EP1482902A1 - Colouring agents - Google Patents

Abstract

The invention relates to moulding bodies for colouring keratin fibres, containing at least one oxidation dye preproduct of the coupler type and which are devoid of oxidation dye preproducts of the developer type. The invention also relates to the use of said agents in the production of hair-colouring preparations in addition to a method for colouring keratin fibres with the aid of said moulded bodies and a kit for the use in said method.

Description

 "Colorants"

The present invention relates to moldings for dyeing keratimic fibers which contain at least one oxidation dye norproduct of the coupler type and are free of oxidation dye norproducts of the developer type, the use of these compositions for the production of hair dye preparations and a ner process for dyeing keratimic fibers with these moldings and a kit for use in this ner driving.

Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with colorants, tinting agents, waving agents and styling preparations. Means for changing or balancing the color of the scalp hair play an outstanding role.

Coloring agents or tinting agents which contain so-called direct draws as the coloring component are usually used for temporary dyeings. These are dye molecules that attach directly to the hair and do not require an oxidative process to form the color. These dyes include, for example, henna, which is known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much undesired shift in shade or even a visible "discoloration" occurs much more quickly.

So-called oxidation colorants are used for permanent, intensive dyeings with appropriate fastness properties. Such colorants usually contain oxidation dye precursors of the developer or coupler type. The developer components form the actual dyes under the influence of oxidizing agents or atmospheric oxygen with one another or under coupling with one or more coupler components. The oxidation colorants are characterized by excellent, long-lasting dyeing results. A mixture of a larger number of oxidation dye precursors usually has to be used for natural-looking dyeings; in many cases direct dyes are still used for shading.

After all, a novel dyeing process has received great attention recently. In this process, precursors of the natural hair dye melanin are applied to the hair; These then form naturally analogous dyes in the hair as part of oxidative processes. Such a process with 5,6-dihydroxyindoline as the dye precursor was described in EP-B 1-530 229. When using agents with 5,6-dihydroxyindoline, in particular several times, it is possible to reproduce the natural hair color for people with gray hair. The coloring can take place with atmospheric oxygen as the only oxidizing agent, so that no further oxidizing agents have to be used. For people with originally medium blonde to brown hair, indoline can be used as the sole dye precursor. For use in people with originally red and in particular dark to black hair color, on the other hand, satisfactory results can often only be achieved by using additional dye components, in particular special oxidation dye precursors.

Hair dyes are usually formulated in the form of aqueous emulsions or coloring gels, which are optionally mixed with an oxidizing agent preparation immediately before use. However, this method still leaves something to be desired with regard to the storage stability of the formulations, the meterability and the simple handling.

Another option is to formulate hair dye as a solid in powder or tablet form. Immediately before application, these hair colorants are usually dissolved in water with stirring. The resulting ready-to-use dye is usually in the form of a gel or cream and is then applied to the hair. When formulating the colorant as a solid, the solution behavior is crucial. There must be no clumping of the solid come, which affects the effectiveness of the ready-to-use colorant. In addition to the optimal theological properties of the colorant, a rapid dissolution of the solid is desirable, particularly when the colorant is formulated in tablets of any design.

In the Offenlegimgsschrift: DE-A-36 09 962, a tablet-brown colorant based on henna and oxidation dye precursors was proposed, which should enable intense black colorations with the shortest possible exposure time. However, this document does not contain any reference to the colored moldings according to the invention.

The published patent application DE-Al-199 61 910 discloses moldings for coloring keratin fibers which, as a multi-phase tablet, contain at least one dye precursor in one phase and an oxidizing agent in a further phase. The tablets are dissolved in water in a corresponding staining process.

The published patent application WO 01/45655 discloses moldings for dyeing keratin fibers which contain indole or indoline derivatives as oxidation dye precursors of the developer type. These moldings are used in a process for dyeing keratin fibers. To produce the ready-to-use colorant, the shaped body is dissolved in water.

The published patent application WO 01/45654 discloses coloring agents in the form of a molded article which contain at least one synthetic direct dye. These shaped bodies are used in a process for dyeing keratin fibers, in which the shaped body is dissolved in water in order to produce the ready-to-use coloring agent.

In all of the above-mentioned shaped bodies, both the solution behavior, in particular in viscous media, such as creams, and the rheology of the application mixture are in need of improvement. Furthermore, the stability of the components in the state Technological molds, especially against oxidative influences, are still open.

It was therefore the task of improving the shaped bodies with regard to the dissolving behavior and the application mixture with regard to their rheology and at the same time to achieve optimal color properties.

It was now. Surprisingly, it was found that by using the shaped bodies according to the invention, the dyeings obtained can be significantly improved in terms of their intensity and fastness properties, and the shaped bodies are distinguished by a significantly reduced dissolution time.

A first object of the present invention are therefore molded articles for dyeing keratim fibers which, in addition to a cosmetically acceptable carrier, contain at least one dissolution accelerator and at least one oxidation dye product of the coupler type and are free of oxidation dye products of the developer type.

According to the invention, keratin fibers are to be understood as furs, wool, feathers and in particular human hair. Although the shaped bodies according to the invention are primarily suitable for dyeing keratin fibers, in principle there is nothing to prevent their use in other fields.

As the oxidation dye precursors of the coupler type, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used. Suitable coupler substances are in particular 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, l-phenyl -3-methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis- (2 ', 4'-diaminophenoxy) propane, 2-chloro-resorcinol, 4-chloro-resorcinol, 2 -Chlor-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, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl -3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenql, 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) -l-methylbenzene and l-amino-3-bis- (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-l-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol,

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

Dimethylresorcin, 2-chlororesorcin, 4-chlororesorcin, pyrogallol and 1,2,4-

trihydroxybenzene,

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

Diamino-2,6-dimethoxy,

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

Moφholinderivate such as 6-Hydroxybenzomoφholin and 6-Amino-benzomoφholin, Quinoxaline derivatives such as 6-methyl-1, 2,3, 4-tetrahydroquinoxaline,

Pyrazole derivatives such as l-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 l-hydroxy-3,4-methylenedioxybenzene, l-amino-3,4-methylenedioxybenzene and l- (2'-hydroxyethyl) - amino-3,4-methylenedioxybenzene.

Particularly preferred in the molded article according to the invention is at least one oxidation dye product of the coupler type selected from 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2- Amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxy-pyridine, resorcinol, 4-chlororesorcinol, 2,4-diaminophenoxyethanol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5- Contain methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

With regard to the coupler components that can be used in the molded bodies according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidationsfarbstoff-Voφrodukte), published as Volume 7 of the "Dermatology" series (Ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials" ", published by the European Community, available in disk form from the Federal Association of German Industry and Commerce for Medicines, Reformed Products and Body Care Products, Mannheim.

The molded body according to the invention contains at least one dissolution accelerator. The term dissolution accelerator encompasses gas-developing components, pre-formed and enclosed gases, disintegrants and mixtures thereof. In a first embodiment of the present invention, gas-developing components are used as the dissolution accelerator. Upon 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 value 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 citric acid in particle form, the particles having a diameter below 100 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 2,000 to 200,000. Homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid are particularly preferred. Preferred bases according to the invention are alkali metal silicates, carbonates, hydrogen carbonates and mixtures thereof. Metasilicates, bicarbonates and carbonates are particularly preferred, bicarbonates are very particularly preferred. Particulate hydrogen carbonates with a particle diameter of less than 100 μm, in particular less than 700 μm, very particularly preferably less than 400 μm are particularly preferred. Sodium or potassium salts of the above bases are particularly preferred. These gas-generating components are preferably contained in the coloring moldings according to the invention in an amount of at least 10% by weight, in particular at least 20% by weight.

In a second embodiment of the present invention, the gas is pre-formed or enclosed so that when the dissolution of the molded body begins, the gas development begins and the further dissolution accelerates. Examples of suitable gases are air, carbon dioxide, NO, oxygen and / or other non-toxic, non-combustible gases. In a particularly preferred embodiment of the present invention, disintegration aids, so-called molded-body explosives, are incorporated into the molded body as dissolution accelerators in order to shorten the disintegration times. According to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology '^''(6th edition, 1987 * p. 182-184), additives are understood to mean auxiliary substances which are suitable for the rapid disintegration of shaped bodies in water or gastric juice and release of the pharmaceuticals in an absorbable form.

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

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred molded bodies such a disintegrant based on cellulose in amounts of 0.5 to 70% by weight, preferably 3 to 30% by weight, based on the total molded body contain. Pure cellulose has the formal empirical composition (C _E H _{S IO} O) ,, and, formally, is a beta-l, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which 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 disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in 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 of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

According to the invention, the cellulose used as disintegration aid cannot be used in finely divided form, but can be converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The disintegration auxiliaries according to the invention are available commercially for example under the name of Arbocel ^® from Rettenmaier. A preferred disintegration aid is, for example, Arbocel ^® TF-30-HG.

Microcrystalline cellulose is used as the preferred disintegrant based on cellulose or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm. Suitable microcrystalline cellulose is available commercially for example under the trade name Avicel ^®.

The accelerated dissolution of the molded body can also be achieved according to the invention by pre-granulating the other components of the molded body. In a preferred embodiment of the shaped bodies according to the invention, they contain a mixture of starch and at least one saccharide to accelerate the dissolution, in particular in addition to at least one cellulose-based disintegrant. Disaccharides are preferred saccharides of this embodiment. Said mixture is preferably in a weight ratio of starch and the saccharides used of 10: 1 to 1:10, particularly preferably from 1: 1 to 1:10, very particularly preferably from 1: 4 to 1: 8 in the molded body.

The disaccharides used are preferably selected from lactose, maltose, sucrose, trehalose, turanose, gentiobiose, melibiose and cellobiose. Lactose, maltose and sucrose are particularly preferably used, and lactose is very particularly preferably used in the shaped bodies according to the invention.

The starch-saccharide mixture is contained in the molded body in an amount of 5 to 70% by weight, preferably 20 to 40% by weight, based on the mass of the entire molded body.

Although the shaped bodies according to the invention, when dissolved, can give application preparations which are weakly acidic, neutral or also alkaline, in a preferred embodiment the shaped bodies contain 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, hydrogen carbonates, phosphates, amino acids, alkali or alkaline earth metal hydroxides and organic amines.

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

In a further embodiment of the present invention, it may be preferred to use alkalizing agents which are distinguished by good water solubility. Compounds of which at least 5 g dissolve in 100 ml of water at 15 ° C. are readily water-soluble. Compounds with a water solubility of more than 7.5 g in 100 ml of water at 15 ° C. are particularly preferred.

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

In the context of this embodiment, aminocarboxylic acids are particularly preferred, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids. Lysine and in particular arginine are again particularly preferred among the α-aminocarboxylic acids.

The amino acids can preferably be added to the shaped bodies according to the invention in free form. In a number of cases, however, it is also possible to use the amino acids in salt form. Preferred salts are then the compounds with hydrohalic acids, in particular the hydrochlorides and the hydrobromides.

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

A very particularly preferred alkalizing agent is arginine, in particular in free form, but also used as hydrochloride, since in addition to its alkaline properties it also significantly increases the penetration capacity of the dyes.

The alkalizing agent is preferably contained in the shaped bodies according to the invention in amounts of 0.5 to 20% by weight, in particular 5 to 15% by weight, based on the total agent. According to the invention, it may be desirable to integrate direct dyes in the molded article. ' Nitro dyes have proven to be particularly suitable. According to the invention, nitro dyes are to be understood as meaning the coloring components which have at least one aromatic ring system which 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 (ß-hydroxyethyl) amino-2-nitrobenzene, 3- nitro-4- (ß-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,

Picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

In addition to the nitro dyes, the azo dyes, anthraquinones or naphthoquinones are also preferred synthetic direct dyes according to the invention. Preferred direct 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 direct dye carries a cationic group. Particular preference is given to (i) cationic triphenylmethane dyes, (ii) aromatic systems which are substituted by a quaternary nitrogen group, and (iii) direct dyes which contain a heterocycle which has at least one 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 disclosed in claims 6 to 11 in particular in EP-A2-998 908, to which explicit reference is made here.

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

CH ₃ SO ₄ ^"

Cl ^"

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

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as those contained in henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, sapwood, sage, blue wood, madder root, catechu, sedre and alkanna root.

The molded articles according to the invention preferably contain the substantive dyes in an amount of 0.01 to 20% by weight.

In a particularly preferred embodiment, the shaped bodies contain at least one pearlescent pigment. Frequently used pearlescent pigments are natural pearlescent pigments such as fish silver (guanine / HypoxantMn mixed crystals from fish scales) or mother-of-pearl (from ground mussel shells), monocrystalline pearlescent pigments such as bismuth oxychloride, as well as pearlescent metal mica pigments or glow / mica-based pigments. The latter pearlescent pigments are provided with a metal oxide coating. By using the pearlescent pigments, sheen and, if appropriate, additional color effects are achieved in the shaped bodies according to the invention. However, the coloring due to the pearlescent pigments used in the molded bodies does not influence the color result of the coloring of the keratin fibers. Pearlescent pigments based on mica and on mica / metal oxide are preferred according to the invention. Mica is one of the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in conjunction with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides include TiO ₂ , Cr ₂ θ3 and Fe ₂ θ ₃ . Appropriate coating gives interference pigments and colored gloss pigments as pearlescent pigments according to the invention. In addition to a glittering optical effect, these pearlescent pigment types also have color effects. Furthermore, the pearlescent pigments which can be used according to the invention can furthermore contain a color pigment which is not derived from a metal oxide.

The grain size of the preferably used pearlescent pigments is preferably between 1.0 and 100 μm, particularly preferably between 5.0 and 60.0 μm.

Particularly preferred pearlescent pigments are pigments which are marketed by the Merck company under the trade names Colorona ^® , the pigments Colorona ^® red-brown (47-57% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 43-50% by weight % Fe ₂ O ₃ (INCI: Iron Oxides Cl 77491), <3% by weight TiO ₂ (INCI: Titanium Dioxide Cl 77891), Colorona ^® Blackstar Blue (39-47% by weight Muscovit Mica (KH ₂ (AlSiO) . _3), 53-61% by weight of Fe ₃ O ₄ (INCI: Iron oxide Cl 77499)), Colorona ^® Fine Siena (35-45% by weight of muscovite mica (KH ₂ (AlSiO _{4). 3),} 55-65 wt % Fe ₂ O ₃ (INCI: Iron Oxides Cl 77491)), Colorona ^® Aboriginal Amber (50-62% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ). 36-44% by weight Fe ₃ O ₄ ( INCI: Iron Oxides Cl 77499), 2-6% by weight TiO ₂ (INCI: Titanium Dioxide Cl 77891)), Colorona ^® Patagonian Puφle (42-54% by weight Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 26 -32% by weight Fe ₂ O ₃ (INCI: Iron Oxides Cl 77491), 18-22% by weight TiO ₂ (INCI: Titanium Dioxide Cl 77891), 2-4% by weight Prussian Blue (INCI: Ferne Ferrocyanide Cl 77510 )), Colorona ^® Chameleon (40-50 wt.% Muscovit Mica (KH ₂ (AlSiO ₄ ) ₃ ), 50-60 wt.% Fe ₂ O ₃ (INCI: Iron Oxides Cl 77491)) and Silk ^® Mica (> 98 wt. % Muscovite Mica (KH ₂ (AlSiO ₄ ) ₃ )). With regard to the pearlescent pigments which can be used in the shaped bodies according to the invention, further express reference is made to the monographs Inorganic Pigments, Chemical technology review No. 166, 1980, pages 161-173 (ISBN 0-8155-0811-5) and Industrial inorganic Pigments, 2nd edition, Weinheim , VCH, 1998, pages 211-231.

Oxidizing agents can also be contained in the molded body according to the invention. Although the choice of the oxidizing agent is in principle not subject to any restrictions, it can be preferred according to the invention to use addition products of hydrogen peroxide, in particular on urea, melamine or sodium borate, as the oxidizing agent. The use of percarbamide is particularly preferred.

It is also possible to carry out the oxidation with the aid of enzymes, the enzymes being used both for producing oxidizing per compounds and for enhancing the action of a small amount of oxidizing agents present.

The enzymes (enzyme class 1: oxidoreductases) can transfer electrons from suitable developer components (reducing agents) to atmospheric oxygen. Oxidases such as tyrosinase and laccase are preferred, but also glucose oxidase, uricase or pyruvate oxidase. Furthermore, the procedure should be mentioned to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The formation of the color can also be supported and increased by adding certain metal ions to the molded 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. In principle, the metal ions can 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, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner. However, it has also proven to be practical To use metal ions in the form of their complexes or also attached to zeolites to increase the coloring power.

In a special embodiment, the molded body according to the invention is free from oxidizing agents.

When perceiving the shaped body, in particular caused by a spherical shape of the shaped body, possibly in conjunction with aromatic fragrance notes, the consumer may like the coloring agent according to the invention with a luxury agent such as e.g. Connect confectionery. In principle, this association, particularly in children, means that oral intake or swallowing of the molded body cannot be ruled out. In a preferred embodiment, the shaped articles according to the invention therefore contain a bitter substance in order to prevent swallowing or accidental ingestion. Bitter substances that are soluble in water at 20 ° C. to at least 5 g / l are preferred.

With regard to an undesired interaction with fragrance components possibly contained in the molded body, in particular a change in the fragrance note perceived by the consumer, the ionogenic bitter substances have proven to be superior to the nonionic ones. Ionic bitterns, preferably consisting of organic cation (s) and organic anion (s), are therefore preferred for the preparations according to the invention.

Quaternary ammonium compounds which contain an aromatic group both in the cation and in the anion are particularly suitable as bitter substances. One such compound is commercially available for example under the trademark Bitrex ^® and with indigenous stin ^® available benzyldiethyl ((2,6-Xylylcarbamoyl) methyl) ammonium benzoate. This compound is also known as Denatonium Benzoate.

The bitter substance is contained in the molded articles according to the invention in amounts of 0.0005 to 0.1% by weight, based on the molded article. Quantities of 0.001 to 0.05% by weight are particularly preferred. Other components

In addition to the ingredients mentioned, the shaped bodies according to the invention can furthermore contain all active ingredients, additives and auxiliaries known for such preparations. Both solids and liquids can be used as further components. If liquids are selected as a further component of the molded body according to the invention, the dosage is to be selected such that a flowable powder is present before tabletting. The liquid further components are preferably sprayed onto the powder to be tabletted by a suitable device before tabletting. A further possibility of incorporating liquid components into the shaped bodies according to the invention is provided by e.g. the previous removal of solvents so that the originally liquid component can be used as a solid.

In many cases, the molded articles contain at least one surfactant, and in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proven advantageous to select the surfactants from 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, ammonium and magnesium and the mono-, di- and trialkanol ammonium salts with 2 or 3 carbon atoms in the alkanol group, linear fatty acids with 10 to 22 carbon atoms (soaps),

Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear one

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, O 03/074014

20

Acyl taurides with 10 to 18 C atoms in the acyl group, acyl isethionates with 10 to 18 C atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 C atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl esters with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, methyl alpha-sulfofatty acid 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-3725 030, sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-3723 354,

Sulfonates of unsaturated fatty acids with 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-3926344,

Esters of tartaric acid and citric acid with alcohols, which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 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 in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as stearic acid, oleic acid , Isostearic acid and palmitic acid.

Non-ionic 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, Cι ₂ -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues and addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil.

Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ © - (Z) _χ . These compounds are, for example, under the trade name Plantacare ^® from

Henkel available and are characterized by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Examples of such alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 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 contain, for example, only a certain alkyl radical R ¹ . Usually, however, these compounds are made from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

Particularly preferred are those alkyl polyglycosides in which R ¹ consists essentially of C ₈ - and Cio-alkyl groups, essentially from C ₂ - and C ₄ -alkyl groups, essentially from C ₈ - to C ₆ alkyl groups or essentially from Cj ₂ - Cι ₆ alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galac tose, arabinose, ribose, xylose, lyxose, AUose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values from 1.1 to 1.6 are preferred. Alkyl glycosides in which x is 1.1 to 1.4 are very particularly preferred.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. In the event that an effect of the perfume oil on the hair beyond the duration of the hair treatment is desired, the person skilled in the art will preferably resort to this substance class as a further ingredient of the preparations according to the invention. An inventively particularly preferred alkyl glucoside is the commercial product Plantacare® ^® 1200G.

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

Furthermore, zwitterionic surfactants can be used, in particular as co-surfactants. Zwitterionic surfactants are surface-active compounds that carry at least one quaternary ammonium group and at least one -COO ^H - or -Sθ ₃ ^W group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammomumglycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and also the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. 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. Ampholytic surfactants are surface-active compounds which, in addition to a Cs-Ci ₈ -alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SOsH group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are the N-coconut alkylaminopropionate, the coconut acylaminoethylaminopropionate and the C ₂ -i ₈ acyl sarcosine.

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

Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimemyla monium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimemylbenzylammonium chloride and tricetylmethylammonium chloride, and the compounds known under the INCI names Quaternium-27 and Quaternium-83 compounds imidazol. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

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

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

The quaternized protein hydrolyzates are further cationic surfactants which can be used according to the invention.

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

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

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products can be used with a "normal" homolog distribution as well as those with a narrow homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcohols. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

Furthermore, the molded articles according to the invention can preferably also contain a conditioning active ingredient selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines, paraffin oils, vegetable oils and synthetic oils. With regard to the cationic surfactants, reference is made to the above statements.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that have a quaternary nitrogen atom, for example in the form of a

Ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and esters and aids of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiaIIyIammoniumchlorid)), Merquat ^® 550 (DimethyldiallylammoniumcWorid-Acrylainid copolymer) and Merquat ^® 280 (dimethyldiallylammonium chloride-acrylic acid copolymer commercially available products copolymers are examples of such cationic polymers. Of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as, for example, vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol and under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

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

Cationic polymers of the first four groups are particularly preferred; polyquaternium-2, polyquaternium-10 and polyquaternium-22 are very particularly preferred.

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

Paraffin oils, synthetically produced oligomeric alkenes and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins. Furthermore, the preparations used according to the invention preferably contain at least one oil component.

Oil components suitable according to the invention are in principle all water-insoluble oils and fatty substances as well as their mixtures with solid paraffins and waxes. According to the invention, such substances are defined as water-insoluble if their solubility in water at 20 ° C. is less than 0.1% by weight.

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 seed oil and the liquid components of coconut oil.

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

Another particularly preferred group of compounds which can be used according to the invention as an oil component are liquid paraffin oils and synthetic hydrocarbons and di-n-alkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, such as, for example, di-n-octyl ether, di -n-decyl ether, di-n-nonyl ether, di-n-undecyl ether, di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl -n-dodecyl ether and n-hexyl-n-undecyl ether and di-tert-butyl ether, di-isopentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, isopentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether. The compounds are available as commercial products l, 3-di- (2-ethyl-hexyl) -cyclohexane (Cetiol ^® S), and di-n-octyl ether (Cetiol ^® OE) may be preferred.

Oil components which can likewise be used according to the invention are fatty acid and fatty alcohol esters. The monoesters of the fatty acids with alcohols having 3 to 24 carbon atoms are preferred. This group of substances concerns the products of the esterification of fatty acids with 6 to 24 carbon atoms such as, for example, 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, elaeostearic 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 oxosynthesis or the dimerization of unsaturated fatty acids, with alcohols such as isopropyl alcohol, capron 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, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, technical alcohol, gadoleyl alcohol, brassole, alcoholic alcohol, gadoleyl alcohol, mixtures thereof, gadoleyl alcohol, mixtures thereof, gadoleyl alcohol, mixtures thereof, eradyl alcohol alcohol, gadoleyl alcohol, mixtures of these, g. B. 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 particularly preferably isopropyl myristate, isononanoic acid C16-18 alkyl ester (Cetiol ^® SN), stearic acid-2-ethylhexyl ester (Cetiol ^® 868), cetyl oleate, glycerol tricaprylate, cocofatty alcohol caprate / caprylate and n-butyl stearate.

Furthermore, dicarboxylic acid esters such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, di- (2-ethylhexyl) succinate and di-isotridecyl acelate as well as diol esters such as ethylene glycol dioleate, ethylene glycol di-isotridecanoate and propylene glycol di (2-ethylhexanoate), propylene glycol di-isostearate, propylene glycol di-pelargonate, butanediol di-isostearate and neopentyl glycol di-caprylate are oil components which can be used according to the invention, and also complex esters such as e.g. B. the diacetyl glycerol monostearate.

Finally, fatty alcohols with 8 to 22 carbon atoms can also be used as oil components acting according to the invention. The fatty alcohols can be saturated or unsaturated and linear or branched. For the purposes of the invention, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, eruca alcohol, ricinol alcohol, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, capryl alcohol, arachidyl alcohol, arachidyl alcohol, arachidyl alcohol , as well as their Guerbet alcohols, this list being exemplary and not limiting Should have character. However, the fatty alcohols are derived from preferably natural fatty acids, and it can usually be assumed that they are obtained from the esters of the fatty acids by reduction. Also suitable according to the invention are those fatty alcohol cuts which are produced by reducing naturally occurring triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols, and thus represent a mixture of different fatty alcohols.

The oil components are preferably used in amounts of 0.05 to 10% by weight, in particular 0.1 to 2% by weight, in the moldings according to the invention.

In a preferred embodiment of the present invention, a gel forms when the shaped bodies are dissolved in water. For this purpose, the shaped body thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, eg. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. For example, bentonite, silicates, such as are for example sold under the trade names Optigel ^® (Süd-Chemie), or Laponite ^® (Solvay), or fully synthetic hydrocolloid colloids such as polyvinyl alcohol was added. Particularly preferred thickeners are xanthans, alginates and highly substituted carboxymethyl celluloses.

Other active ingredients, auxiliaries and additives are, for example, zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, anionic polymers such as, for example, 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 particles,

Structurants such as maleic acid and lactic acid,

Protein hydrolyzates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolyzates, their condensation products with fatty acids and quaternized protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solvents and mediators such as ethylene glycol, propylene glycol, glycerin and diethylene glycol, active substances which improve fiber structure, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl l-alkylamidoethyl-2-alkylimida2: olinium methosulfate defoamers such as silicones, dyes for coloring the agent,

Anti-dandruff agents such as piroctone olamine, zinc omadine and climbazole, light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,

Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,

Active ingredients such as allantoin, pyrrolidone carboxylic acids and their salts as well as bisabolol, vitamins, provitamins and vitamin precursors, in particular those from 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 flowers, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, kiwi , Melon, orange, grapefruit, sage, rosemary, birch, mallow, cuckoo flower, quendel, yarrow, thyme, lemon balm, squirrel, coltsfoot, marshmallow, meristem, ginseng and ginger root, cholesterol,

Consistency generators such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax and paraffins, fatty acid,

Complexing agents such as EDTA, NTA, ß-alaninediacetic acid and phosphonic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and 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, stabilizing agents for the oxidizing agent, antioxidants.

Shaped body geometries

The shaped bodies according to the invention can have any geometric shape, such as, for example, concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, seven-ellipsoid, five and octagonal-prismatic and rhombohedral shapes. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. The design as a table, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side faces, and in particular cylindrical configurations with a circular or oval cross section and molded bodies with spherical geometry are preferred according to the invention. Shaped bodies in the form of spherical geometry are particularly preferred.

The cylindrical design covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter greater than 1. If the basic form body has corners and edges, these are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“chamfered”) edges is preferred. In addition to a spherical shape, the spherical configuration also comprises a hybrid of spherical and cylindrical shapes, each base area of the cylinder being capped with a hemisphere. The hemispheres preferably have a radius of approximately 4 mm and the entire molded body of this embodiment has a length of 12-14 mm.

A shaped body according to the invention with a spherical configuration can be produced by the known methods. It is possible to produce the molded body by extrusion of a premix followed by shaping, as described in more detail, for example, in WO-A-91/02047, to which reference is expressly made in the context of this application.

In a further preferred embodiment, almost spherical shaped bodies are therefore produced, in particular by extrusion and subsequent rounding for shaping.

In a further embodiment, the portioned compacts can each be designed as separate individual elements which correspond to the predetermined metered amount of the oxidation dye products of the coupler type. However, it is also possible to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. Forming the portioned compacts as tablets in the shape of cylinders or cuboids can be expedient, a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 being preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

Another possible spatial shape of the molded body according to the invention has a rectangular base, the height of the molded body being smaller than the smaller rectangular side of the base. Rounded corners are preferred with this offer.

Another molded body that can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual Segments of this "bolt" at the predetermined breaking points, which represent the short, thin segments, can be broken off and used in portions. This principle of the "bar-shaped" shaped body can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.

If the shaped bodies according to the invention contain at least one further component in addition to the coupler component, it can be advantageous in a further embodiment not to address the various components exclusively to form a uniform tablet. In this embodiment, tablets are obtained with tableting which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence each other negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the components are not already in the process of being dissolved react with each other.

The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely detached. In the stack-like arrangement, the stack axis can be arranged as desired to the tablet axis. In the case of a cylindrical tablet, for example, the stacking axis can be parallel or perpendicular to the height of the cylinder.

However, according to a further embodiment, it may also be preferred if the inner layer (s) is completely covered by the layer (s) lying further outwards, which prevents the premature dissolution of components of the inner layer (s). en) leads. Shaped bodies in which the layers are coated with the different active substances are preferred. For example, let a layer (A) be completely of the layer (B) and this in turn be completely of the Layer (C) wrapped. Shaped bodies may also be preferred in which, for example, layer (C) is completely encased by layer (B) and in turn is completely encased by layer (A).

Similar effects can also be achieved by coating individual components of the composition to be held or the entire molded body. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method. For example, the use of a coating of hydroxypropyl methyl cellulose, cellulose, PEG stearates and color pigments has been found to be suitable according to the invention.

The (trough) shaped bodies produced according to the invention can, as described above, be provided with a coating in whole or in part. Processes in which there is an aftertreatment in the application of a coating layer to the molded body surface (s) in which the filled cavity (s) are located or in the application of a coating layer to the entire molded body are preferred according to the invention.

The molded article according to the invention has a preferred breaking hardness of 30-100 N, particularly preferably 40-80 N, very particularly preferably 50-60 N (measured according to European Pharmacopoeia 1997, 3rd edition, ISBN 3-7692-2186-9, " 2.9.8 Breaking strength of tablets "; Page 143-144 with a Schleuniger 6D tablet hardness tester).

Furthermore, the molded body according to the invention can consist of a molded body which is known per se by known tabletting processes and which has a depression and is described with the term “basic molded body”. In this embodiment, the basic molded body is preferably produced first and the further molded part is added in a further step The resulting product is referred to below with the generic term “trough shaped body” or “trough tablet”. According to the invention, the basic shaped body can in principle assume all realizable spatial shapes. The spatial shapes already mentioned are particularly preferred. The shape of the trough can be chosen freely, with molded bodies being preferred according to the invention, in which at least one trough is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid , five-, seven- and octagonal-prismatic and rhombohedral shape can take. Completely irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized. As with the basic molded bodies, troughs with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The size of the trough in comparison to the entire molded body depends on the intended use of the molded body. Depending on whether a smaller or larger amount of active substance should be contained in the second pressed part, the size of the trough can vary. Regardless of the intended use, molded articles are preferred in which the weight ratio of basic molded articles to trough filling is in the 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 regarding the surface proportions that make up the basic molded body or the trough filling on the overall surface of the molded body. Shaped bodies are preferred here in which the surface of the pressed-in trough filling makes up 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface area of the filled basic shaped body.

If, for example, the overall molded body has dimensions of 20 x 20 x 40 mm and thus a total surface area of 40 cm ² , trough 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 Have 1.2 to 6 cm ² and in particular from 1.6 to 4 cm ² .

The trough filling and the basic molded body are preferably colored to be optically distinguishable. In addition to the optical differentiation, trough tablets show application-technical advantages on the one hand through different solubilities of the different areas on the other hand also through the separate storage of the active substances in the different molded body areas.

Molded bodies in which the pressed-in mold filling dissolves more slowly than the basic molded body are preferred according to the invention. The solubility of the trough filling can be varied in a targeted manner by incoφoration of certain constituents, on the other hand the release of certain ingredients from the trough filling can lead to advantages in the dyeing process. Ingredients, which are preferably located at least partially in the trough filling, are, for example, the conditioning agents, oil bodies, vitamins and plant agents described in the paragraph "further components".

tableting

It can be preferred according to the invention to encapsulate individual active ingredients separately before they are incorporated into the molded body; For example, it is conceivable to use particularly reactive components or the fragrances in encapsulated form.

The moldings according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby known methods can be used. To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower stamp. With this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the top punch (and hence from a certain pressure on the premix) of the plastic deformation, wherein ^"of the particles coalesce and results in the formation of the molded article begins. Depending on the physical properties of the premix is also a part of the premix particles crushed The sintering of the premix occurs at even higher pressures. With increasing pressing speed, ie high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting the finished molded article is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded article is finally determined, since the compacts due to physical processes (stretching, crystallographic effects, abbr cooling etc.) can still change their shape and size.

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower stamp, but several stamps can also be attached to one eccentric disc, the number of die holes being correspondingly increased. 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 selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower stamp, with the pressing pressure being active only by the upper or lower die. Lower stamp, but can also be built up by both stamps. The die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. At locations where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, pull-down rails and lifting tracks. 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 pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. With suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also 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 simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million molded articles per hour.

When tableting with concentricity presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

- Matching the filler paddle speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed

To reduce the build-up of stamps, all non-stick coatings known from technology are available. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating stamps, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

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

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

However, the process for producing the molded body is not limited to the fact that only a particulate nor mixture is pressed into a molded body. Rather, the method can also be expanded to the effect that multilayer molded articles are produced in a manner known per se by preparing two or more premixes which are pressed onto one another. In this case, the premix which has been filled in first is lightly pre-pressed in order to obtain a smooth upper surface which runs parallel to the mold body bottom, and after the second premix is filled in the finished mold body is finally pressed. In the case of three-layer or multi-layer molded bodies, a further preliminary treatment is carried out after each premix addition, before the molded body is finally pressed after addition of the last premix.

The particulate composition can be pressed into the trough analogously to the production of the basic shaped body on tablet presses. A procedure is preferred in which the basic molded body is first produced with a depression, then filled and then re-pressed. This can be done by ejecting the basic molded body from a first tablet press, filling and transporting it to a second tablet press, in which the final addressing takes place. Alternatively, the endveφressung can also be done by pressure rollers that roll over the molded body located on a conveyor belt. However, it is also possible to provide a rotary tablet press with different stamp sets, so that a first stamp set presses depressions into the molded body and the second set of stamps after filling by oberflächeachveφressung ensures a flat molded body surface. A second object of the invention is a process for dyeing keratin-containing

Fibers characterized in that

(I) one or more shaped bodies according to the invention are dissolved in a medium M to form preparation A, (Η) the resulting preparation A is mixed with an oxidizing agent preparation B to form a ready-to-use coloring agent F,

(III) the dye F is applied to the fibers and

(IV) is rinsed off after an exposure time.

Preparation A and oxidizing agent preparation B are preferably mixed in a weight ratio of about 2: 1 to 1: 2, particularly preferably in a weight ratio of about 1: 1.

It is of course also possible within the scope of the method to use a powder or granules instead of the shaped body according to the invention which, in addition to a cosmetically acceptable carrier, contains at least one dissolution accelerator and at least one oxidation dye product of the coupler type and is free of oxidation dye products of the developer type.

The ready-to-use colorant F should preferably have a pH in the range from 6 to 12. It is particularly preferred to use the hair dye in a weakly alkaline environment. 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. If no carrier containing high tensides was used, it may be preferred to subsequently clean the hair treated in this way with a shampoo.

In a further embodiment, the medium M is preferably a gel or an O / W or W / O emulsion.

The medium M has a viscosity of 500-100000 mPa-s, preferably 3000-70000 mPa-s, particularly preferably 6000-50000 mPa-s and very particularly preferably from 10000-30000 mPa-s. The viscosities are measured with a Brookfield RVT viscometer at a temperature of 20 ° C at 4 φm with spindle No. 4. However, the choice of the spindle for measuring the above-mentioned viscosities is preferably carried out according to the viscosity range (measured under the above-mentioned test conditions) according to Table 1.

: 1

Spmdel number viscosity range [mPa-s]

1 - 2500

2> 2500 - 10000

3> 10000 - 25000

4> 25000 - 50000

5> 50000 - 100000

In a special embodiment, the medium M has a viscosity of 500-50000 mPa-s, particularly preferably 500-25000 mPa-s, very particularly preferably 500-

15000 mPa-s. The measurement of the viscosities of this special embodiment is carried out with a Brookfield RVT viscometer at 20 ° C with the spindle 4 and 20 φm.

In a preferred embodiment of the process according to the invention, the medium M contains at least one oxidation dye precursor of the developer type. It can be preferred according to the invention to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. P-Phenylenediamine derivatives of the formula (E1) are particularly preferred

in which

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

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

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

G ⁴ represents a hydrogen atom, a halogen atom or a C} - to C - 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, for example, an ethylenedioxy group.

Examples of the Cr 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. Ci to C ₄ alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C 1 -C 4 -hydroxyalkyl group Hydroxymethyl -, - a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ - to C polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms according to the invention are F, Cl or Br atoms, Cl atoms are very particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups of formula (El) are especially the amino groups, Ci to C monoalkylamino, Ci to C ₄ dialkylamino, Ci to C - trialkylammonium groups, Ci to C ₄ -Monohydroxyalkylaminogruppen, Imidazolimum and ammonium.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4 -Amino-3-methyl- (N, N-diethyl) aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) -amino-2 -methylaniline, 4-N, N-bis- (ß-hydroxyethyl) -amino-2-chloroaniline, 2- (ß-hydroxyethyl) -p-phenylenediamine, 2- (α, ß-dihydroxyethyl) -p-phenylenediamine, 2 -Fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (ß-hydroxypropyl) -p-phenylenediamine, 2-

Hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, ß-hydroxyethyl) -p-phenylenediamine, N- (ß, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (ß-

Hydroxyethyloxy) -p-phenylenediamine, 2- (ß-acetylaminoethyloxy) -p-phenylenediamine, N- (ß-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-l, 4-dioxane and their physiologically tolerable salts.

According to the invention, particularly preferred p-phenylenediamine derivatives of the formula (E1) are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N -Bis- (ß-hydroxyethyl) -p-phenylenediamine. It can further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted with amino and / or hydroxyl groups.

Among the binuclear developer components which can be used in the coloring compositions according to the invention, one can name in particular the compounds which correspond to the following formula (E2) and their physiologically tolerable salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C 1 -C ₄ -alkyl radical, by a C 1 -C ₄ -hydroxyalkyl radical and / or by a bridging Y or the is optionally part of a bridging ring system, the bridging Y represents an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is formed by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen or sulfur - or nitrogen atoms can be interrupted or terminated and possibly substituted by one or more hydroxyl or Ci to C ₈ alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C 1 -C ₄ -alkyl radical, a -C 1 -C monohydroxyalkyl radical, a C ₂ -C ₄ polyhydroxyalkyl radical, a C 1 -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 Ci to C ₄ alkyl radical, with the provisos that

- The compounds of formula (E2) contain only one bridge Y per molecule and

- The compounds of formula (E2) contain at least one amino group which carries at least one hydrogen atom.

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

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

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

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

G ¹³ stands for a hydrogen atom, a halogen atom, a Cp to C alkyl radical, a Ci to C ₄ monohydroxyalkyl radical, a C ₂ to C polyhydroxyalkyl radical, a (Cp to C ₄ ) alkoxy (Cp to C ₄ ) -alkyl radical, a Cp to C ₄ -aminoalkyl radical, a hydroxy- (Cp to C ₄ ) -alkylamino radical, a Cp to C -hydroxyalkoxy radical, a Cp to C -hydroxyalkyl- (Cpbis C) -aminoalkyl radical or a (di-Cp to C -

Alkylamino) - (Cp to C) alkyl, and

G ¹⁴ represents a hydrogen or halogen atom, a Cp to C ₄ alkyl radical, one

Cp to Gp monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a (Cp to C) alkoxy (Cp to C) alkyl radical, a Cp to C ₄ aminoalkyl radical or a Cp to C ₄ cyanoalkyl radical,

G ¹⁵ represents hydrogen, a Cp to C - alkyl radical, a Cp to C -

Monohydroxyalkylrest, a C ₂ - to C -polyhydroxyalkylrest, a phenylrest or a benzylrest, and

G ¹⁶ represents hydrogen or a halogen atom.

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

Preferred p-aminophenols of the formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 2-hydroxymethylamino-4-aminophenol, 4 - Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino -2-aminomethylphenol, 4-amino-2- (ß-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, ß-dihydroxyethyl) phenol, 4-amino- 2-fluoφhenol, 4-amino-2-chlθφhenol, 4-amino-2,6-dichloφhenol, 4-amino-2- (diethylaminomethyl) phenol and their physiologically tolerable salts.

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

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

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

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

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

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

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently represent a hydrogen atom, a Cp to C ₄ alkyl radical, an aryl radical, a Cp to C ₄ hydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical a ( Cp to C ₄ ) alkoxy- (Cp to C) -alkyl, a Cp to C ₄ -aminoalkyl, which can optionally be protected by an acetyl-ureide or a sulfonyl residue, a (Cp to C ₄ ) -alkylamino - (Cp to C ₄ ) alkyl radical, a di- [(Cp to C ₄ ) alkyl] - (Cp to C ₄ ) aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain links , a Cp to C ₄ hydroxyalkyl or a di (Cp to C) - [hydroxyalkyl] - (Cp to C ₄ ) - aminoalkyl radical, the X radicals independently of one another represent a hydrogen atom, a Cp to C ₄ alkyl radical , an aryl radical, a Cp to C ₄ hydroxyalkyl radical, a C ₂ to C polyhydroxyalkyl radical, a Cp to C ₄ aminoalkyl radical, a (Cp to C ₄ ) alkylamino (Cp to C ₄ ) alkyl radical, a di - [(Cp to C ₄ ) alkyl] - (Cp to C ₄ ) aminoalkyl radical, where the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain links, one Cp to C ₄ hydroxyalkyl or a di (Cp to C ₄ hydroxyalkyl) anino alkyl radical, an amino radical, a Cp to Gp alkyl or di (Cp to C hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or one Sulphonic 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 Is 0 when p + q is 2, n is 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 1, n is 1, and the groups NG ^{, 7} G ¹⁸ (or NG ^I9 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 defined analogously to the above statements.

If the pyrazole- [1,5-a] pyrimidine of the above formula (E4) contains a hydroxyl group at one of the 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-Dimemyl-pyrazole [l, 5-a] -pyrimidm-3,7-diamine;

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

2,7-dimethyl-pyr-ιzol- [l, 5-a] -pyrinidine-3,5-diamine;

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

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

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

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

2 - [(3-aminopyrazole- [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;

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

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

2,6-dimethylpyrazole [l, 5-a] pyrimidine-3,7-diamine;

3-Amino-7-dimemylammo-2,5-dimethylpyrazole [l, 5-a] pyrimidine; as well as their physiologically acceptable salts and their tautomeric forms when there is a tautomeric equilibrium.

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

The medium M can contain at least one coupler component and / or at least one substantive dye in addition to the developer components. The coupler components or direct dyes preferably used in this embodiment correspond to those which have already been mentioned above. The statements made in the relevant sections apply.

It is not necessary that the oxidation dye products used in the medium M or the substantive dyes each represent uniform compounds. Rather, due to the manufacturing process for the individual dyes, further components may be contained in minor amounts in the shaped bodies according to the invention, provided that these do not result in the coloring result adversely affect or for other reasons, e.g. B. toxicological, must be excluded.

The oxidation dye products are contained in the medium M preferably in amounts of 0.01 to 20% by weight, preferably 0.5 to 5% by weight, based in each case on the entire medium M.

Those indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes. These groups can carry further substituents, e.g. B. in the form of etherification or esterification of the hydroxy group or an alkylation of the amino group.

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

(Ia)

R ¹

in the independently of each other

R represents hydrogen, a CpC ₄ alkyl group or a CpC 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 represents hydrogen or a CpC ₄ alkyl group,

R ⁴ represents hydrogen, a CpC ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a CpC ₄ alkyl group, and

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

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

Of particular note within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially that 5,6-Dihydroxyindolin.

Derivatives of 5,6-dihydroxyindole of the formula (Ib) are also outstandingly suitable as precursors of nature-analogous hair dyes,

in the independently of each other

R ¹ represents hydrogen, a CpC ₄ alkyl group or a CpC 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 represents hydrogen or a CpC ₄ alkyl group,

R ⁴ represents hydrogen, a CpC ₄ alkyl group or a group -CO-R ⁶ , in which

R ⁶ represents a CpC ₄ alkyl group, and

R ⁵ stands for one of the groups mentioned under R ⁴ , as well as physiologically tolerable salts of these compounds with an organic or inorganic acid. Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5, 6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Within this group, particular mention should be made of N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and in particular 5.6 -Dihydroxyindol.

The indoline and indole derivatives can be used in the colorants used in the process according to the invention both as free bases and in the form of their physiologically tolerable salts with inorganic or organic acids, for. B. the hydrochloride, sulfates and hydrobromides can be used. The indole or indoline derivatives are usually contained in these in amounts of 0.05-10% by weight, preferably 0.2-5% by weight.

In particular when using dye precursors of the indoline or indole type, it has proven to be advantageous to use an amino acid and or an oligopeptide as the alkalizing agent.

The oxidizing agent preparation B contains at least one oxidizing agent. On the one hand, the oxidizing agent can serve to lighten the fibers to be treated. On the other hand, the addition of an oxidizing agent can also serve to develop the actual dye from the dye precursors.

The actual oxidative coloring of the fibers can basically be done with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or its adducts with urea, melamine and sodium borate are suitable as oxidizing agents. According to the invention, however, the oxidation colorant can also be applied to the hair together with a catalyst which is responsible for the oxidation of the Farbstoffvoφrodukte, for example, activated by atmospheric oxygen. Such catalysts are, for example, metal ions, iodides, quinones or certain enzymes.

The formation of the color can also be supported and increased by adding certain metal ions to the molded 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. In principle, the metal ions can 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, the formation of the coloring can be accelerated and the color shade can be influenced in a targeted manner. However, it has also proven practical to use the metal ions in the form of their complexes or also attached to zeolites to increase the coloring power.

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

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

Glucose oxidase and D-glucose,

Glycerin oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts,

- alcohol oxidase and alcohol (MeOH, EtOH),

Lactate oxidase and lactic acid and their salts,

Tyrosinase oxidase and tyrosine,

Uricase and uric acid or salts thereof,

Choline oxidase and choline,

- Amino acid oxidase and amino acids. With regard to other optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, e.g. B. Kh. Schrader, Basics and Formulations of Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

A third object of the present invention is the use of the shaped bodies described above for the production of an agent for coloring keratin fibers.

A fourth object of the present invention is a kit for use in the method according to the invention, characterized in that it contains three separately assembled components in the containers K1, K2 and K3, container K1 the medium M, container K2 one or more molded bodies and containers according to the invention K3 contains the oxidizing agent preparation B.

Packaging of the molded articles

The shaped bodies according to the invention can be packed after production, the use of certain packaging systems having proven particularly useful since these packaging systems on the one hand increase the storage stability of the ingredients, but on the other hand also significantly improve the long-term adhesion of a trough filling. Furthermore, packaging systems increase protection against destruction of the molded body by mechanical influences. In the context of the present invention, the term “packaging system” always characterizes the primary packaging of the molded articles in the container K2, ie the packaging that is in direct contact with the inside of the molded article surface. The usual requirements are placed on an optional secondary packaging, so that here All known materials and systems can be used It is preferred according to the invention to package the molded body in a transparent packaging system or to package this packaging system, if necessary, in a transparent secondary packaging. Packaging systems which have only a low moisture permeability are preferred according to the invention. In this way, the coloring ability of the molded bodies according to the invention can be maintained over a longer period of time, even if, for example, hygroscopic components are used in the molded bodies. Packaging systems which have a moisture vapor permeability rate of 0.1 g / m / day to less than 20 g / m / day are particularly preferred if the packaging system is stored at 23 ° C. and a relative equilibrium moisture content of 85%. The specified temperature and humidity conditions are the test conditions that are mentioned in DIN standard 53122, whereby according to DIN 53122 minimal deviations are permissible (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of current 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 determined from the surface of the container which is closed with the material to be tested (permeation surface), the weight gain 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 weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as “relative air humidity”, is 85% at 23 ° C. when measuring the moisture vapor transmission rate in the context of the present invention. The air absorption rate for 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 ° there is already saturation with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) -100 = 83%. If you cool this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie, if it cools further, a precipitate is formed in the form of fog (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture.

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

The combinations of molded body and packaging system can of course themselves be packaged in secondary packaging, for example cardboard boxes or trays, whereby the usual requirements must be placed on the secondary packaging. The secondary packaging is therefore possible, but not necessary.

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

The packaging system of the combination according to the invention can consist of a wide variety of materials and can take on any external shape. For economic reasons and for reasons of easier processing, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive and ecologically compatible.

In a first preferred combination according to the invention, the packaging system consists of non-dimensionally stable packaging such as, for example, a sack or pouch made of single-layer or laminated paper and / or plastic film and / or metal foil. The shaped bodies can be unsorted, i.e. as a loose fill, be filled into a bag made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the moldings individually or in groups in sacks or bags. These packaging systems can then - again preferably sorted - be optionally packed in packaging, which underlines the compact form of the molded article.

The sacks or bags made of single-layer or laminated paper or plastic film or metal foil, which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is caused by heat (hot melting), adhesives or adhesive tapes. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded. 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. Figure 111 shown there gives at the same time Indications of the water vapor permeability of the materials mentioned. Although it is possible to use wax-coated papers in the form of cardboard boxes as packaging systems for the foils, in addition to the foils or papers, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper.

In a further embodiment, the film body is stored in a dimensionally stable packaging, such as a blister. In this embodiment, the blister can be sealed with a metal foil or with corresponding foil laminates.

Customary requirements are placed on the optional secondary packaging, so that all known materials and systems can be used here.

In a further embodiment, the packaging system is designed to be resealable. For example, it has proven to be practical to use a reclosable tube made of glass, plastic or metal as the packaging system. In this way it is possible to optimize the meterability of the hair dyeing products, so that the consumer can be instructed, for example, to use one shaped body per defined hair length unit. Packaging systems which have a microperforation can also be preferably implemented according to the invention.

In a particularly preferred embodiment, the container K2 is attached to the packaging unit of the container Kl. The container K2 can be mechanically connected to the container Kl, for example by attaching or plugging it on. A connection of the two containers by means of an adhesive is also possible.

If the molded body is assembled in a blister, it is preferred to attach the blister to the packaging unit of the container Kl in such a way that the sealing of the blister also represents a wall of the container Kl. Now the sealing of the blister by mechanical pressure on the blister or on the Foπnköφer broken through, the molded body has access to the medium M located in the container Kl. This type of attachment enables the consumer, within the scope of the method according to the invention, to conveniently dose the molded body into the medium M without directly contacting him.

Examples

The following hair color molded articles with a mass of 0.4 g and a breaking hardness of 60 to 80 N were produced. The tablets were pressed with a force of 3.5 kN.

example 1

¹ microcrystalline cellulose (FMC Coφoration)

Mixture of lactose monohydrate and corn starch (weight ratio 85:15) (Meggle) ³ coated mica (INCI name: Mica, CI 77491 (Iron Oxides), CI 77891

(Titanium Dioxide)) (MERCK)

Example 2:

Example 3:

Claims

claims

1. molded body for coloring keratin fibers, characterized in that the foam body contains, in addition to a cosmetically acceptable carrier, at least one dissolution accelerator and at least one oxidation dye product of the coupler type and is free from oxidation dye products of the developer type.

2. Molded body according to claim 1, characterized in that the dissolution accelerator is a disintegration aid.

3. molded article according to claim 2, characterized in that the disintegrant is cellulose-based.

4. molded article according to one of claims 1 to 3, characterized in that the molded article additionally contains a mixture of starch and at least one saccharide.

5. molded article according to claim 4, characterized in that the saccharide is a disaccharide.

6. molded article according to claim 5, characterized in that the disaccharide is selected from the group formed from lactose, maltose, sucrose, trehalose, turanose, gentiobiose, melibiose and cellobiose.

7. molded article according to claim 6, characterized in that the disaccharide is selected from the group formed from lactose, maltose and sucrose.

8. molded article according to claim 7, characterized in that the disaccharide is lactose.

9. molded article according to one of claims 4-8, characterized in that the starch and the saccharides used are contained in a weight ratio of 1:10 to 10: 1.

10. Foπnköφer according to claim 9, characterized in that the starch and the saccharides used are contained in a weight ratio of 1: 1 to 1:10.

11. Foπnköφer according to claim 10, characterized in that the starch and the saccharides used are contained in a weight ratio of 1: 4 to 1: 8.

12. Molded body according to one of claims 1-11, characterized in that the foiled body contains an alkalizing agent.

13. Foπnköφer according to any one of claims 1-12, characterized in that the molded body contains at least one substantive dye.

14. Foπnköφer according to any one of claims 1-13, characterized in that the molded body contains at least one pearlescent pigment.

15. Foπnköφer according to any one of claims 1-14, characterized in that the molded body contains at least one bitter substance.

16. Foπnköφer according to any one of claims 1-15, characterized in that individual components of the composition to be veφressenden or the entire molded body is coated.

17. molded body according to any one of claims 1-16, characterized in that the Foπnköφer is encased by a primary packaging.

18. Shaped body according to one of claims 1-17, characterized in that the foam body has a breaking hardness of 30-100 N, preferably 40-80 N, particularly preferably 50-60 N (measured according to European Pharmacopoeia 1997, 3rd Edition, ISBN 3-7692-2186-9, "2.9.8 Breaking strength of tablets"; page 143-144 with a tablet hardness tester Schleuniger 6D).

19. Use of the shaped body according to one of claims 1-18 for the production of an agent for coloring keratin fibers.

20. A process for dyeing keratin fibers, characterized in that

(I) one or more foils according to one of claims 1 to 18 are dissolved in a medium M to form preparation A,

(II) the resulting preparation A is mixed with an oxidizing agent preparation B to form a ready-to-use coloring agent F,

(III) the dye F is applied to the fibers and

(IV) is rinsed off after an exposure time.

21. The method according to claim 20, characterized in that the medium M a

Has a viscosity of 500-100000 mPa-s, preferably 3000-70000 mPa-s, particularly preferably 6000-50000 mPa-s and very particularly preferably 10000-30000 mPa-s (Brookfield RVT viscometer at a temperature of 20 ° C at 4 φm with spindle no.4).

22. The method according to any one of claims 20 - 21, characterized in that the medium M is a gel or a W / O emulsion or O / W emulsion.

23. Kit for use in a method according to any one of claims 19 - 22, characterized in that it contains three separately assembled components in the containers K1, K2 and K3, container K1 the medium M, container K2 one or more molded bodies according to one of the Claims 1-18 and container K3 containing the oxidizing agent preparation B.