DE10059290A1 - Solid dye for keratinic fibers, particularly hair, comprises a synthetic direct dye in a carrier - Google Patents

Abstract

Solid dye for keratinic fibers a synthetic direct dye in a carrier, is new.

Description

The present invention relates to molded articles for dyeing keratinic fibers which contain at least one synthetic substantive dye, the use these means for the production of hair coloring preparations and a method for coloring keratin fibers with these moldings.

Today, human hair is made with hair cosmetic preparations in a variety of ways treated. This includes about cleaning the hair with shampoos, the care and re generation with rinses and cures as well as bleaching, dyeing and shaping of the Hair containing coloring, tinting, waving and styling preparations. Play it Means for changing or nuancing the color of the scalp hair an outstanding one Role.

For temporary colorations, coloring or tinting agents are usually used contain so-called direct pullers as coloring components. This is Dye molecules that are absorbed directly onto the hair and do not cause an oxidative process Need training of color. This already belongs to these dyes, for example Henna known from ancient times for coloring the body and hair. These colorations are usually much more sensitive to shampooing than oxidative ones Coloring, so that a much faster, often undesirable Shift in nuances or even a visible "discoloration" occurs.

For permanent, intense colorations with appropriate fastness properties so-called oxidation colorants are used. Such colorants usually contain Oxidation dye precursors, so-called developer components and couplers components. The developer components form under the influence of Oxidizing agents or of atmospheric oxygen with each other or under coupling with a or more coupler components from the actual dyes. the Oxidation dyes are characterized by excellent, long-lasting dyeing results the end. For natural-looking colorations, a mixture of one usually has to be used larger number of oxidation dye precursors are used; in many cases Substantive dyes are still used for shading.

Finally, a new type of dyeing process has recently attracted a great deal of attention. In this process, precursors of the natural hair dye melanin are added to the Hair brings up; these then form natural analogs in the course of oxidative processes in the hair Dyes from. Such a process with 5,6-dihydroxyindoline as dye precursor was described in EP-B1-530 229. With, especially multiple, use of With 5,6-dihydroxyindoline it is possible to treat people with graying hair to reproduce natural hair color. The coloring can be done with atmospheric oxygen as only oxidizing agent take place, so that no further oxidizing agent must be resorted to. For people who were originally medium blonde to brown In hair, the indoline can be used as the sole dye precursor. For the Use in people who were originally red and especially dark to black Hair color, on the other hand, can often only give satisfactory results by using it further dye components, in particular special oxidation dye precursors, be achieved.

Hair colorants are usually in the form of aqueous emulsions or color gels formulated, if necessary, immediately before application with a Oxidizing agent preparation are mixed. However, this method leaves with regard to the Storage stability of the formulations, dosability and easy handling Wishes open.

In DE-A-36 09 962 a tablet-shaped colorant based on henna and Oxidation dye precursors suggested that with the shortest possible exposure time to enable intense black colorations. However, this writing is by no means indicative refer to the dye tablets according to the invention.

The object was therefore to improve the behavior of the tint moldings in terms of their dissolving behavior and the rheology of the application mixture as well as the coloring properties optimize.

It has now been found, surprisingly, that by using the inventive Moldings the achievable colorations in terms of their intensity and Fastness properties can be significantly improved, and the moldings can be through are characterized by a significantly reduced dissolution time.

A first subject of the present invention is therefore molded articles for coloring keratinic fibers, which in a cosmetically acceptable carrier at least one contain synthetic substantive dye.

According to the invention, keratinic fibers include furs, wool, feathers and in particular understand human hair. Although the moldings according to the invention are primarily Line suitable for dyeing keratinic fibers is in principle one Use in other areas does not prevent it.

Synthetic substantive dyes

In principle, all substantive dyes can be used according to the invention. Nitro dyes have proven to be particularly suitable. According to the invention are under Nitro dyes to understand the coloring components, the at least one have aromatic ring system that carries at least one nitro group.

Particularly preferred nitro dyes are HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 12, HC Violet 1 and 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, Picric acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3- nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

In addition to the nitro dyes, there are also the azo dyes, anthraquinones or Synthetic substantive dyes preferred according to the invention for naphthoquinones. Preferred substantive dyes of this type are, for example, Disperse Orange 3 Disperse Blue 3, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9 and Acid Black 52 and 2-hydroxy-1,4-naphthoquinone.

Furthermore, it can be preferred according to the invention if the synthetic substantive dye carries a cationic group. Are particularly preferred

• a) cationic triphenylmethane dyes,
• b) aromatic systems substituted with a quaternary nitrogen group are and
• c) substantive dyes that contain a heterocycle of at least one has quaternary nitrogen atom.

Examples of dyes of class (i) are in particular Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14.

Examples of dyes of class (ii) are in particular Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17.

Examples of dyes of class (iii) are given in particular in EP-A2-998 908 which is explicitly referred to at this point, disclosed in claims 6 to 11.

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

The compounds of the formulas (DZ1), (DZ3) and (DZ5) are very particularly preferred cationic substantive dyes of group (iii).

The moldings according to the invention preferably contain the substantive dyes in an amount from 0.01 to 20% by weight.

Alkalizing agents

Although the moldings according to the invention during their dissolution Application preparations can result that are weakly acidic, neutral or even alkaline are set, contain the moldings in a preferred embodiment at least one alkalizing agent.

In principle, the alkalizing agents are not subject to any restrictions. Suitable Alkalizing agents are, for example, ammonium salts, carbonates, amino acids, Alkali or alkaline earth hydroxides and organic amines.

In a preferred embodiment of the present invention, there are solid Alkalizing agents are used.

In a further embodiment of the present invention, it may be preferred Use alkalizing agents that are characterized by good water solubility. According to the invention, compounds are readily soluble in water, of which at least 5 g are in Dissolve 100 ml of water at 15 ° C. Particularly preferred are compounds with a Water solubility of more than 7.5 g in 100 ml of water at 15 ° C.

Furthermore, the alkalizing agents have proven to be particularly preferred after their incorporation into the moldings according to the invention only has a low partial pressure develop outside of the molding.

In a preferred embodiment of the present invention, as Alkalizing agents Amino acids or oligopeptides with at least one amino group and a carboxy or sulfo group, the 2.5% strength aqueous solution of which is one Has a pH greater than 9.0.

In the context of this embodiment, aminocarboxylic acids are particularly preferred, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids. Among the α-aminocar In turn, lysine and, in particular, arginine are particularly preferred.

The amino acids can preferably be added to the moldings according to the invention in free form be admitted. However, in a number of cases it is also possible to use the amino acids to be used in salt form. Preferred salts are then the compounds with Hydrohalic acids, especially the hydrochlorides and the hydrobromides.

Furthermore, the amino acids can also be in the form of oligopeptides and protein hydrolysates are used if it is ensured that the required amounts of Amino acids used according to the invention are contained therein. In this context Menhang is referred to the disclosure of DE-OS 22 15 303, to which expressly Is referred to.

A very particularly preferred alkalizing agent is arginine, especially in free form Form, but also used as a hydrochloride, as it has both its alkaline properties the penetration capacity of the dyes is also significantly increased.

The alkalizing agent is preferably present in the moldings according to the invention in amounts from 0.5 to 20% by weight, in particular from 5 to 15% by weight, based on the total Means included.

Dye precursors

In addition to the substantive dyes, the moldings according to the invention can also be used as dye precursors

• - Oxidation dye precursors of the developer and coupler type, and
• - precursors of nature-analogous dyes, such as indole and indoline derivatives,

as well as mixtures of representatives of these groups.

Primary aromatic amines with a further, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4- Aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives are used.

According to the invention, it may be preferred to use a p-phenylenediamine derivative or one of its physiologically compatible salts as the developer component. Particularly preferred are p-phenylenediamine derivatives of the formula (E1)

whereby

• - G ¹ stands for 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 stands for 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 which is substituted with a nitrogen-containing group;
• - G ³ stands for 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 ₁ to C ₄ -Hydroxyalkoxyradikal, a C ₁ - to C ₄ -Acetylaminoalkoxyradikal, a C ₁ - to C ₄ - Mesylaminoalkoxyradikal or a C ₁ - to C ₄ -Carbamoylaminoalkoxyradikal;
• - G ⁴ stands for a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• - If G ³ and G ^{4 are} in the ortho position to one another, 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, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group can be mentioned as preferred examples of a C ₁ - to C _{4 -hydroxyalkyl group.} A 2-hydroxyethyl group is particularly preferred. According to the invention, examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of the formula (II) 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-tolylenediamine, 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-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-tolylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine and N, N-bis (β-hydroxyethyl) -p-phenylenediamine.

According to the invention, it can furthermore be preferred as a developer component Use compounds that contain at least two aromatic nuclei with Amino and / or hydroxyl groups are substituted.

Among the binuclear developer components that can be used in the dyeing compositions according to the invention, one can in particular mention the compounds which correspond to the following formula (E2), as well as their physiologically tolerable salts:

whereby:

• - 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 stands for an alkylene group with 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms can be and may 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 - bis 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 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 bridge Y per molecule and
• - The compounds of the formula (E2) contain at least one amino group which carries at least one hydrogen atom.

According to the invention, the substituents used in formula (E2) are analogous to the above Executions defined.

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

Very particularly preferred binuclear developer components of the formula (E2) are N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2- hydroxy-5-aminophenyl) methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane and 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane or one of its physiological compatible salts.

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as the developer component. Particularly preferred are p-aminophenol derivatives of the formula (E3)

whereby:

• - G ¹³ stands for a hydrogen atom, a halogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl 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 -Hydroxyalkoxyradikal, 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 stands for 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.

According to the invention, the substituents used in formula (E3) are analogous to the above Executions defined.

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- (2- 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-fluorophenol, 4-amino-2-chlorophenol, 2,6-dichloro-4-aminophenol, 4-amino-2 - ((diethylamino) methyl) phenol as well as theirs physiologically compatible salts.

Particularly preferred compounds of the formula (E3) are p-aminophenol, 4- Amino-3-methylphenol, 4-amino-2-aminomethylphenol and 4-amino-2- ((diethylamino) methyl) phenol.

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

Furthermore, the developer component can be selected from heterocyclic ones 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-aminopyridine, 2,3-diamino-6-methoxypyridine, 2- (β- Methoxyethyl) amino-3-amino-6-methoxypyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are in particular the compounds in German Patent DE 23 59 399, the Japanese laid-open specification JP 02019576 A2 or in the Offenlegungsschrift WO 96/15765 are described, 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-diatinopyrimidine and 2,5,6- Triaminopyrimidine.

Preferred pyrazole derivatives are in particular the compounds described in patents DB 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, EP 740931 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- (2'- aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4 (β- hydroxyethyl) amino-1-methylpyrazole.

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

whereby:

• - 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 be protected by an acetyl ureide or sulfonyl radical can, 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, the dialkyl radicals optionally forming 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 ₁ to C ₄ alkyl radical, an aryl radical, a C ₁ to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ - to C ₄ aminoalkyl radical, a (C ₁ - to C ₄ ) alkylamino (C ₁ - to C ₄ ) alkyl radical, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, the dialkyl radicals optionally forming 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 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,

with the proviso 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 positions (2, 3); (5, 6); (6, 7); (3, 5) or (3.7);
• - if p + q is equal to 1, n has the value 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy positions (2, 3); (5, 6); (6, 7); (3, 5) or (3, 7);

According to the invention, the substituents used in formula (E4) are analogous to the above Executions defined.

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

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-dimethylpyrazole- [1,5-a] -pyrimidine-3,7-diamine;
• Pyrazole [1,5-a] pyrimidine-3,5-diamine;
• - 2,7-dimethylpyrazole- [1,5-a] -pyrimidine-3,5-diamine;
• - 3-amino pyrazol- [1,5-a] -pyrimidin-7-ol;
• - 3-amino pyrazol- [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-dimethylpyrazole- [1,5-a] -pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazole- [1,5-a] -pyrimidine-3,7-diamamine;
• - 2,5, N7, N7-tetramethylpyrazole- [1,5-a] -pyrimidine-3,7-diamine;

as well as their physiologically acceptable salts and their tautomeric forms, if a tautomeric equilibrium is present.

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

As a rule, m-phenylenediamine derivatives, naphthols, Re sorcin and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are used. as Coupler substances are particularly suitable 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resor cinmonomethylether, m-phenylenediamine, 1-phenyl-3-methyl-pyrazolone-5, 2,4-dichloro-3- aminophenol, 1,3-bis- (2,4-diaminophenoxy) -propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3-hydroxypyridine, 2-methylresorcinol, 5- Methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Coupler components preferred according to the invention are:

• - m-aminophenol and its derivatives such as 5-amino-2-methylphenol, 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-amino benzomorpholine,
• - Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• - Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• - Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7- Hydroxyindole,
• - Pyrimidine derivatives, such as 4,6-diaminopyrimidine, 4-amino-2,6- dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2- Amino-4-methylpyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine and 4,6- Dihydroxy-2-methylpyrimidine, or
• - methylenedioxybenzene derivatives such as 1-hydroxy-3,4- methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) - amino-3,4-methylenedioxybenzene.

Particularly preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7- Dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3- hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

It is not necessary that the oxidation dye precursors or the substantive Dyes each represent uniform compounds. Rather, in the inven appropriate hair dyes, due to the manufacturing process for the individual Dyes, other components may be contained in subordinate quantities, as long as these do not adversely affect the dyeing result or for other reasons, e.g. B. toxicological, must be excluded.

With regard to those which can be used in the hair coloring and tinting compositions according to the invention Dyes is also expressly referred to the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive dyes) and Chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the series "Dermato logy "(Ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of Cosmetic Raw Materials" published by European Community, available in diskette form from the Bundesverband Deutscher Industrial and trading company for pharmaceuticals, health foods and personal care products tel e. V., Mannheim, referred to.

The oxidation dye precursors are preferably used in the agents according to the invention Quantities of 0.01 to 20 wt .-%, preferably 0.5 to 5 wt .-%, each based on the total funds included.

Such indoles and indolines are preferred as precursors of nature-analogous dyes set, the at least one hydroxy or amino group, preferably as a substituent on Six-membered ring. These groups can carry further substituents, e.g. B. in shape an etherification or esterification of the hydroxyl group or an alkylation of the amino group.

Derivatives of 5,6-dihydroxyindoline of the formula (Ia) are particularly suitable as precursors of hair dyes analogous to nature.

in the independent
R ¹ stands for hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
R ³ stands for hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ stands for hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ in which
R ⁶ stands for a C ₁ -C ₄ alkyl group, and
R ⁵ stands for one of the groups mentioned ^{under R 4,}
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-hydroxy indoline, 6-aminoindoline and 4-aminoindoline.

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

Derivatives of 5,6-dihydroxyindole of the formula (Ib) are also excellently suitable as precursors of natural hair dyes,

in the independent
R ¹ stands for hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxyalkyl group
R ² stands for hydrogen or a -COOH group, where the -COOH group can also be present as a salt with a physiologically compatible cation,
R ³ stands for hydrogen or a C ₁ -C ₄ -alkyl group,
R ⁴ stands for hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ in which
R ⁶ stands for a C ₁ -C ₄ alkyl group, and
R ⁵ stands for one of the groups mentioned ^{under R 4,}
and 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-dihy droxyindole, 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.

To be 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 esp special the 5,6-dihydroxyindole.

The indoline and indole derivatives can be used in the context of the Ver according to the invention The coloring agents used in the past both as free bases and in the form of their physiolo gically compatible salts with inorganic or organic acids, e.g. B. the Hydrochlo ride, the sulfates and hydrobromides, can be used. The indole or indoline derivatives are in these usually in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-% contain.

Especially when using dye precursors of the indoline or indole type it has proven to be advantageous to use an amino acid and / or an alkalizing agent Use oligopeptide.

Furthermore, the preparations according to the invention can also occur naturally Dyes such as red henna, neutral henna, black henna, chamomile blossom, Sandalwood, black tea, buckthorn bark, sage, blue wood, madder root, catechu, Contains sedre and alkanna root.

Oxidizing agent

The shaped bodies according to the invention can furthermore contain an oxidizing agent. On the one hand, the oxidizing agent can serve to lighten the fibers to be treated. Such "discolored" fibers can then in the same operation with the synthetic substantive dyes are colored, so that a wider range of nuances becomes accessible. The addition of an oxidizing agent can also be used on the other hand Develop the actual dye from the dye precursors.

Although the choice of oxidizing agent is in principle not subject to any restrictions According to the invention, it may be preferred to use adducts of as oxidizing agent Use hydrogen peroxide, especially urea, melamine or sodium borate. The use of percarbamide is particularly preferred.

It is also possible to carry out the oxidation with the aid of enzymes, the Enzymes are used both for the production of oxidizing per-compounds as also to enhance the effect of a small amount of oxidizing agents present.

So the enzymes (enzyme class 1: oxidoreductases) electrons from suitable Transfer developer components (reducing agents) to atmospheric oxygen. Are preferred thereby oxidases such as tyrosinase and laccase but also glucose oxidase, uricase or Pyruvate oxidase. Furthermore, the procedure should be mentioned, the effect of small amounts (e.g. 1% and less, based on the total mean) hydrogen peroxide through peroxidases to reinforce.

The development of the color can also be supported and increased by adding certain metal ions to the shaped body. Such metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . ^{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. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the development of the color can be accelerated and the color shade can be influenced in a targeted manner. However, it has also proven to be practicable to use the metal ions in the form of their complexes or also attached to zeolites to increase the coloring power.

Dissolution accelerator

In a preferred embodiment, the shaped body according to the invention contains present invention a dissolution accelerator. The term Dissolution accelerator includes gas-evolving components, preformed and enclosed gases, explosives and their mixtures.

In one embodiment of the present invention, gas-evolving components are used as the dissolution accelerator. When they come into contact with water, these components react with one another to form gases in-situ, which generate a pressure in the tablet which causes the tablet to disintegrate into smaller particles. An example of such a system are special combinations of suitable acids with bases. Mono-, di- or trivalent acids with a pK _a of 1.0 to 6.9 are preferred. Preferred acids are citric acid, malic acid, maleic acid, malonic acid, itaconic acid, tartaric acid, oxalic acid, glutaric acid, glutamic acid, lactic acid, fumaric acid, glycolic acid and mixtures thereof. Citric acid is particularly preferred. It can be very particularly preferred to use the citric acid in particle form, the particles having a diameter of less than 1000 μm, in particular less than 700 μm, very particularly preferably less than 400 μm. Further alternative suitable acids are the homopolymers or copolymers of acrylic acid, maleic acid, methacrylic acid or itaconic acid with a molecular weight of 2000 to 200,000. Homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid are particularly preferred. According to the invention, preferred bases are alkali metal silicates, carbonates, hydrogen carbonates and mixtures thereof. Metasilicates, hydrogen carbonates and carbonates are particularly preferred, and hydrogen carbonates are very particularly preferred. Particulate hydrogen carbonates with a particle diameter of less than 1000 μm, in particular less than 700 μm, very particularly preferably less than 400 μm, are particularly preferred. Sodium or potassium salts of the bases mentioned above are particularly preferred. These gas-evolving components are contained in the colored tablets according to the invention preferably in an amount of at least 10% by weight, in particular at least 20% by weight.

In a further embodiment of the present invention, the gas is preformed or enclosed, so that when the shaped body begins to dissolve, the development of gas begins and accelerates further dissolution. Examples of suitable gases are air, carbon dioxide, N ₂ O, oxygen and / or other non-toxic, non-flammable gases.

In a third, particularly preferred embodiment of the present invention are used as dissolution accelerators, so-called disintegration aids Shaped body disintegrant incorporated into the shaped body to reduce the disintegration times shorten. Shaped body disintegrants or disintegration accelerators are in accordance with Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceuticals Technologie "(6th edition, 1987, pp. 182-184) understood auxiliaries that are necessary for the rapid Disintegration of shaped bodies in water or gastric juice and for the release of the pharmaceuticals in absorbable form.

These substances, which are also known as "explosives" due to their effect, increase in volume (swelling) when water gets in. Source end 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.

Cellulose-based disintegrants are used as preferred disintegrants in the context of the present invention, so that preferred moldings contain such a cellulose-based disintegration agent in amounts of 0.5 to 50% by weight, preferably 3 to 30% by weight, based on the total molding contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, represents a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5000 glucose units and consequently have average molar masses of 50,000 to 500,000. Cellulose derivatives that can be obtained from cellulose by polymer-analogous reactions can also be used as cellulose-based disintegrants in the context of the present invention. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups that are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used as the only cellulose-based disintegration agent, but are used in a mixture with cellulose. The cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose, which is free from cellulose derivatives, is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as a disintegration aid is preferably not in finely divided form used, but before adding to the to be pressed Premixes converted into a coarser form, for example granulated or compacted. The particle sizes of such disintegrants are mostly above 200 µm, preferably at least 90% by weight between 300 and 1600 μm and in particular too at least 90% by weight between 400 and 1200 µm. The invention Disintegration aids are, for example, commercially available under the name Arbocel® available from Rettenmaier. A preferred disintegration aid is for example Arbocel® TF-30-HG.

As another cellulose-based disintegrant or as a component of this Component can be used microcrystalline cellulose. This microcrystalline Cellulose is made by partial hydrolysis of celluloses under such conditions obtained that only the amorphous areas (approx. 30% of the total cellulose mass) of the Celluloses attack and completely dissolve, but the crystalline areas (approx. 70%) leave undamaged. A subsequent disaggregation of the hydrolysis resulting microfine celluloses provides the microcrystalline celluloses, which Have primary particle sizes of about 5 microns and, for example, to granules with a mean particle size of 200 microns are compactable. Suitable microcrystalline Cellulose is commercially available, for example, under the trade name Avicel®.

According to the invention, the accelerated dissolution of the shaped bodies can also be achieved by Pre-granulation of the other constituents of the shaped body can be achieved.

Other components

In addition to the ingredients mentioned, the moldings according to the invention can also be used contain all active ingredients, additives and auxiliaries known for such preparations. In many Cases contain the moldings at least one surfactant, in principle both anionic cal as well as zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven to be advantageous to use the surfactants choose anionic, zwitterionic or nonionic surfactants.

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

• - linear fatty acids with 10 to 22 carbon 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 with 10 to 22 carbon atoms and x = 0 or 1 to 16,
• - acyl sarcosides with 10 to 18 carbon atoms in the acyl group,
• - acyl taurides with 10 to 18 carbon atoms in the acyl group,
• - acyl isethionates with 10 to 18 carbon atoms in the acyl group,
• - Sulphosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates with 12 to 18 carbon atoms,
• - linear alpha-olefin sulfonates with 12 to 18 carbon atoms,
• - Alpha-sulfofatty acid methyl esters of fatty acids with 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 with 10 to 18 carbon 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,
• - Sulphonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds applications according to DE-A-39 26 344,
• - Esters of tartaric acid and citric acid with alcohols, the addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide on fatty alcohols with 8 to 22 Represent carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 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 especially unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Nonionic surfactants contain z. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections 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 with 8 to 22 carbon atoms, with fatty acids with 12 to 22 carbon atoms and with alkylphenols with 8 to 15 carbon atoms in the alkyl group , C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• - C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs as well
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened Ri interest oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These compounds are available, for example, under the trade name Plantacare® from Henkel and are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be both linear and branched ver. Primary linear aliphatic radicals which are methyl-branched in the 2-position are preferred. Such alkyl radicals are, for example, 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 which can be used according to the invention can, for example, contain ^{only one specific alkyl radical R 1.} Usually these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R present are mixtures corresponding to the starting compounds or corresponding to the respective work-up of these compounds.

Alkyl polyglycosides in which R ¹

• - Essentially from C ₈ - and C ₁₀ -alkyl groups,
• - Essentially from C ₁₂ and C ₁₄ alkyl groups,
• - Essentially from C ₅ - to C ₁₆ -alkyl groups or
• - consists essentially of C ₁₂ - to C ₁₆ -alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Usually sugars with 5 or 6 carbon atoms and the corresponding ones are used Oligosaccharides are used. Such sugars are, for example, glucose, fructose, and galac tose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar components are glucose, fructose, galactose and arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 Sugar units. Alkyl polyglycosides with x values of 1.1 to 1.6 are preferred. Quite Particularly preferred are alkyl glycosides in which × is 1.1 to 1.4.

In addition to their surfactant effect, the alkyl glycosides can also serve to fix to improve fragrance components on the hair. The specialist will be there for the case that an effect of the perfume oil that goes beyond the duration of the hair treatment the hair is desired, preferably to this class of substances as a further ingredient resort to the preparations according to the invention. A special one according to the invention the preferred alkyl glucoside is the commercial product Plantacare® 1200 G.

The alkoxylated homologues of said alkyl polyglycosides can fiction are used accordingly. These homologues can contain an average of up to 10 ethylene contain oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds which have 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 the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyl dimethylammonium glycinate, N-acyl aminopropyl-N, N-dimethylammonium glycinate, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each with 8 to 18 C atoms in the alkyl or acyl group and cocoacylamino ethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are also particularly suitable as co-surfactants. Am pholytic 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 and are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodi propionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C _{12- 18} acyl sarcosine.

According to the invention, as cationic surfactants, in particular those of the quar tary ammonium compounds, esterquats and amidoamines are used.

Preferred quaternary ammonium compounds are ammonium halides, in particular other chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylam monium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methylammonium chloride, as well as those under the NCI names Quaternium-27 and Quatemium-83 known imidazolium compounds. The long alkyl chains of the above The surfactants mentioned preferably have 10 to 18 carbon atoms.

Esterquats are known substances that have at least one ester function tion as well as 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 esters salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products will be for example under the trademarks Stepantex®, Dehyquart® and Armocare expelled. The products Armocare © VGH-70, an N, N-Bis (2-Palmitoyloxy ethyl) dimethylammonium chloride, as well as Dehyquart® F-75 and Dehyquart® AU-35 Examples of such esterquats.

The alkylamidoamines are usually natural or synthetic by amidation table fatty acids and fatty acid cuts with dialkylaminoamines. An inventor According to this, a particularly suitable compound from this group of substances is assumed under the name Tegoamid® S 18 commercially available stearamidopropyl-dimethylamine represent.

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

Also suitable according to the invention are cationic silicone oils such as, for example, those im Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trim thylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-mo differentiated silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (Manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium-80).

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

The compounds with alkyl groups used as surfactants can each be act uniform substances. However, it is usually preferred in manufacturing of these substances from native vegetable or animal raw materials, so that one Mixtures of substances with different, depending on the respective raw material Maintains alkyl chain lengths.

In the case of surfactants, the addition products of ethylene and / or propylene oxide to fat Alcohols or derivatives of these addition products can represent both products with a "normal" homolog distribution as well as those with a narrowed homolo gene distribution can be used. Under "normal" homolog distribution, Understood mixtures of homologues that one in the implementation of fatty alcohol and Alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates obtained as catalysts. Narrowed homolog distributions are on the other hand, if, for example, hydrotalcites, alkaline earth metal salts of Ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates as catalysts be used. The use of products with a narrow homolog distribution may be preferred.

Furthermore, the moldings according to the invention can preferably also have one conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic ones Oils formed contain. With regard to the cationic surfactants, refer to the referenced above.

Cationic polymers can be preferred as conditioning active ingredients. These are in usually polymers containing a quaternary nitrogen atom, for example in the form of an Am monium group.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as they are under the names Celquat® and Po lymer JR® are commercially available. 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 as well as esters and amides of acrylic acid and methacrylic acid. The one among the Designations Merquat®100 (poly (dimethyldiallylammonium chloride)), Mer quat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) and Merquat® 280 (Dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products are examples of such cationic polymers.
• - Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminomethacrylate copolymers. Such connections are under the names Gafquat®734 and Gafquat®755 are commercially available.
• - Vinylpyrrolidone methoimidazolinium chloride copolymers, as they are under the designation Luviquat® can be offered.
• - quaternized polyvinyl alcohol

as well as those under the designations

• - Polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the Po lymer main chain.

Cationic polymers of the first four groups mentioned are particularly preferred, whole Polyquaternium-2, Polyquaternium-10 and Polyquaternium-22 are particularly preferred.

Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes such as dimethylpolysiloxane and methylphenylpolysi loxane, as well as their alkoxylated and quaternized analogs. Examples of such silicones are those from Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 as well as the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also known as amodimethicone be is distinguished), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary Polydimethylsiloxane, Quaternium-80).

Synthetic paraffin oils can also be used as conditioning agents manufactured 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 wise soy lecithin, egg lecithin and cephalins.

Furthermore, the preparations used according to the invention preferably contain min at least one oil component.

Oil components suitable according to the invention are in principle all water-insoluble oils and fatty substances and their mixtures with solid paraffins and waxes. as According to the invention, those substances are defined as insoluble in water, the solubility of which is in Water at 20 ° C is less than 0.1 wt .-%.

A preferred group of oil components are vegetable oils. Examples of such Oils are sunflower oil, olive oil, soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, Wheat germ oil, peach kernel oil and the liquid parts of coconut oil.

However, other triglyceride oils such as the liquid components of beef tallow are also suitable as well as synthetic triglyceride oils.

Another, particularly preferred group is used according to the invention as an oil component More accessible compounds are liquid paraffin oils and synthetic hydrocarbons as well Di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms Atoms, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n- undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n- undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether and di-tert-buty lether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso-pentyl-n- octyl ether and 2-methyl-pentyl-n-octyl ether. The Verbin available as commercial products 1,3-Di- (2-ethylhexyl) -cyclohexane (Cetiol® S) and di-n-octyl ether (Cetiol® OE) can be preferred.

Oil components which can also be used according to the invention are fatty acid and fatty alcohol esters. The monoesters of fatty acids with alcohols having 3 to 24 carbon atoms are preferred. This group of substances is the products of the esterification of fatty acids with 6 to 24 carbon atoms such as 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 and their technical mixtures, the z. B. in the pressure splitting of natural fats and oils, in the oxidation of aldehydes from Roelen's oxo synthesis or the dimerization of unsaturated fatty acids, with alcohols such as isopropyl alcohol, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, Myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, Li nolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, as well as their technical mixtures, eriducyl alcohol and brass. B. arise in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. According to the invention, isopropyl myristate, isononanoic acid C _16-18 alkyl ester (Cetiol® SN), stearic acid 2-ethylhexyl ester (Cetiol® 868), cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprinate / caprylate and n-butyl stearate are particularly preferred.

Furthermore, dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, Di- (2-ethylhexyl) succinate and di-isotridecyl celaate and diol esters such as ethylene glycol dioleate, ethylene glycol di-isotridecanoate, propylene glycol di (2-ethylhexanoate), propy lenglycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate and Neopentyl glycol di-caprylate which can be used according to the invention is also oil components complex esters such as B. the diacetyl glycerol monostearate.

Finally, fatty alcohols with 8 to 22 carbon atoms can also be used according to the invention kend oil components are used. The fatty alcohols can be saturated or unsaturated saturated and linear or branched. Usable in the context of the invention are, for example wise decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, Decadienol, oleyl alcohol, eruca alcohol, ricinol 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, this list being an example and not of a limiting nature should have. The fatty alcohols, however, come from preferably natural fatty acids, usually being obtained from the esters of the fatty acids by reduction can be assumed. Such fatty alcohols can also be used according to the invention cuts made 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 from their transesterification products formed with corresponding alcohols fatty acid esters are generated, and thus represent a mixture of different fatty alcohols.

The oil components are preferably in Menden from 0.05 to 10 wt .-%, in particular from 0.1 to 2% by weight are used in the moldings according to the invention.

In a preferred embodiment of the present invention, is formed Dissolution of the shaped body in water to form a gel. For this purpose, the molded body Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, Karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, z. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions ons and derivatives such as amylose, amylopectin and dextrins, clays such as. B. Bentonite, Silicates, such as those used under the trade names Optigel® (Süd-Chemie) or Laponite® (Solvay) are sold, or fully synthetic hydrocolloids such. B. Polyvinyl alcohol added. Particularly preferred thickeners are xanthans, Alginates and highly substituted carboxymethyl celluloses.

Further active ingredients, auxiliaries and additives are, for example

• - zwitterionic and amphoteric polymers such as acrylamidopropyl-tri methylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacryl lat / tert-butylaminoethyl methacrylate / 2-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 acid anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide Terpolymers,
• - structurants such as maleic acid and lactic acid,
• - Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids as well as quaternized protein hydrolysates,
• - perfume oils, dimethyl isosorbide and cyclodextrins,
• - Solvents and mediators such as ethylene glycol, propylene glycol, glycerin and Diethylene glycol,
• - Active ingredients that improve fiber structure, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fruit sugar and lactose,
• - Quaternized amines such as methyl 1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• - defoamers such as silicones,
• - dyes for coloring the product,
• - Anti-dandruff ingredients such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and Triazines,
• - Substances for adjusting the pH, such as common acids, esp special food acids and bases,
• - Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol,
• - Vitamins, provitamins and vitamin precursors, especially those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as the extracts from green tea, oak bark, nettle, Witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden blossoms, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, Coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, Sage, Rosmann, birch, mallow, cuckoo herb, quendel, yarrow, thyme, Lemon balm, grouse, coltsfoot, marshmallow, meristem, ginseng and ginger root,
• - cholesterol,
• - Consistency factors such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as whale rat, beeswax, montan wax and paraffins,
• - fatty acid alkanolamides,
• - complexing agents such as EDTA, NTA, β-alanine diacetic acid and phosphonic acids,
• - Swelling and penetration substances such as glycerine, propylene glycol monoethyl ether, carbo nates, hydrogen carbonates, guanidines, ureas as well as primary, secondary and tertiary Phosphates,
• - Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• - Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate,
• - pigments,
• - stabilizing agent for the oxidizing agent,
• - antioxidants.

With regard to further optional components as well as the amounts of this com components, reference is expressly made to the relevant manuals known to the person skilled in the art, z. B. Kh.Schrader, basics and recipes of cosmetics, 2nd edition, Hüthig book Verlag, Heidelberg, 1989, referenced.

It can also be preferred according to the invention to incorporate individual active ingredients before they are incorporated encapsulate separately in the molded body; so it is, for example, conceivable, especially to use reactive components or even the fragrances in encapsulated form.

Shaped body geometries

The shaped bodies according to the invention can assume any geometric shape, such as e.g. concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, seven- and octagonal-prismatic and rhombohedral shapes. Also completely irregular Basic areas such as arrow or animal shapes, trees, clouds, etc. can be realized. The training as a board, the rod or bar shape, cube, cuboid and the corresponding Room elements with flat side surfaces and, in particular, cylindrical ones Configurations with a circular or oval cross-section are in accordance with the invention preferred. This cylindrical configuration covers the form of presentation of the Tablet up to compact cylinder pieces with a ratio of height to Diameter greater than 1. If the base molding has corners and edges, then these are preferably rounded. As an additional visual differentiation is one Embodiment with rounded corners and beveled ("chamfered") edges preferred.

In a first preferred embodiment, the portioned compacts can thereby each be designed as separate individual elements that correspond to the predetermined Dosage corresponds to the dye and / or the oxidizing agent. But it is the same possible to form compacts that have a plurality of such mass units in one Connect compact, in particular by predetermined breaking points the light Separability of portioned smaller units is provided. The training of the portioned pellets as tablets in cylinder or cuboid shape can be useful, a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 being preferred is. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.

The preferred three-dimensional shape of the molded bodies according to the invention is rectangular Base on, the height of the shaped body is smaller than the smaller side of the rectangle the base area. Rounded corners are preferred for this type of offer.

Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which thin the short ones Represent segments, broken off and can be used in such portions. This principle of the "bar-shaped" shaped body can also be used in other geometrical forms Shapes, for example perpendicular triangles, only on one of their sides are connected alongside one another.

In a second preferred embodiment, the various components not compressed into a uniform tablet, but rather during tableting Shaped bodies are obtained which have a plurality of layers, that is to say at least two layers. It is also possible that these different layers are different Have release speeds. Advantageous application technology can be derived from this Properties of the molded body result. For example, if components are in the Moldings are contained that mutually negatively influence each other, so it is possible to integrate one component in the more rapidly soluble layer and the other Incorporate component into a more slowly soluble layer, so that the components do not react to one another during the dissolving process.

According to the invention, it is particularly preferred if the shaped bodies consist of at least three Layers exist, with a first layer (A) the dye preparation and the Contains alkalizing agent, a second layer (B) is an inert separating layer and a third layer (A) contains the oxidizing agent preparation.

The layered structure of the molded bodies can be in the form of a stack, with a The process of dissolving the inner layer (s) at the edges of the molding is then already done occurs when the outer layers are not yet completely dissolved. A preferred one Stacking order is (A), (B), (C). In the stacked arrangement, the stack axis be arranged arbitrarily to the tablet axis. The stacking axis can for example be a cylindrical tablet parallel or perpendicular to the height of the cylinder.

However, according to a further embodiment, it can also be preferred if a complete covering of the inner layer (s) by the outer layer (s) Layer (s) is reached, preventing the early resolution of Components of the inner layer (s) leads. Shaped bodies in which the Layer (A) completely from layer (B) and this in turn completely from the Layer (C) is wrapped. Shaped bodies in which the layer (C) completely from layer (B) and this in turn completely from layer (A) is wrapped.

Similar effects can also be achieved by coating individual components the composition to be compressed or the entire molding. For this can, for example, the body to be coated with aqueous solutions or Emulsions are sprayed, or via the process of hot-melt coating one Received coating.

After pressing, the moldings have a high level of stability. The breaking strength of cylindrical shaped bodies can be determined from the measurable variable of the diametrical breaking stress. This can be determined according to

Here, σ stands for the diametral fracture stress (DFS) in Pa, P is the force in N that leads to the pressure exerted on the molded body that causes the Cause breakage of the molding, I) is the molding diameter in meters and t is the Height of the moldings.

The moldings of the present invention preferably have a density of 0.3 g / cm ³ to 2.0 g / cm ³ , in particular 0.5 g / cm ³ to 1.1 g / cm ³ .

In a third preferred embodiment, there are those according to the invention Molded body made of one, described by the term "basic molded body", by itself known tabletting processes produced molded body, which has a trough. The basic molding is preferably produced first and the other is pressed Part in a further work step on or in this base molding on or brought in. The resulting product is hereinafter referred to as the generic term "Troughed shaped body" or "Troughed tablet" referred to.

According to the invention, the basic shaped body can in principle have all realizable three-dimensional shapes accept. The three-dimensional shapes already mentioned above are particularly preferred. Form the trough can be freely selected, with molded bodies being preferred according to the invention, in which at least one trough has a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, seven- and octagonal-prismatic as well as rhombohedral shape. Also completely irregular hollow shapes such as arrow or animal shapes, trees, clouds, etc. can will be realized. As with the basic moldings, depressions are rounded Corners and edges or with rounded corners and chamfered edges are preferred.

The size of the depression in comparison to the entire molding depends on the desired use of the molded body. Depending on whether pressed in the second Part of the should contain a lesser or greater amount of active ingredient, the The size of the hollow may vary. Shaped bodies are independent of the intended use preferred, in which the weight ratio of base tablet to cavity filling in Range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly preferably from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1.

Similar statements can be made about the surface proportions that the Basic shaped body or the cavity filling on the entire surface of the shaped body turn off. Shaped bodies are preferred here in which the surface of the pressed-in Well filling 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular makes up 4 to 10% of the total surface of the filled basic tablet.

For example, if the overall molding has dimensions of 20 × 20 × 40 mm and thus a total surface area of 40 cm ² , cavity fillings are preferred which have a surface area of 0.4 to 10 cm ² , preferably 0.8 to 8 cm ² , particularly preferably of 1.2 to 6 cm ² and in particular from 1.6 to 4 cm ² .

The cavity filling and the base molding are preferably visually distinguishable colored. In addition to the optical differentiation, there are hollow tablets Application advantages on the one hand due to the different solubilities of the different areas on the other hand, but also through the separate storage of the Active ingredients in the various molded body areas.

Moldings in which the pressed-in cavity filling dissolves more slowly than the Basic tablets are preferred according to the invention. By incorporating certain Constituents, on the one hand the solubility of the cavity filling can be varied in a targeted manner, on the other hand, the release of certain ingredients from the cavity filling can increase Lead advantages in the dyeing process. Ingredients that are preferably at least partially in the Well filling are localized, are for example those described below conditioning agents, oil bodies, vitamins and plant agents.

Tableting

The moldings according to the invention are first produced by the dry process Mixing the ingredients, which can be fully or partially pre-granulated, and on Closing information, in particular compression into tablets, based on known Procedure can be used. For the production of the invention The pre-mix is molded into a so-called die between two punches condensed into a solid compressed file. This process, which is briefly referred to below as Tableting is divided into four sections: dosing, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting shaped body due to the position of the lower one Stamp and the shape of the pressing tool can be determined. The constant Dosing, even with high throughputs of molded bodies, is preferably via a volumetric dosing of the premix reached. In the further course of the tableting the upper punch touches the premix and lowers further in the direction of the Lower stamp. During this compression, the particles of the premix get closer pressed together, the void volume within the filling between the Stamping decreases continuously. From a certain position of the upper punch (and so from a certain pressure on the premix) the plastic begins Deformation in which the particles flow together and form the shaped body comes. Depending on the physical properties of the premix, there will also be a part the premix particle crushes and one occurs at even higher pressures Sintering of the premix. With increasing pressing speed, so high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting moldings can have more or less large cavities. In the last step of the tableting, the finished molding is pushed through the lower punch pushed out of the die and through subsequent transport devices transported away. At this point, only the weight of the molded article is final specified, since the pressed parts due to physical processes (back expansion, crystallographic effects, cooling, etc.) can still change their shape and size.

The tableting takes place in commercially available tablet presses, which are principally equipped with single or double stamps can be equipped. In the latter case, not only the Upper punch used to build up pressure, the lower punch also moves during of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities, in which the stamp or stamps are attached to an eccentric disk, which in turn is attached to an axis is mounted with a certain rotational speed. The movement this ram is comparable to the operation of a conventional four-stroke engine. The pressing can be done with an upper and a lower punch, but it can also several stamps can be attached to an eccentric disc, the number of Die bores is expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are chosen, with those on one so-called die table a larger number of dies is arranged in a circle. The number of dies varies between 6 and 55, depending on the model, although larger ones are also possible Matrices are commercially available. Each die on the die table is a top and Assigned to the lower punch, with the pressing pressure being active only through the upper or lower punch. Lower stamp, but can also be built up by both stamps. The matrix table and the punches move about a common perpendicular axis, the Stamp with the help of rail-like cam tracks during the rotation in the positions for filling, compression, plastic deformation and ejection. To the Places where a particularly serious raising or lowering of the stamp is required (filling, compressing, ejecting), these cam paths are through additional low-pressure pieces, pull-down rails and lifting tracks are supported. the The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressure on the premix is via the press paths for the upper and lower punches individually adjustable, the pressure build-up by rolling past the Stamp shaft heads happen on adjustable pressure rollers.

Rotary presses can also be equipped with two filling shoes to increase throughput are provided, with only a semicircle going through for the production of a tablet must become. For the production of two-layer and multi-layer moldings, several Filling shoes arranged one behind the other without the lightly pressed first layer in front of the further filling is ejected. By appropriate process management are on this Way also coat and point tablets can be produced, which have an onion skin-like Have structure, in the case of the point tablets the top of the core or the Core layers is not covered and thus remains visible. Even Rotary tablet presses can be equipped with single or multiple tools so that for example, an outer circle with 50 and an inner circle with 35 holes can be used for pressing at the same time. The throughputs more modern Rotary tablet presses produce over a million moldings per hour.

In the case of tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible fluctuations in the weight of the tablet. In this way, the fluctuations in the hardness of the tablet can also be reduced. Slight weight fluctuations can be achieved in the following ways:

• - Use of plastic inserts with low thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Adjustment of the filling shoe wing speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of the filling shoe and powder feed

In order to reduce the caking of the stamps, everything from technology can be used well-known non-stick coatings. Plastic coatings are particularly advantageous, Plastic inserts or plastic stamps. Rotating punches have also proven to be proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible should be. In the case of rotating stamps, a plastic insert can usually be used be waived. Here the stamp surfaces should be electropolished.

It was also found that long pressing times are advantageous. These can be with Pressure rails, several pressure rollers or low rotor speeds can be set. Since the fluctuations in the hardness of the tablet due to the fluctuations in the pressing forces are caused, systems should be used that limit the pressing force. here elastic stamps, pneumatic compensators or resilient elements can be used in the Kraftweg are used. The pressure roller can also be designed to be resilient.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Fann Instruments Company, Houston, Texas (USA), Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers are, for example, Dr. Herbert Pete, Vienna (AT), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). Particularly suitable is for example the hydraulic double pressure press HPF 630 from LAEIS, D. Tableting tools are, for example, from the companies Adams tableting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Toolmaking, Tamm available. Other providers are z. B. Senss AG, Reinach (CH) and the Medicopharm, Kamnik (SI).

The process for producing the molded body is not limited to that only a particulate premix is compressed to form a shaped body. Much more the method can also be extended to the effect that one can in a manner known per se producing multilayer moldings by preparing two or more premixes, which are pressed together. Here, the premix poured in first becomes light Pre-pressed to have a smooth top side that runs parallel to the bottom of the molded body get, and after filling the second premix to the finished molded body end-pressed. In the case of three-layer or multi-layer moldings, after each premix Add another pre-compression before, after adding the last premix, the Molded body is end-pressed.

The compression of the particulate composition into the trough can be analogous to Production of the basic moldings take place on tablet presses. One is preferred Procedure in which the base moldings are first produced, then felt and then be pressed again. This can be done by ejecting the base molding a first tablet press, filling and transport into a second tablet press happen in which the final compression takes place. Alternatively, the final compression can also be used by pressure rollers that roll over the moldings on a conveyor belt, take place. But it is also possible to use a rotary tablet press with different To provide stamp sets, so that a first stamp set depressions in the molded body presses in and the second set of dies after filling by repressing for a plane Shaped body surface ensures.

packaging

The moldings produced according to the invention can be 11445 00070 552 001000280000000200012000285911133400040 0002010059290 00004 11326 - as described above - completely or partially provided with a coating. Procedures in which a Post-treatment in applying a coating layer to the molded body surface (s), in which / where the filled trough (s) are located, or in the application of a coating layer consists of the entire shaped body, are preferred according to the invention.

The moldings according to the invention can be packaged after production, wherein the use of certain packaging systems has proven to be particularly effective, as these On the one hand, packaging systems increase the storage stability of the ingredients, on the other hand if necessary, however, also significantly improve the long-term adhesion of the cavity filling. Of the The term "packaging system" denotes in the context of the present invention always the primary packaging of the molded body, d. H. the packaging that is on its inside is in direct contact with the molded body surface. An optional No requirements are placed on secondary packaging, so here all the usual ones Materials and systems can be used.

According to the invention, packaging systems which have only a low level of moisture permeability are preferred. In this way, the coloring power of the moldings according to the invention can be maintained over a longer period of time, even if, for example, hygroscopic components are used in the moldings. Packaging systems which have a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is stored at 23 ° C. and a relative equilibrium humidity of 85% are particularly preferred. The specified temperature and humidity conditions are the test conditions specified in DIN standard 53122, whereby according to DIN 53122 minimal deviations are permissible (23 ± 1 ° C, 85 ± 2% rel. Humidity). The moisture vapor transmission rate of a given packaging system or material can be determined by further standard methods and is also, for example, in ASTM standard E-96-53T ("Test for measurable water vapor transmission of materials in sheet form") and in TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of common methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. The moisture vapor permeability rate can be reduced from the surface of the container which is closed with the material to be tested (permeation area), the increase in weight of the calcium chloride and the exposure time

Calculate, where A is the area of the material to be tested in cm ² , x is the increase in weight of calcium chloride in g and y is the exposure time in h.

The equilibrium relative humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate in the context of the present invention. The ability of air to absorb water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 °, saturation is already present with 10 g of water vapor. Relative humidity is the ratio, expressed in percent, of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air at 17 ° contains 12 g / m ^{3 of} water vapor, the relative humidity = (12 / 14.4) .100 = 83%. If this air is cooled, then saturation (100% r. L.) is reached at the so-called dew point (in the example: 14 °), ie, with further cooling, precipitation in the form of fog (dew) forms. Hygrometers and psychrometers are used for the quantitative determination of humidity.

The relative equilibrium humidity of 85% at 23 ° C can be, for example, in Laboratory chambers with humidity control depending on the device type to +/- 2% r. L. exactly to adjust. Even over saturated solutions of certain salts form in closed Systems at a given temperature are constant and well-defined relative Humidity from which on the phase equilibrium between partial pressure of the Water, saturated solution and sediment.

The combinations of molded body and packaging system can of course in turn packed in secondary packaging, for example cardboard boxes or trays no further requirements are placed on the secondary packaging have to. Secondary packaging is therefore possible, but not necessary.

Depending on the embodiment of the invention, the packaging system encloses one or several moldings. It is preferred according to the invention either a shaped body to make such that it includes a unit of application of the colorant, and this To pack moldings individually, or the number of moldings in one Packing a packaging unit that in total comprises one application unit. This The principle can of course be expanded so that combinations according to the invention also contain three, four, five or even more moldings in one packaging unit can. Of course, two or more shaped bodies can be in one package have different compositions. In this way it is possible to separate certain components spatially, for example To avoid stability problems.

The packaging system of the combination according to the invention can consist of the consist of a wide variety of materials and take on any external shape. the end economic reasons and for reasons of easier processability are, however Packaging systems are preferred in which the packaging material is light in weight is easy to process, inexpensive and environmentally friendly.

In a first combination preferred according to the invention, that consists Packaging system from a sack or pouch made of single-layer or laminated Paper and / or plastic film. The moldings can be unsorted, d. H. as loose Bulk, to be filled into a bag made of the materials mentioned. But it's over aesthetic reasons and for sorting the combinations in secondary packaging preferably, the shaped bodies are sorted individually or in groups in sacks or bags to fill. These packaging systems can then - again, preferably sorted - can optionally be packed in outer packaging, which makes the Shaped body underlines.

The bags or bags made of single-layer or laminated paper or plastic film, which are preferably used as a packaging system, can be designed in a wide variety of ways, for example as inflated bags without a central seam or as bags with a central seam, which are sealed by heat (hot melting), adhesives or adhesive tapes will. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be coextruded. Plastic films which can be used as a packaging system in the context of the present invention are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193. The Fig. 111 shown there also provides information on the water vapor permeability of the materials mentioned.

Although it is possible, in addition to the foils or papers mentioned, also wax-coated ones To use paper in the form of cardboard boxes as a packaging system for the moldings, it is preferred in the context of the present invention if the packaging system does not include boxes of wax-coated paper.

No requirements are placed on the optional secondary packaging, so that all common materials and systems can be used here.

Embodiments in which the packaging system is designed to be resealable. For example, it has been found to be practical as Packaging system a resealable tube made of glass, plastic or also Use metal. In this way it is possible to adjust the dosability of the To optimize hair dye products so that the consumer can be guided, for example can use one shaped body per defined hair length unit. Even Packaging systems which have a microperforation can be used according to the invention Realize with preference.

A second object of the present invention is the use of the above described molded body for the production of an agent for coloring keratinic fibers.

A third subject of the present invention is a method of dyeing keratin fibers, in which one or more shaped bodies are dissolved in water, the The resulting preparation is applied to the fibers and again after an exposure time is rinsed off.

Although it is preferred in principle, all of the active ingredients required for hair coloring except for the solvent can nevertheless be incorporated into the shaped bodies according to the invention be preferred, the preparation obtained by dissolving the tablet in water further Add active ingredients. For example, the consumer can be instructed to a special coloring component for further nuances or one for further lightening add further oxidation component. It can also be preferred according to the invention this preparation is not stable in the shaped body immediately before use formulatable active ingredients, such as special enzyme preparations or liquid care components to be added.

The application temperatures can be in a range between 15 and 40 ° C, preferably at the temperature of the scalp. The exposure time is usually about 5 to 45, in particular 15 to 30 minutes. Unless a strong ten sid-containing carrier was used, it may be preferred to use the hair treated in this way then clean with a shampoo.

Examples

All quantities in the examples are in percent by weight.

The following hair coloring bodies were produced:

example 1

1 coloring tablet - Blond Gold (2 g)

Example 2

1 coloring tablet - red (2 g)

Example 3

1 coloring tablet - brown (2 g)

Claims (17)

1. Shaped body for coloring keratinic fibers containing in a cosmetic acceptable carrier at least one synthetic substantive dye. 2. Shaped body according to claim 1, characterized in that the synthetic substantive dye is a nitro dye. 3. Shaped body according to claim 1 or 2, characterized in that the synthetic Dye an azo dye, an anthraquinone derivative or a naphthoquinone derivative is. 4. Shaped body according to one of claims 1 or 2, characterized in that the synthetic substantive dye is cationic. 5. Shaped body according to claim 4, characterized in that the cationic substantive dye is selected from

• a) cationic triphenylmethane dyes,
• b) aromatic systems which are substituted with a quaternary nitrogen group, and
• c) substantive dyes which contain a heterocycle which has at least one quaternary nitrogen atom.

6. Shaped body according to one of claims 1 to 4, characterized in that it is a Contains alkalizing agent. 7. Shaped body according to one of claims 1 to 6, characterized in that it furthermore contains at least one developer component as dye precursor. 8. Shaped body according to one of claims 1 to 7, characterized in that it furthermore contains a derivative of indole and / or indoline as dye precursor. 9. Shaped body according to one of claims 7 or 8, characterized in that it is used as Oxidizing agent contains an addition product of hydrogen peroxide. 10. Shaped body according to claim 9, characterized in that it is used as an oxidizing agent Contains percarbamide. 11. Shaped body according to one of claims 1 to 10, characterized in that it has a Contains dissolution accelerator. 12. Shaped body according to claim 11, characterized in that the Dissolution accelerator is a disintegration aid. 13. Shaped body according to one of claims 1 to 12, characterized in that individual components of the composition to be compressed or the whole Moldings are coated. 14. Shaped body according to one of claims 1 to 13, characterized in that at forms a gel upon dissolution. 15. Shaped body according to one of claims 1 to 14, characterized in that it is of is wrapped in primary packaging. 16. Use of a shaped body according to one of claims 1 to 15 for production an agent for coloring keratin fibers. 17. A method for coloring keratinic fibers, characterized in that one or several shaped bodies according to one of claims 1 to 15 are dissolved in water, the resulting preparation then applied to the fibers and after a Reaction time is rinsed off again.