addition to a destructible partition, it may also be advantageous to provide a fixed partition with a one-way valve. Such a one-way valve could open, for example, by increasing the internal pressure in one of the two chambers and thus convert the component from one chamber into the other chamber. The increase in internal pressure can be achieved by the flexible design of the entire container and its compression by the user's hand. Also, additional pumping means are quite conceivable.

In addition to the design of a mixing device with a single container and different chambers separated by partitions, which serve as a reservoir, it may be advantageous to provide an empty mixing chamber in addition to the storage chambers before the start of the mixing process. In such an embodiment is located between the storage chambers and the mixing chamber, an element for transferring the components from the individual storage chambers in the mixing chamber. Such elements may, as already described above embodiments, destructible walls, but also one-way valves in the direction of the mixing chamber.

The above-described devices for mixing the oxidizing agent with the dye component and possible other components are of course only examples and do not limit the present application. Also, combinations of all of the mixing devices shown above are conceivable within the scope of the present invention.

Furthermore, it has proven to be particularly preferred if the resulting application liquid is formulated thin liquid. Application fluids which have a viscosity of from 0 to 2000 mPas when mixed with the oxidizer formulation (measured at 22 ° C. in a Brookfield viscometer with spindle 4 and a speed of 4 rpm) have proved to be particularly preferred. A viscosity of 0 to 100 mPas, measured under the conditions mentioned, is particularly preferred according to the invention. A viscosity of 50 to 500 mPas (measured at 20 ^° C. (Brookfield viscometer type RV-T, spindle 4 with a rotation speed of 20 rpm) is very particularly preferred according to the invention.

In addition to the essential oxidation dye precursors according to the invention, the application liquid may contain further components which contribute to the coloring.

In a first embodiment of the present invention, the application liquid may therefore contain at least one naturally-analogous dye precursor. As precursors of naturally-analogous dyes such indoles and indolines are preferably used which have at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

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

in the independently of each other

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

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

G ₂ i is hydrogen or a C 1 -C ₄ -alkyl group,

G ₂₂ is hydrogen, a C 1 -C ₄ -alkyl group or a group -CO-G ₂₄ , in which G ₂₄ is a C 1 -C ₄ -alkyl group, and

- G ₂₃ is one of the groups mentioned under G ₂₂ , and physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

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

in the independently of each other

G ₂₅ is hydrogen, a C 1 -C ₄ -alkyl group or a C 1 -C ₄ -hydroxyalkyl group,

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

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

G ₂₈ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-G ₃₀ wherein G ₃₀ represents a C-rC ₄ alkyl group, and

G ₂₉ is one of the groups mentioned under G ₂₈ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

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

The indoline and indole derivatives can be used in the colorants of the invention both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, for. As the hydrochlorides, sulfates and hydrobromides are used. The indole or indoline derivatives are contained therein usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%. In a further embodiment, it may be preferred according to the invention to use the indoline or indole derivative in colorants in combination with at least one amino acid or an oligopeptide. The amino acid is advantageously an α-amino acid; Very particularly preferred α-amino acids are arginine, ornithine, lysine, serine and histidine, in particular arginine.

In a second preferred embodiment of the present invention, the application liquid may contain at least one substantive dye.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 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 well-known compounds as well

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.

Furthermore, the applicator liquids according to the invention may contain a cationic substantive dye. Particular preference is given here to a) cationic triphenylmethane dyes, such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, b) aromatic systems which are substituted by a quaternary nitrogen group, for example Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as for example in EP-A2-998 908, to which reference is explicitly made will be mentioned in claims 6 to 11.

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

CH ₃ SO ₄ ^"

Cl ^"

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

The cationic substantive dyes sold under the trademark Arianor® are also very particularly preferred cationic substantive dyes according to the invention. The agents according to the invention according to this embodiment contain the substantive dyes preferably in an amount of 0.01 to 20 wt .-%, based on the total applicator.

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

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

With regard to the dyes which can be used in the hair-dyeing and tinting compositions according to the invention, reference is expressly made to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250, direct dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "Dermatology" (Editor: Ch., Culnan and H. Maibach), published by Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", Issued by the European Community, available in disk form from the Federal Association of German industrial and commercial enterprises for pharmaceuticals, health products and personal care registered association, Mannheim, reference is made.

In the context of the present invention, it has proven to be preferred if the oxidation dye precursors are incorporated in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purposes of the present invention, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as, for example, shampoos, or other preparations which are suitable for use on the hair.

With regard to the definition of an "aqueous-alcoholic solution", reference should firstly be made to the above statements.

Particularly preferred according to the invention is a water-containing carrier which contains at least one C ₁ -C ₄ -alkoxy and at least one further organic solvent. It may be preferred according to the invention, when the water is a proportion of 20 to 60% by weight, preferably from 30 to 50% by weight, the C 1 -C ₄ -alcohol contains from 20 to 60% by weight, preferably from 30 to 50% by weight, and the organic solvent accounts for 1 to 30 wt .-%, preferably from 5 to 15 wt .-%, each based on the total application liquid have. In the context of this embodiment, a composition containing water, ethanol and propylene carbonate may be particularly preferred.

The application liquid according to the invention is preferably adjusted to a pH of from 5 to 11, in particular from 7.5 to 11, by means of acids and / or alkalizing agents.

For this purpose, preferred alkalizing agents are alkali or alkaline earth hydroxides, ammonia or organic amines. The organic amines are preferably selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1 , 3-propanediol, 2-amino-2-methylbutanol and triethanolamine. In particular, monoethanolamine, triethanolamine and 2-amino-2-methyl-propanol and 2-amino-2-methyl-1, 3-propanediol are preferred within the scope of this group. Also, the use of amino acids and / or oligopeptides such as ω-aminocaproic acid as the alkalizing agent is preferred in the context of the present invention.

Furthermore, preference is given to using those amino acids and oligopeptides whose 2.5% strength by weight solutions have a pH of 9 or greater in water. Such an amino acid is arginine which is preferably used.

Furthermore, organic or inorganic acids can be used to adjust the pH. Hydrochloric acid, sulfuric acid and phosphoric acid are to be mentioned in particular as preferred inorganic acids. Preferred organic acids are acetic acid, glycolic acid, citric acid, tartaric acid, lactic acid and malic acid. Malic acid is a particularly preferred acid used.

Furthermore, the application liquids according to the invention may contain all known in such preparations active ingredients, additives and excipients. Although it has proved to be preferred, when the application liquids are formulated free of surfactants, the application liquids according to the invention may in another embodiment also contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants. Anionic surfactants may be very particularly preferred.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 C-men men. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanol ammonium salts with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C atoms (Soap),

Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear

Alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,

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

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

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

Sulfobernsteinsäuremono- and -dialkylester having 8 to 18 carbon atoms in the alkyl group and

Sulfosuccinic acid mono-alkylpolyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 C atoms, linear α-olefin sulfonates having 12 to 18 C atoms,

Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,

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

A-37 23,354,

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

Esters of tartaric acid and citric acid with alcohols containing adducts of about 2-

15 molecules of ethylene oxide and / or propylene oxide to fatty alcohols having 8 to 22 carbon atoms.

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

Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and on

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

C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol,

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

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

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

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

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

| - and do-alkyl groups essentially of C ₂ - and C alkyl polyglycosides are those in which R ¹ consists essentially of C ₈ are particularly preferred _4- alkyl groups, essentially from C ₈ - to C- | ₆ alkyl groups or consisting essentially of Ci ₂ - to Ci ₆ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred. The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further ingredient of the preparations according to the invention in the event that an action of the perfume oil on the hair which exceeds the duration of the hair treatment is desired.

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

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO * ^" '- or -SO ₃ ⁽⁾ group in the molecule Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N , N-dimethylammonium glycinates, for example, the cocoalkyl dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacylaminopropyl- dimethylammoniumglycinat, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazoline with 8 each A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are to be understood as meaning those surface-active compounds which, apart from a C ₈ -C 20 -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C-1 ₂ - ₁₈ acylsarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

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

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

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

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride". The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

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

Furthermore, the agents used in the process according to the invention may preferably also contain a conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils.

Cationic polymers may be preferred as conditioning agents. These are in the

Rule Polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and amides of acrylic acid and methacrylic acid. The products obtainable under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)), Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer are examples of such cationic polymers. Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and - methacrylate such as, for example, quaternized with diethyl sulfate, vinylpyrrolidone dimethylaminomethacrylate copolymers such compounds are available under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.. Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, such as those available under the name Luviquat ^® , quaternized polyvinyl alcohol and those under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the polymer main chain.

Particular preference is given to cationic polymers of the four first-mentioned groups, very particular preference to polyquaternium-2, polyquaternium-10 and polyquaternium-22.

Also suitable as conditioning active ingredients are silicone oils, in particular dialkyl and alkylaryl siloxanes, for example dimethylpolysiloxane and methylphenylpolysiloxane, and also their alkoxylated and quaternized analogs. Examples of such silicones are the Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 products sold and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Dow Corning ^® 929 emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt, di-quaternary polydimethylsiloxanes, quaternium-80).

Also usable as conditioning active ingredients are paraffin oils, synthetically prepared oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach kernel oil.

Likewise suitable hair-conditioning compounds are phospholipids, for example soya lecithin, egg lecithin and cephalins.

Further active ingredients, auxiliaries and additives are, for example, nonionic polymers, for example vinylpyrrolidone / vinyl acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylpolysiloxane;

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

Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic,

Karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g.

Methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and

Derivatives such as amylose, amylopectin and dextrins, clays such. B. bentonite or fully synthetic

Hydrocolloids such as e.g. polyvinyl alcohol,

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

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber-structure-improving agents, especially mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl-2 -alkylimidazolinium methosulfate

Defoamers like silicones,

Dyes for staining the agent,

Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,

Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

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

Cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

fatty acid,

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

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

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

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

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

pigments

Stabilizer for hydrogen peroxide and other oxidants,

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

Antioxidants.

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

The constituents of the water-containing carrier are used to prepare the inventive application liquid in amounts customary for this purpose; For example, emulsifiers are used in concentrations of 0.5 to 30 wt .-% and thickening agents in concentrations of 0.1 to 25 wt .-% of the total colorant.

B e i s p e e l e

1 application device

Other features of the invention will become apparent from the single drawing, which shows a generic application device in perspective and will be explained in more detail below.

The application device 1 shown in FIG. 1 is designed for use with a liquid hair dye. In principle, however, such an application device 1 can also generally serve for the application of any application fluid for keratinic fibers, the application fluid being applied by brushing movements to the fibers. The application device 1 has a container 2 which receives the hair dye or the application liquid and stores it until it is used. For this purpose, it may be useful to provide an absorbent storage element in the interior of the container, which is designed, for example, as a fibrous or sponge-shaped, in order to receive the hair dye or the application liquid.

The container 2 has two separate areas inside. In the first, larger area, the application liquid is prepared before the application. In the second, smaller area, the powdery oxidizing agent preparation is formulated before the application. Immediately before the application, the partition wall between the two areas is pierced by an externally actuated mandrel, so that there is a mixing of the two separately assembled components. In this embodiment, the container 2 thus serves the separate packaging, the mixture of the components and also as a storage container during use.

An application head 3, by means of which the hair dye is applied to the hair, is fastened to an open container end. The application head 3 essentially comprises a porous application body 31 and a plurality of comb teeth 33, which in turn are advantageously integrally connected to at least one comb element 34. FIG. 1 shows the application device 1 in the ready-to-use operating position, ie. H. with open application head 3. Outside the application times, the application head 3 is covered by a cap, not shown, which is attached, for example, to a thread 4 on the container 2. Thus, the application head 3 is sealed from the environment, so that drying of the liquid hair dye is effectively prevented.

Specifically, the applicator body 31 communicates with the liquid hair dye or the application liquid in conjunction to the liquid in the manner of a wick To promote capillary action from the container and to provide for the application to the hair. For this purpose, the porous application body 31 has a material structure with continuous pores in order to achieve the corresponding capillary action. The application body 31 consists in particular of a fibrous, sponge, foam, felt or sintered material-like material. The advantage of such a designed applicator body 31 is not only in the reliable promotion of the hair dye but also in the high fluid absorbency. Namely, the high liquid absorption capability prevents unwanted leakage or dripping of the hair dye from the application device 1. Geometrically, the application body 31 is preferably block-shaped (not shown) or designed with a plurality of pin-shaped projections 32. In particular, the embodiment with a plurality of pin-shaped projections 32 increases the effective surface of the application body 31, so that better coloring results are achieved when sweeping the hair.

The comb teeth 33, which are likewise formed immediately adjacent to the application body 31 on the application head 3, are used for disentangling the hair during application of the application device 1. This disentangling of the hair results in a more uniform application of the color to the hair. In particular, the individual comb teeth 33 are integrally connected to at least one comb element 34 in order to simplify handling and production in general. Furthermore, it makes sense to attach the comb teeth 33 or comb elements 34 releasably to the application head 3, in order to permit an application without comb teeth 33 or comb elements 34, depending on the particular case of use. In general, the comb teeth 33 protrude in the longitudinal direction of the application device 1 with respect to the application body 31 in order to prevent contact of the scalp with the application body 31 or the application fluid, especially in hair applications.

According to a further embodiment not shown, the comb teeth 33 are arranged in a circle around the applicator body 31 lying around on the application head 3. Thus, the hair is first unraveled during the application of the application device 1, regardless of the respective coating movement direction, before the actual application of the hair dye takes place. This gives improved staining results. 2 application liquids

The following information is by weight unless otherwise stated.

Colorant A

Ethanol 20.0

Texapon.RTM ^® NSO UP 5.0

1, 2-propanediol 7.0

Sodium sulfite 0.5

Ascorbic acid 0.5

Ammonium sulfate 1, 2

Turpinal SL ^® 0.2

Ammonia (25% aqueous solution) ad pH 9.5 p-toluenediamine 0.4

2-methylresorcinol 0.15

4-chlororesorcinol 0.05

Resorcinol 0.03

3-Amino-2-methylamino-6-methoxypyridine 0.06

Water ad 100

The resulting colorant was mixed with percarbamide in the mixing ratio of colorant: developer 10: 1 immediately before use as described above. Subsequently, the application liquid was applied with the application device according to the invention on the fibers and rinsed after a contact time of 30 minutes.

Colorant B

Dehydrol® ^® LS2 4.9

Eumulgin ^® CS 50 5.0

Kokoslorol ^® 8.0

Edenor ^® PK 1805 6.8

Isopropanol 14.5

1, 2-propylene glycol 6,8

Texapon ^® NSO UP 4,5

Merquat ^® 280 2.0

Miranol ^® C2M SF 1, 0

Monoethanolamine 5.0 L-arginine ad pH 10

Sodium sulfite 0.2

Ascorbic acid 0.2

Turpinal SL ^® 0.2 p-toluenediamine 1, 9

4-amino-3-methylphenol 0.5

Resorcinol 0.6m-aminophenol 0.05

5-amino-2-methylphenol 0.15

2-amino-6-chloro-4-nitrophenol 0.07

Perfume 0.6

Water ad 100

The resulting colorant was mixed with percarbamide in the mixing ratio of colorant: developer 10: 1 immediately before use as described above. Subsequently, the application liquid was applied with the application device according to the invention on the fibers and rinsed after a contact time of 30 minutes.

List of used commercial products

The commercial products used in the examples are defined as follows:

Dehydol ^® LS 2 ₁₂ C -i ₄ fatty alcohol with about 2-EO units (INCI name:

Laureth-2) (Cognis Pulcra)

Edenor ^® PK 1805 oleic acid (INCI name: Oleic Acid) (Cognis)

Eumulgin ^® CS 50 Cetylstearylalkohol with about 50 EO units (INCI name:

Ceteareth-50) (Cognis) Kokoslorol ^® C _{12-i 8} fatty alcohol (INCI name: Coconut Alcohol) (Cognis)

Merquat ^® 280 dimethyldiallylammonium acrylic acid copolymer (about 35

Active substance in water; INCI name: Polyquaternium-22) (Ondeo-Nalco)

Miranol ^® C2M SF approx. 38-40% solids; INCI name: Disodium

Cocoamphodipropionate (Rhodia)

Texapon.RTM ^® NSO UP lauryl ether sulfate, sodium salt (about 27.5% of active substance; INCI

Name: Sodium Laureth Sulfate) (Cognis)

Turpinal ^® SL 1-hydroxyethane-1, 1-diphosphonic acid (about 58 - 61%

Active substance content; INCI name: Etidronic Acid, Aqua (Water)) (Solutia)

Claims

Patent claims

1. Application device (1) for applying an application liquid to keratinic fibers with at least one container (2) for receiving the application liquid, with an application head (3) which is connected to the at least one container (2) and a porous applicator body (31) has for applying the application liquid by sweeping the fibers, characterized in that the application liquid contains at least one oxidation dye precursor and is mixed immediately before use with an oxidizing agent preparation.

2. Application device according to claim 1, characterized in that the application liquid contains at least one developer component.

3. Application device according to one of claims 1 or 2, characterized in that the oxidizing agent preparation is powdery.

4. Application device according to claim 3, characterized in that the oxidizing agent is selected from a percarbamide, a percarbonate or a perborate.

5. Application device according to one of claims 1 to 4, characterized in that the application liquid after mixing with the oxidizing agent preparation has a viscosity of 0 to 2000 mPas (measured at 22 ° C in Brookfield viscometer with spindle 4 and a speed of 4rpm).

6. Application device according to one of claims 1 to 5, characterized in that the anmontierte container has two separate areas, the contents of which can be combined immediately prior to use by actuation of a trigger mechanism.

7. Application device (1) according to one of claims 1 to 6, characterized in that the porous application body (31) has continuous pores to achieve a capillary action.

8. Application device (1) according to one of claims 1 to 7, characterized in that the application body (31) preferably has a fibrous, sponge, foam, felt or sintered material-like material structure.

9. application device (1) according to one of claims 1 to 8, characterized in that the porous applicator body (31) has a plurality of pin-shaped projections (32).

10. Application device (1) according to one of claims 1 to 9, characterized in that the application head (3) has a plurality, optionally releasably arranged, comb teeth (33).

11. Application device (1) according to claim 10, characterized in that the comb teeth (33) protrude with respect to the porous applicator body (31).

12. Application device (1) according to any one of claims 10, 11, characterized in that the comb teeth (33) of the application head (3) are arranged in a circle around the applicator body (31) around.