DE102004035348A1 - Agent for the treatment of keratinic fibers - Google Patents

Abstract

The invention relates to agents for coloring keratinic fibers, consisting of at least two spatially separately present preparations, of which at least one preparation is aqueous and at least one preparation is non-aqueous and coated and which each contain at least one Oxofarbstoffvorprodukt. The coating consists of a material which, when the coated, nonaqueous preparation is added to the aqueous preparation, allows mixing of the components of both preparations. Furthermore, the invention relates to the use of these agents for dyeing keratin-containing fibers and to a process for dyeing keratin-containing fibers, in particular human hair.

Description

The Invention relates to means for coloring Keratinic fibers consisting of at least two spatially separated present preparations, of which at least one preparation aqueous and at least one preparation is non-aqueous and enveloped and each containing at least one Oxofarbstoffvorprodukt. Furthermore, the invention relates to the use of these agents for coloring keratinhaltiger Fibers and a process for dyeing keratin-containing fibers, especially human hair.

The Requirements that users of means of treatment keratinischer Provide fibers, in particular hair treatment products, to these means, have increased steadily over time. This led u. a. for that Means in many cases from an ever-growing Number of components exist to all the users desired Effects in as much as possible optimal way to achieve. With the complexity of these mixtures is increasing but also the number of drug combinations, although the desired Properties unfold in a single formulation, in particular if it is an aqueous mixture but are no longer stable on storage.

in the The area of hair treatment are known a number of means which are in the form of separate preparations which are either immediate be mixed before application to the hair or in separate Procedures are applied sequentially to the hair; to simplify the handling for the user and last but not least to minimize the packaging costs will be in the development new products wherever possible the formulation in the form of an agent sought.

• A Verbindungen, die eine reaktive Carbonylgruppe enthalten, mit Komponente
• B Verbindungen, ausgewählt aus (a) CH-aciden Verbindungen, (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen, (c) Aminosäuren, (d) aus 2 bis 9 Aminosäuren aufgebauten Oligopeptiden

gefärbt. Diese Färbemethode der Oxofärbung wird beispielweise in den Druckschriften WO-A1-99/18916, WO-A1-00/38638, WO-A1-01/34106 und WO-A1-01/47483 beschrieben. Die resultierenden Färbungen besitzen teilweise Farbechtheiten auf der keratinhaltigen Faser, die mit denen der Oxidationsfärbung vergleichbar oder diesen überlegen sind. Das mit der schonenden Oxofärbung erzielbare Nuancenspektrum ist sehr breit und die erhaltene Färbung weist oftmals eine große Brillanz und Farbtiefe auf. Die vorgenannten Komponenten A und B, im weiteren als Oxofarbstoffvorprodukte bezeichnet, sind im allgemeinen selbst keine Farbstoffe, und eignen sich daher jede für sich genommen allein nicht zur Färbung keratinhaltiger Fasern. In Kombination bilden sie in einem nichtoxidativen Prozess Farbstoffe aus.In particular, in the case of colorants which only allow staining by the chemical reaction of two dye precursors to form a dye, the separate storage of the respective reactants is advantageous. This advantage can also be used in the so-called oxo dyeing. In the context of oxo dyeing, the substrate to be colored is provided with an agent containing a combination of component

• A Compounds containing a reactive carbonyl group with component
• B Compounds selected from (a) CH-acidic compounds, (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds, (c) amino acids, (d) from 2 up to 9 amino acids oligopeptides

colored. This staining method of oxo staining is described, for example, in the publications WO-A1-99 / 18916, WO-A1-00 / 38638, WO-A1-01 / 34106 and WO-A1-01 / 47483. The resulting dyeings sometimes have color fastnesses on the keratin-containing fiber that are comparable or superior to those of the oxidation dyeing. The Nuancenspektrum achievable with the gentle oxo staining is very broad and the color obtained often has a great brilliance and color depth. The aforementioned components A and B, hereinafter referred to as Oxofarbstoffvorprodukte, are generally not themselves dyes, and are therefore each alone taken not for coloring keratin-containing fibers. In combination, they form dyes in a non-oxidative process.

Become the components A and B, which prior to application to the keratin-containing Fibers must be mixed stored separately, so the mixing process should be as uncomplicated and fast be formable and, as already said above, the additional Packaging costs as possible keep low. It should quickly create a homogeneous mixture, which allows a uniform dyeing of the fibers after application. The color reaction should be as possible take place in the hair to a coloring to achieve good color fastness. For this purpose is a fast resolution the serving essential.

The Document DE-A1-197 55 420 relates to agents for the treatment of keratin-containing Fibers consisting of two separately stored components directly in front the application are mixed. One of the components is to this Purpose of a serving surrounded, which dissolves in the other component, so that both components can mix. The application of this technique to the oxo dyeing is described in this document not described.

It has now been found that these requirements are met to a high degree if the component to be stored separately or the components to be stored separately are provided with a cladding which, when the preparations are combined, allow the components of both preparations to be mixed in a period of time acceptable to the user. As accepted by the user period can usually be considered an interval of up to 5 minutes, if the mixing process of both preparations with no further, complicated procedures, eg. B. constant stirring, is connected.

• • mindestens einer wässrigen Zubereitung (Zubereitung 1) und
• • mindestens einer davon räumlich getrennt und umhüllt vorliegenden nichtwässrigen Zubereitung (Zubereitung 2),

wobei

• i) eine Umhüllung der nicht-wässrigen Zubereitung aus einem Material besteht, das bei Zugabe der nicht-wässrigen Zubereitung zu der wässrigen Zubereitung eine Vermischung der Komponenten beider Zubereitungen ermöglicht und
• ii) eine der Zubereitungen als eine Komponente A mindestens eine reaktive Carbonylverbindung enthält und eine andere Zubereitung, welche keine Komponente A enthält, als Komponente B mindestens eine Verbindung, ausgewählt aus der Gruppe, die gebildet wird, aus aus (a) CH-aciden Verbindungen und (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen, enthält.

A first subject of the invention is thus an agent for dyeing keratinic fibers, which is prepared immediately before use

• • at least one aqueous preparation (preparation 1) and
• At least one spatially separated and coated non-aqueous preparation (preparation 2),

in which

• i) a coating of the non-aqueous preparation consists of a material which, when the non-aqueous preparation is added to the aqueous preparation, permits mixing of the components of both preparations, and
• ii) one of the preparations contains as component A at least one reactive carbonyl compound and another preparation which does not contain component A contains as component B at least one compound selected from the group consisting of (a) CH-acidic compounds and (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

The aqueous Formulations 1 preferably have a water content of at least 30 wt .-%, particularly preferably of at least 90 wt .-%, respectively based on the preparation 1, on. Under an aqueous Preparation 1 can also be understood water itself.

The non-aqueous Preparations 2 preferably have a water content below from 20% by weight, preferably below 12% by weight, more preferably below 8% by weight, more preferably below 4% by weight, in particular below 2% by weight, in each case based on the preparation 2 without wrapping material, on.

Of course, the teaching of the invention includes also means that can be mixed by mixing several spatially separated Preparations 1 if desired several, spatially separate, non-aqueous preparations 2, each according to the teaching of the invention wrapped are to be produced. This is especially the case when the color intensity or shade by adding a certain number of Portions of preparation 2 to a certain number of portions the preparation 1 by the consumer using a color table of the instructions for use should be determined. So the quality of the coloring can be customized adapted to the hair type of the consumer.

• a) von Aminen und deren Derivate unter Bindung von Iminen oder Oximen als Additionsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Additionsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung (Komponente A leitet sich in diesem Fall c) von einem Aldehyd ab)

an das Kohlenstoffatom der Carbonylgruppe der reaktiven Carbonylverbindung.In the context of oxo dyeing, reactive carbonyl compounds which form the actual dyestuff in the hair after reaction with a component B are used as component A in the colorant according to the invention. Preferred reactive carbonyl compounds are aldehydes and ketones in which the reactive carbonyl group is present either as a carbonyl group or derivatized or masked such that the reactivity of the carbon atom of the derivatized carbonyl group with respect to the compounds of component B is always present. These derivatives are preferably addition compounds

• a) amines and their derivatives with the binding of imines or oximes as addition compound
• b) of alcohols to form acetals or ketals as addition compound
• c) of water with formation of hydrates as addition compound (component A is derived in this case c) from an aldehyde)

to the carbon atom of the carbonyl group of the reactive carbonyl compound.

wobei

• • AR steht für Benzol, Naphthalin, Pyridin, Pyrimidin, Pyrazin, Pyridazin, Carbazol, Pyrrol, Pyrazol, Furan, Thiophen, 1,2,3-Triazin, 1,3,5-Triazin, Chinolin, Isochinolin, Indol, Indolin, Indolizin, Indan, Imidazol, 1,2,4-Triazol, 1,2,3-Triazol, Tetrazol, Benzimidazol, 1,3-Thiazol, Benzothiazol, Indazol, Benzoxazol, Chinoxalin, Chinazolin, Chinolizin, Cinnolin, Acridin, Julolidin, Acenaphthen, Fluoren, Biphenyl, Diphenylmethan, Benzophenon, Diphenylether, Azobenzol, Chromon, Cumarin, Diphenylamin, Stilben, wobei die N-Heteroaromaten auch quaterniert sein können,
• • R³ steht für ein Wasserstoffatom, eine C₁-C₆-Alkyl-, C₂-C₆-Acyl-, C₂-C₆-Alkenyl-, C₁-C₄-Perfluoralkyl-, eine ggf. substituierte Aryl- oder Heteroarylgruppe,
• • R⁴, R⁵ und R⁶ stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkyl-, C₁-C₆-Alkoxy-, C₁-C₆-Aminoalkyl-, C₁-C₆-Hydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkyloxygruppe, eine C₂-C₆-Acylgruppe, eine Acetyl-, Carboxyl-, Carboxylato-, Carbamoyl-, Sulfo-, Sulfato-, Sulfonamid-, Sulfonamido-, C₂-C₆-Alkenyl-, eine Aryl-, eine Aryl-C₁-C₆-alkylgruppe, eine Hydroxy-, eine Nitro-, eine Pyrrolidino-, eine Morpholino-, eine Piperidino-, eine Amino- bzw. Ammonio- oder eine 1-Imidazol(in)iogruppe, wobei die letzten drei Gruppen mit einer oder mehrerer C₁-C₆-Alkyl-, C₁-C₆-Carboxyalkyl-, C₁-C₆-Hydroxyalkyl-, C₂-C₆-Alkenyl-, C₁-C₆-Alkoxy-C₁-C₆-alkyl-, mit ggf. substituierten Benzylgruppen, mit Sulfo-(C₁-C₄)-alkyl- oder Heterozyklus-(C₁-C₄)-alkylgruppen substituiert sein können, wobei auch zwei der Reste aus R⁴, R⁵, R⁶ und -Z-Y-R³ zusammen mit dem Restmolekül einen ankondensierten gegebenenfalls substituierten 5-, 6- oder 7-Ring, der ebenfalls einen ankondensierten aromatischen Ring tragen kann, bilden können, wobei das System AR in Abhängigkeit von der Größe des Ringes weitere Substituenten tragen kann, die unabhängig voneinander für die gleichen Gruppen stehen können wie R⁴, R⁵ und R⁶,
• • Z steht für eine direkte Bindung, eine Carbonyl-, eine Carboxy-(C₁-C₄)-alkylen-, eine gegebenenfalls substituierte C₂-C₆-Alkenylen-, C₄-C₆-Alkadienylen-, Furylen-, Thienylen-, Arylen-, Vinylenarylen-, Vinylenfurylen-, Vinylenthienylengruppe, wobei Z zusammen mit der -Y-R³-Gruppe auch einen gegebenenfalls substituierten 5-, 6- oder 7-Ring bilden kann,
• • Y steht für eine Gruppe, die ausgewählt ist aus Carbonyl, einer Gruppe gemäß Formel (Ox2) und einer Gruppe gemäß Formel (Ox3),
  
  wobei
• • R⁷ steht für ein Wasserstoffatom, eine Hydroxygruppe, eine C₁-C₄-Alkoxygruppe, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe,
• • R⁸ und R⁹ stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine Arylgruppe oder bilden gemeinsam zusammen mit dem Strukturelement O-C-O der Formel (Ox3) einen 5- oder 6-gliederigen Ring.

Component A is preferably selected from compounds of the formula (Ox1),

in which

• • AR is benzene, naphthalene, pyridine, pyrimidine, pyrazine, pyridazine, carbazole, pyrrole, pyrazole, furan, thiophene, 1,2,3-triazine, 1,3,5-triazine, quinoline, isoquinoline, indole, indoline, Indolizine, indan, imidazole, 1,2,4-triazole, 1,2,3-triazole, tetrazole, benzimidazole, 1,3-thiazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, quinolizine, cinnoline, acridine, julolidine, Acenaphthene, fluorene, biphenyl, diphenylmethane, benzophenone, diphenyl ether, azobenzene, chromone, coumarin, diphenylamine, stilbene, where the N-heteroaromatics may also be quaternized,
• R ³ represents a hydrogen atom, a C ₁ -C ₆ alkyl, C ₂ -C ₆ acyl, C ₂ -C ₆ alkenyl, C ₁ -C ₄ perfluoroalkyl, an optionally substituted aryl or heteroaryl group,
• R ⁴ , R ⁵ and R ⁶ independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -aminoalkyl, C ₁ - C ₆ hydroxyalkyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy, C ₂ -C ₆ acyl, acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, Sulfonamide, sulfonamido, C ₂ -C ₆ alkenyl, an aryl, an arylC ₁ -C ₆ alkyl group, a hydroxy, a nitro, a pyrrolidino, a morpholino, a piperidino, an amino or ammonio or a 1-imidazole (in) amino group, the last three groups having one or more C ₁ -C ₆ -alkyl, C ₁ -C ₆ -carboxyalkyl, C ₁ -C ₆ - Hydroxyalkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl, with optionally substituted benzyl groups, with sulfo (C ₁ -C ₄ ) alkyl or heterocycle - (C ₁ -C ₄ ) -alkyl groups may be substituted, wherein two of the radicals of R ⁴ , R ⁵ , R ⁶ and -ZYR ³ together with the remainder of a fused molecule optionally substituted 5-, 6- or 7-ring, which may also carry a fused aromatic ring form, the system AR may carry depending on the size of the ring further substituents which may stand independently for the same groups as R ⁴ , R ⁵ and R ⁶ ,
• Z is a direct bond, a carbonyl, a carboxy (C ₁ -C ₄ ) -alkylene, an optionally substituted C ₂ -C ₆ -alkenylene, C ₄ -C ₆ -alkadienylene, furylene, Thienylene, arylene, vinylenarylene, vinylenfururylene, vinylenthienylene group, wherein Z together with the -YR ³ group can also form an optionally substituted 5-, 6- or 7-membered ring,
• • Y is a group which is selected from carbonyl, a group according to formula (Ox2) and a group according to formula (Ox3),
  
  in which
• R ⁷ represents a hydrogen atom, a hydroxy group, a C ₁ -C ₄ -alkoxy group, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl group,
• R ⁸ and R ⁹ independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, an aryl group or form together with the structural element OCO of the formula (Ox 3) a 5- or 6-membered ring.

Component A is more preferably selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxybutyrophenone, 4- Hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone, 2,4,6- Trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethylketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4- Morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4-carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4 , 4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7- Trihydroxyflavone, 4,5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluoro non, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3- dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4- Hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde 3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxy-benzaldehyde, 2-hydroxy-4-methoxy- benzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2, 4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-Tr imethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-methylbenzaldehyde, 2,4-dihydroxy-6-methyl- benzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxy-6-methylbenzaldehyde, 3,4-dihydroxy-2- methoxy-benzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4, 6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydrox y-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy 1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy 1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1 naphthaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-one methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8- hydroxy-1H, 5H-benzo [ij] ch inolizin-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),
2-indolealdehyde, 3-indolealdehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ', 3 ', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3-pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine , 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrin-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromon-3-aldehyde, 3- (5 'Nitro-2'-furyl) acrolein, 3- (2'-furyl) acrolein and imidazole-2-aldehyde,
1,3-diacetylbenzene, 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) acetophenone and 2- (3'-pyridoyl) acetophenone,
Benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4-diethylaminobenzylideneacetone, 3-Benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-benzylidenecyclohexanone, 2- (4'- Hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- (4'-dimethylaminobenzylidene) - 1,3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxy 3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone, 2 '- (4-hydroxybenzylidene ) -cyclopentanone, 2- (4'-dimethyl laminobenzylidene) cyclopentanone, 5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-piperidinophenyl) penta-2,4-dienal, 5 - (4-morpholinophenyl) penta-2,4-dienal, 5- (4-pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5 -dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- ( 4-morpholinophenyl) hexa-3,5-dien-2-one, 6- (4-pyrrolidinophenyl) hexa-3,5-dien-2-one,
5- (4-Dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy 3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzene dehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2, 6-Dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3- nitrosalicylaldehyde, 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4-dimethyl-3-carbazolaldehyde, 1,4,9-trimethyl-3-carbazolaldehyde,
4-Formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium-2-formyl-1-ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1 benzylpyridinium 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl-1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium, 2 Acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methylquinolinium, 6-formyl-1-methylquinolinium, 7-formyl-1-methylquinolinium, 8-formyl-1 methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl 1-benzyl-quinolinium, 7-formyl-1-benzyl-quinolinium, 8-formyl-1-benzyl-quinolinium, 5-formyl-1-allyl-quinolinium, 6-formyl-1-allyl-quinolinium, 7-formyl-1-allyl-quinolinium and 8 -Formyl-1-allyl-quinolinium, 5-acetyl-1-methyl-quinolinium, 6-acetyl-1-methyl-quinolinium, 7-acetyl-1-methyl-quinolinium, 8-acetyl-1-methyl-quinoline ium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium, 6-acetyl 1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquinolinium, 5-acetyl-1-allylquinolinium, 6-acetyl-1-allylquinolinium, 7-acetyl-1-allylquinolinium and 8 Acetyl-1-allyl quinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1,3-dimethyl-2- (4'-formylphenyl) benzimidazolium, 1, 3-Dimethyl-2- (4'-formylphenyl) imidazolium, 2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4'-methyl) Formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-furyl) -3-methylbenzothiazolium, 2- (5 '-Formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro -2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3,5-di methylbenzothiazolium benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate, tetrafluoroborate, isatin, 1-methylisatin, 1-allyl isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxy-isatin, quinisatin, 1-methyl-chinisatin, and any mixtures of the above compounds.

worin

• • R¹⁰, R¹¹und R¹² stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine Aminogruppe, eine C₁-C₆-Dialkylaminogruppe, eine Di(C₂-C₆-hydroxyalkyl)aminogruppe, eine Di(C₁-C₆-alkoxy-C₁-C₆-alkyl)aminoguppe, eine C₁-C₆-Hydroxyalkyloxygruppe, eine Sulfonylgruppe, eine Carboxylgruppe, eine Sulfonsäuregruppe, eine Sulfonamidogruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine C₂-C₆-Acylgruppe, eine Acetylgruppe oder eine Nitrogruppe,
• • Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• • R¹³ und R¹⁴ stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.

Benzaldehyde, cinnamaldehyde and naphthaldehyde and their derivatives, in particular with one or more hydroxyl, alkoxy or amino substituents, are used with particular preference as component A in the compositions according to the invention. Again, the compounds according to formula (Ox4) are preferred,

wherein

• R ¹⁰ , R ¹¹ and R ¹² independently of one another represent a hydrogen atom, a halogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, an amino group, a C ₁ -C ₆ - Dialkylamino group, a di (C ₂ -C ₆ hydroxyalkyl) amino group, a di (C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl) amino group, a C ₁ -C ₆ hydroxyalkyloxy group, a sulfonyl group, a carboxyl group , a sulfonic acid group, a sulfonamido group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group, an acetyl group or a nitro group,
• Z 'is a direct bond or a vinylene group,
• • R ¹³ and R ¹⁴ represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

Very particularly preferred compounds of component A are selected from the group consisting of vanillin, coniferyl aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3- dimethoxy-benzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-me ethylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3 Hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4- Ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4- Trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxy-3-methylbenzaldehyde, 2,4-dihydroxy-5-me ethylbenzaldehyde, 2,4-dihydroxy-6-methylbenzaldehyde, 2,4-dihydroxy-3-methoxy-benzaldehyde, 2,4-dihydroxy-5-methoxy-benzaldehyde, 2,4-dihydroxy-6-methoxy benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,4-dihydroxy-2-methylbenzaldehyde, 3,4-dihydroxy-5-methylbenzaldehyde, 3,4-dihydroxybenzaldehyde 6-methyl-benzaldehyde, 3,4-dihydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxy-benzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5- Trihydroxybenzaldehyde, 2,3,6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4- Methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2, 4-Dihydroxy-1-naphthaldehyde, 4-hydroxy-3-methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy 1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino 2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal.

The Compounds of component B are selected from (a) CH-acidic compounds and (b) compounds with primary or secondary Amino or hydroxy group selected from aromatic hydroxy compounds, primary or secondary aromatic amines and nitrogen-containing heterocyclic compounds. CH-acidic compounds have one attached to a carbon atom acidic hydrogen which is formed using a base to abstract from the carbon atom.

The CH-acidic compounds of component B are preferably selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1,2,3,3-Tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, Rhodanine, Rhodanine-3-acetic acid, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylacetate, 2-coumaranone, 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl-pyrazolin-5-one, Indan-1,2-dione, indan-1,3-dione, indan-1-one, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methyl-benzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-Trimethylchinoxaliniumiodid, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium-p-toluenesulfonate, 1,2,3-trimethylquinoxaluminum p-toluenesulfonate, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium hydrogensulphate, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-4,6-dimethyl-1,3-dipropyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxo-pyrimidinium hydrogensulphate and 2-dihydro-1,3,4,5,6-pentamethyl-2-oxopyrimidinium chloride.

in der

• • R¹⁵ für eine Hydroxy- oder eine Aminogruppe, die durch C₁-C₆-Alkyl-, C₁-C₆-Hydroxyalkyl-, C₁-C₆-Alkoxy- oder C₁-C₆-Alkoxy-C₁-C₆-alkylgruppen substituiert sein kann, steht,
• • R¹⁶, R¹⁷, R¹⁸, R¹⁹ und R²⁰ unabhängig voneinander für ein Wasserstoffatom, eine Hydroxy- oder eine Aminogruppe, die durch C₁-C₆-Alkyl-, C₁-C₆-Hydroxyalkyl-, C₁-C₆-Alkoxy-, C₁-C₆-Aminoalkyl- oder C₁-C₆-Alkoxy-C₁-C₆-alkylgruppen substituiert sein kann, stehen, und
• • Z'' für eine direkte Bindung, eine gesättigte oder ungesättigte, ggf. durch Hydroxygruppen substituierte Kohlenstoffkette mit 1 bis 4 Kohlenstoffatomen, eine Carbonyl-, Sulfonyl- oder Iminogruppe, ein Sauerstoff- oder Schwefelatom, oder eine Gruppe mit der Formel (Ox6)
  
  in der
• • Q eine direkte Bindung, eine CH₂- oder CHOH-Gruppe bedeutet,
• • Q' und Q'' unabhängig voneinander für ein Sauerstoffatom, eine NR²¹-Gruppe, worin R²¹ ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe oder C₁-C₆-Hydroxyalkylgruppe, wobei auch beide Gruppen zusammen mit dem Restmolekül einen 5-, 6- oder 7-Ring bilden können, bedeutet, die Gruppe O-(CH₂)_p-NH oder NH-(CH₂)_p'-O, worin p und p' 2 oder 3 sind, stehen und
• • o eine Zahl von 1 bis 4 bedeutet, wie insbesondere 4,4'-Diaminostilben und dessen Hydrochlorid, 4,4'-Diaminostilben-2,2'-disulfonsäure-mono- oder -di-Na-Salz, 4-Amino-4'-dimethylaminostilben und dessen Hydrochlorid, 4,4'-Diaminodiphenylmethan, 4,4'-Diaminodiphenylsulfid, 4,4'-Diaminodiphenylsulfoxid, 4,4'-Diaminodiphenylamin, 4,4'-Diaminodiphenylamin-2-sulfonsäure, 4,4'-Diaminobenzophenon, 4,4'-Diaminodiphenylether, 3,3',4,4'-Tetraaminodiphenyl, 3,3',4,4'-Tetraamino-benzophenon, 1,3-Bis-(2,4-diaminophenoxy)-propan, 1,8-Bis-(2,5-diaminophenoxy)-3,6-dioxaoctan, 1,3-Bis-(4-aminophenylamino)propan,, 1,3-Bis-(4-aminophenylamino)-2-propanol, 1,3-Bis-[N-(4-aminophenyl)-2-hydroxyethylamino]-2-propanol, N,N-Bis-[2-(4-aminophenoxy)-ethyl]-methylamin, N-Phenyl-1,4-phenylendiamin und Bis-(5-amino-2-hydroxyphenyl)-methan.

The primary and secondary aromatic amines of component B are preferably selected from the group consisting of N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine , 2,5-dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2 Hydroxymethyl-4-aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5-diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethol, 4-amino-3-ol methylphenol, 2- (2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminopheno xy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5- aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethylamino) phenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5- ( 2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2-hydroxymethylphenol, 2- (diethylaminomethyl) -4-aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1 Hydroxy-2-amino-5-methylbenzene, 1-hydroxy-2-amino-6-methylbenzene, 2-amino-5-acetamidophenol, 1,3-dimethyl-2,5-diaminobenzene, 5- (2-amino-5-methylbenzene) 3-hydroxypropylamino) -2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2-methylphenol , 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2-hydroxyethoxy) -toluene, 2,4-diamino-5-methylphenol, 3,5-diamino-2-methoxy-1-methylbenzene , 2-amino-4- (2-hydroxyethylamino) -anisole, 2,6-bis (2-hydroxyethylamino) -1-methylbenzene, 1,3-diamino -2,4-dimethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenylacetic acid, 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3-diaminobenzoic acid, 2 , 4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3-amino-4-hydroxybenzoic acid, 4-amino-3-hydroxybenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6-amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4- hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 1,3,5-triaminobenzene, 1,2,4- Triaminobenzene, 1,2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, pentaaminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobrcatechol, 4,6-diaminopyrogallol, 1- (2-H ydroxy-5-aminobenzyl) -2-imidazolidinone, 4-amino-2 - ((4 - [(5-amino-2-hydroxyphenyl) methyl] piperazinyl) methyl) phenol, 3,5-diamino-4-hydroxy-catechol, 1,4-bis (4-aminophenyl) -1,4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, nitro group containing amino compounds such as 3-amino-6-methylamino-2-nitro-pyridine, picric acid, [8 - [(4-amino-2-nitrophenyl) -azo] -7-hydroxynaphth-2-yl] -trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) -azo) -7-hydroxynaphth-2-yl] -trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2 -nitro-4- [bis (2-hydroxyethyl) amino] benzene, 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow No. 5), 1-amino-2- nitro-4 - [(2-hydroxyethyl) amino] benzene (HC Red No. 7), 2-chloro-5-nitro-N-2-hydroxyethyl-1,4-phenylenediamine, 1 - [(2-hydroxyethyl) amino] -2-nitro-4-amino-benzene (HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro o-toluidine, 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] -6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4 - [(2,3- dihydroxypropyl) amino] -5-chlorobenzene (HC Red No. 10), 2- (4-amino-2-nitroanilino) benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro 4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol-3,6-disulfonic acid disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy-4 -nitrophenylazo) -8-naphthol-3,6-disulphonic acid disodium salt (Palatinchrome green), 1-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulphonic acid disodium salt ( Gallion), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid disodium salt, 2,4-diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone-2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) -benzene, 2- [2- (Diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, in particular nitro group-containing anilines, such as 4-nitroaniline, 2-nitroaniline, 1,4-diamino-2-nitrobenzene, 1 , 2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2-nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2 Nitro-1-amino-4- [bis (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 1-amino-5-chloro-4- (2-hydroxyethylamino ) -2-nitrobenzene, aromatic anilines or phenols with a further aromatic radical, as shown in the formula (Ox5)

in the

• R ^{15 represents} a hydroxy or an amino group represented by C ₁ -C ₆ -alkyl, C ₁ -C ₆ -hydroxyalkyl, C ₁ -C ₆ -alkoxy or C ₁ -C ₆ -alkoxy-C ₁ C ₆ alkyl groups may be substituted,
• R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ independently of one another represent a hydrogen atom, a hydroxy or an amino group represented by C ₁ -C ₆ -alkyl, C ₁ -C ₆ -hydroxyalkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -aminoalkyl or C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl groups may be substituted, and
• • Z '' for a direct bond, a saturated or unsaturated, optionally substituted by hydroxy groups Carbon chain of 1 to 4 carbon atoms, a carbonyl, sulfonyl or imino group, an oxygen or sulfur atom, or a group of the formula (Ox 6)
  
  in the
• Q signifies a direct bond, a CH ₂ or CHOH group,
• • Q 'and Q''independently represent an oxygen atom, an NR ²¹ group, wherein R ^{21 is} a hydrogen atom, a C ₁ -C ₆ alkyl group or C ₁ -C ₆ hydroxyalkyl group, whereby both groups together with the remainder molecule may form a 5-, 6- or 7-membered ring, means the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _p '-O, wherein p and p' are 2 or 3, and
• O is a number from 1 to 4, such as in particular 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulfonic acid mono- or di-Na salt, 4-amino 4'-dimethylaminostilbene and its hydrochloride, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4 'Diaminobenzophenone, 4,4'-diaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenyl, 3,3 ', 4,4'-tetraaminobenzophenone, 1,3-bis- (2,4-diaminophenoxy) propane, 1,8-bis (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, 1,3-bis (4-aminophenylamino) -2 propanol, 1,3-bis [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl -1,4-phenylenediamine and bis (5-amino-2-hydroxyphenyl) -methane.

The nitrogen-containing heterocyclic compounds of the component B are preferably selected from the group consisting of 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-aminopyridine, 2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4-dimethylpyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) amine, 2,4-dihydroxy-5,6-diaminopyrimidine, 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino-4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6-methylpyrimidine, 3,5-diaminopyrazole, 3,5-diamino-1,2,4-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-aminoquinoline 4-aminoquinaldine, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino-aniline and indole and indoline derivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Farther as heterocyclic compounds according to the invention in DE-U1-299 08 573 disclosed hydroxypyrimidines are used. The aforementioned compounds can both in free form and in the form of their physiologically acceptable Salts, e.g. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used.

The Aromatic hydroxy compounds of component B are preferred selected from the group consisting of 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, Pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3-dimethylamino-phenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 1- (2,4-dihydroxyphenyl) acetic acid, 1- (3,4-dihydroxyphenyl) acetic acid , Gallic acid, 2,4,6-trihydroxybenzoic acid, acetophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino-4-hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

A number of hair treatment products are applied to the hair in a slightly heated form. Heating is typically achieved by combining components that release heat during mixing. A component is often an anhydrous salt which dissolves in an aqueous phase with release of heat; Alternatively, one can also use neutralization heats, mixture heats of liquid components, etc. The proportions of the components to be mixed in these cases are preferably adjusted so that the mixture within a very short time, ie a few seconds, a temperature slightly above the temperature of the human body, ie about 38 ° C, assumes. With this type of agent, it is therefore sufficient if the mixing of the components of the coated nonaqueous preparation with the components of the aqueous preparation A occurs within 5 minutes a temperature of 38 ° C is carried out. Apart from occasional shaking of the mixture, no further activities on the part of the user should be necessary.

The by far the most prevalent Number of hair treatment products are stored at room temperature and also applied to the hair at this temperature. According to one preferred embodiment The invention is the envelope the preparation 2 therefore chosen so that one Mixing of the components of preparations 1 and 2 within of a maximum of 5 minutes even at room temperature, d. H. especially a temperature of 20 ° C, takes place.

According to one preferred embodiment the invention is in the envelope of the preparation 2 to a capsule.

Appropriate wrappings in capsule form are known from pharmacy. One type of these capsules are Films in capsule form, in which the substances to be coated completely from a layer of the wrapping material are included and those wrapped Substances only after destruction the serving can be released again. Here come as materials for the serving preferably certain cellulose derivatives, polyacrylates, polymethacrylates, Polyvinylpyrrolidone and in particular polyvinyl alcohols into consideration. In this context, expressly refers to the monograph by K.H. Bauer, K. -H. Fromming and C. Leader, Pharmaceutical Technology, Gustav Fischer Verlag, Stuttgart, Jena, Lübeck, Ulm, 4th edition, 1997, pages 315-323, incorporated by reference.

two-piece Capsules usually consist of two cylindrical halves, the each closed at one end. Here is the inner diameter one half, which is also referred to as a capsule cap, slightly larger than the outside diameter the other half called capsule bottom, so that the two halves under wrapping the one to be included Components can be pushed together, the capsule by special devices are "locked." This type of capsules is also referred to as capsules and is a preferred according to the invention Serving. In principle, both gelantins and capsules come as capsule materials synthetic or natural Polymers into consideration. Polyvinyl alcohol has proven to be particularly suitable wrapping material proved.

According to one first preferred embodiment the entire plug-in capsule is made of polyvinyl alcohol.

It but can also be provided that only a part of the plug capsule, in particular the capsule cap or parts of the capsule cap, of water-soluble Material according to the definition of the invention consists. It is then possible for example, the capsule bottom of a less water-soluble Produce material. It is thus more flexible in attitude the desired mechanical properties, eg. As the rigidity of the capsules. Regarding this wrapping form is also on the above mentioned Monograph by K.H. Bauer, K.-H. Frömming and C. Leader, pages 324-335, incorporated by reference.

The wrapper can also be designed in the form of a small bag. Such bags are made in a known manner from polymer films, from which by welding or gluing the individual ingredients containing bags are made. Further information on such bags are, for example, the article by J. Korn, Die Neue Verpackung, 10, 1150-1155 (1962) and the EP 493 392 can be found in the bags made of polyvinyl alcohol for dust-free packaging of bleaching agents.

Farther it is preferred that the wrapping material consists of substances that are in colorants additionally still develop positive qualities. Also in this context is polyvinyl alcohol due to its conditioning properties a preferred wrapping material.

The Layer thickness of the envelope the specialist will choose that on the one hand a hermetic conclusion of the to be wrapped Preparation guaranteed on the other hand, however, the mixing of the preparations 1 and 2 not by a too thick envelope unnecessarily is slowed down. Strengthen the serving in the range of 10 to 30 microns have in the context of the teaching of the invention proved to be particularly suitable.

It is preferred according to the invention to select the coating for the preparation 2 such that the three-dimensional macroscopic surface of the coating of the preparation 2 is at least 10%, preferably at least 20%, more preferably between 20 and 100%, most preferably between 30 and 50% greater as the two-dimensional geometric surface.

The Determination of the three-dimensional surface is based on the reference surface determined, which has the shape of the geometric surface and in its position in the Room coincides with the main direction of the real surface.

The in comparison to the two-dimensional geometric surface enlarged three-dimensional macroscopic surface bears down to an improved water solubility of the preparation according to the invention 2 at.

at these servings it is preferred that at least one surface of the envelope is a three-dimensional Structure, preferably an impressed three-dimensional structure, having.

The Outside- and / or inner surface the serving can be at least 50%, preferably at least 70%, on preferably at least 90% and in particular substantially completely with a three-dimensional, preferably embossed, be provided structure.

in the Frame of the present invention denotes the inner surface of the wrapping the plane Area that contact the cosmetic preparation can. In the presence of a foil bag is thus the surface of the Foil in the bag interior, the inner surface and the film surface outside of the bag inside the outer surface. The Outside surface stands not in contact with the preparation 2.

at the one on a surface the serving impressed Structure is in a preferred embodiment around a regular imprinted three-dimensional Structure in the form of a pattern.

The impressed Structure points to the surface in a preferred embodiment a regular three-dimensional Pattern on. The regular pattern can have any conceivable form, such as checks, Diamonds, stamped cylinders, ovals, etc. In a preferred Embodiment exists the regular pattern in a periodically recurring array of elevations and Recesses of the envelope surface.

The embossed pattern can influence both the haptic properties of the coated preparation 2 and its dissolution rate. It has therefore proved to be advantageous for the embossed pattern to have at least 4, preferably at least 6, more preferably between 8 and 50, more preferably between 10 and 25 depressions or elevations per 1 cm ^{2 of} the two-dimensional surface. Embossed depressions or elevations in the context of the present invention have in their greatest extent at least a diameter of 2 μm and a depth or height of at least 2 μm, preferably at least 5 μm.

In a further preferred embodiment indicates the surface the serving circular and / or triangular and / or square and / or polygonal depressions on.

The surfaces the servings can but also in a further embodiment cuboid, round, angular, oval, sawtooth or triangular pointed to the surface ongoing increases exhibit.

In a preferred embodiment indicates the surface the serving a grid-shaped one or honeycomb three-dimensional textured pattern. These patterns are preferable imprinted or stamped on the envelope surface and thus give the surface a three-dimensional profile. In a preferred embodiment shows the envelope by imprinting a grid-shaped one or honeycomb Pattern's gridlines on. The gridlines are preferred formed by a juxtaposition of edges delimiting the recesses.

The preferred grid-shaped Patterns are preferably applied to the surfaces of the envelopes imprinted, so the ratio the average width of gridline to the maximum Extension of the plane of the recess less than 20: 1, preferably less than 10: 1, more preferably less than 1: 1, more preferably less than 0.5: 1 and in particular less than 0.25: 1.

Particularly in the case of embossed patterns, it has proved to be advantageous that the ratio of the average diameter of the depression to the depth of the depression is below 20: 1, preferably 10 : 1 to 1:10, especially 8: 1 to 1: 1, especially 6: 1 to 4: 1.

The preparations according to the invention 2 can wrappings have only one side impressed three-dimensional pattern have, especially only on the not with the cosmetic preparation outside in contact the envelope surface. Prefers It is, however, that the wrappings are bilateral an imprinted have three-dimensional structured pattern, d. h. that both the inside as well as the outside the serving this pattern is wearing.

Preferably have the preparations according to the invention 2 servings on, whose mean strength 10 to 100 μm, preferably 15 to 50 microns and in particular 20 to 40 microns is. The chosen ones Wear wrapping thicknesses in particular, when the sheaths are water-soluble and / or water dispersible films, at an optimum rate of water dissolution and also to a good processability of the films. So had shown to be particularly in the range of a medium film thicknesses between 10 and 100 μm thermal sealing, in particular liquid-tight sealing, carried out easily can be. The film thickness may be subregions or, preferably, the entire enveloping material Respectively. The mean film thickness refers to the cross-sectional profile and has been over the increases and depressions averaged along a 1 cm long profile line. A 1 square centimeter large foil piece (1 cm × 1 cm) of the wrapping material becomes equidistant in 5 Strip 2 mm in pieces) and in each case the mean film thickness along of the profile. The mean of the 5 measurements is the average film thickness. The determination of the average film thickness along the cross-sectional profile determined by video light microscopy.

The Material of water-soluble and / or water-dispersible coating of the preparation 2 in a preferred embodiment wholly or partly of a thermoplastic, selected from the group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, Polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, starch and Derivatives of the abovementioned substances and / or mixtures of the abovementioned polymers, wherein polyvinyl alcohol is particularly preferred.

The polyvinyl alcohols described above are commercially available, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and Clariant L648.

Further as a material for the sheath suitable polyvinyl alcohols are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).

In a further preferred embodiment has the wrapping material the preparation 2 in addition Polymers selected from the group comprising acrylic acid Polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, Polyurethanes, polyesters, polyethers and / or mixtures of the above Polymers, on.

It is preferred if the shell material of preparation 2 is a partially acetalized polyvinyl alcohol having a saponification degree of from 70 to 100 mol%, preferably from 80 to 96 mol%, particularly preferably from 82 to 94 mol% and in particular from 85 to 89 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl acetate whose average molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , more preferably from 12,000 to 80,000 gmol ^-1 , in particular from 13,000 to 70,000 gmol ^-1, and especially from 20,000 to 40,000 gmol ^-1 . The average molecular weights were determined by gel permeation chromatography. It has surprisingly been found that the dissolution rate can be significantly improved by the specific choice of the molecular weight.

In another embodiment, includes the wrapping material the thermoplastics mentioned in quantities of at least 50% by weight, preferably at least 70% by weight, more preferably at least 80% Wt .-% and in particular of at least 90 wt .-%, each based on the weight of the entire wrapping material.

The coating of the preparation 2 can be present in different forms of presentation, which is predetermined, for example, by the method for producing the coated preparation 2. In preferred Embodiments, the envelope of the preparation 2 in the form of bag, capsule, injection molding or thermoformed or blow molding, but particularly preferred are produced from polymer films bags, in particular by means of a thermoforming process or a bag sealing method.

According to one special embodiment the teaching of the invention it may be desired be that the wrapping the preparation 2 is designed so that a mixing of the preparation 2 with an aqueous medium as the preparation 1 only after a latency of 20, in particular 30 seconds takes place. This is for the case that, for example in a user with wet or wet hands, who has a capsule with the Preparation 2 in a vessel (eg. a bottle) with the preparation 1, already parts of the preparation while This process is already free on the hands.

The known in the art liquid dyeing systems for keratin materials contained as a solvent almost exclusively Water or mixtures of water with low molecular weight alcohols such as Ethanol and / or isopropanol. For the choice of these solvents play on the one hand a physiological viewpoints a role, for Other is a staining the hair inside only with suitable transport media and a reaction at reactive Ensures systems only with a suitable reaction medium. These conditions are for water or water / alcohol mixtures optimally fulfilled. The use of the cited solvent However, this is not just about benefits. So subject some dyes when stored in aqueous or aqueous-alcoholic Media of the hydrolysis or dissolve only insufficient. These disadvantages can in principle by a storage, for. B. overcome in powder form become. But this type of preparation does not always stop optimal solution So that's for one far-reaching solution Of all components necessary finely divided dispersion often not ensured.

In a further preferred embodiment Show the hair dye or hair dye precursors, in particular the component A of the oxohera dye, a water solubility below 5 wt .-%, preferably below 2 wt .-%, in particular below 1% by weight.

Suitable poorly water-soluble hair dye precursors are known from the German patent application DE 29 32 489 from which aromatic aldehydes are known, and from the German patent application DE 196 30 275 , in which vinylogous, aromatic aldehydes are described known. The cited references describe numerous compounds which have only a limited water solubility of less than 1 g / l (20 ° C.). Particular preference is given to the isatin derivatives known from WO 95/24886. Dyes selected from the group of isatin derivatives or aromatic or vinylogous carbonyl compounds are particularly preferred since these dyes are often sparingly soluble in water. These dye precursors are often used for the oxo dyeing. Particularly preferred cosmetic preparations comprise the 1-allyl isatin, the 1-diethylaminomethylisatin, the 1-diethylaminomethylisatin, the 1-pi-peridinomethylisatin, the 4-hydroxy-3-methoxycinnamaldehyde, the glutaconaldehyde tetra-butylammonium salt and the 2- (1,3 , acetaldehyde 3-trimethyl-2-indolylidene).

Preferably the dyes or dye precursors have a good oil solubility. Under oil soluble in In the context of the present invention, substances are understood their solubility in paraffin oil at 20 ° C above 0.1 wt .-% is.

It has been shown, in particular, for the production of non-aqueous Preparations 2 additional oils used can be. Preference is given to liquid oil components used.

The oil components are preferably at least 30% by weight, more preferably 90% Wt .-%, each based on the weight of non-aqueous Preparation without wrapping, in the non-aqueous Preparation included.

Liquid oil components For the purposes of the present invention, all physiologically acceptable, in 20 ° C liquid mineral, animal, vegetable or synthetic oil components. Examples of such oil components are z. B. paraffin oils, Silicone oils, triglyceride oils, z. Claw oil, lard oil, mink oil, Olive oil, sunflower oil, almond oil, liquid wax esters such as B. sperm oil, jojoba oil, synthetic esters such. Glycerol tricaprylate, n-hexyl laurate, Isopropyl myristate, 2-ethylhexyl stearate, Butyl oleate, synthetic ethers such. Di-n-octyl ether, synthetic Hydrocarbons such. As diisooctyl-cyclohexane, squalane, synthetic Alcohols such. For example, 2-octyl-dodecanol or 2-hexyl-decanol.

• a) Mineralöle, vorzugsweise Paraffinöle,
• b) pflanzliche Öle, vorzugsweise Sonnenblumenöl, Rapsöl, Sojabohnenöl, Rizinusöl,
• c) Silikonöle, vorzugsweise quarternisierte Silikone,
• d) Ester von C₁₀-C₃₆-Fettsäuren, vorzugsweise Ester von C₁₄-C₂₈-Fettsäuren und
• e) Dialkylether mit mindestens einem Kohlenstoffrest, der 6 oder mehr Kohlenstoffatome trägt.

Particularly preferably, the preparations 2 additionally contain an oil selected from the group

• a) mineral oils, preferably paraffin oils,
• b) vegetable oils, preferably sunflower oil, rapeseed oil, soybean oil, castor oil,
• c) silicone oils, preferably quaternized silicones,
• d) esters of C ₁₀ -C ₃₆ fatty acids, preferably esters of C ₁₄ -C ₂₈ fatty acids and
• e) dialkyl ethers having at least one carbon radical bearing 6 or more carbon atoms.

• a) Alkali- oder Erdalkalisalze, vorzugsweise Alkali- oder Erdalkalihalogenide und/oder -sulfate, insbesondere Caliumchlorid und/oder Magnesiumsulfat und/oder dehydratisierte Zeolithe und
• b) niedermolekulare Polyole, vorzugsweise Glycerin, Propylenglycol oder Polyethylenglycol.

In a further preferred embodiment, the preparations 2 advantageously contain components which release a heat of hydration when dissolved in the aqueous preparation 1 and lead to an improved color lift due to the heat development, in particular in hair dye preparation. The cosmetic preparations preferably contain one or more components having an exothermic solubility behavior in water, preferably selected from the group

• a) alkali metal or alkaline earth metal salts, preferably alkali or alkaline earth halides and / or sulfates, in particular calcium chloride and / or magnesium sulfate and / or dehydrated zeolites and
• b) low molecular weight polyols, preferably glycerol, propylene glycol or polyethylene glycol.

• a) Ester oder Amide von Di-, Tri-, Tetra- oder Polyolen, insbesondere Dextrin ein oder mehrfach verestert mit Palmitinsäure oder N-Lauroyl-1-glutaminsäure,α,γ-di-n-butylamid,
• b) Ester von Di- oder Oligocarbonsäuren, insbesondere Di-behenylfumarsäureester,
• c) Schichtsilikaten, vorzugsweise organisch modifizierte, insbesondere hydrophob modifizierte Schichtsilikate,
• d) Mono- oder Diglyceride von C₁₂-C₂₂-Fettsäuren
• e) Alkali-, Erdalkali- und Aluminiumsalze von Fettsäuren und/oder Hydroxycarbonsäuren, insbesondere die Lithiumsalze von C3-C14-Hydroxycarbonsäuren,
• f) Pigmente von SiO₂ und/oder TiO₂, (Aerosil^®, Degussa) besonders bevorzugt solche mit einer mittleren Partikelgröße unterhalb von 100 μm, insbesondere unterhalb von 100 μm,
• g) Polyole, vorzugsweise Polyethylenglycole und/oder Polypropylenglycole, besonders bevorzugt Polyole mit einem mittleren Molekulargewicht unterhalb von 20000,
• h) Dibenzyliden-Sorbitole sowie deren Derivate,
• i) Copolymere mit Aminodithiazolen,
• j) Pfropfcopolymere von Polyvinylpyridin mit sulfoniertem Polyisobutylen,
• k) Vernetzte Polyamine und/oder Polyimine
• l) Polymere ausgewählt aus i) Gummi-basierten Blockcopolymeren, ii) Silikonölen mit einer Viskosität oberhalb von 2000 mPas, iii) mikrokristalline Wachse und
• m) Ethylen-Vinylacetat-Copolymere.

For the non-aqueous, preferably oil-containing preparations 2, it has surprisingly been found that the viscosity build-up of non-polar or semi-polar oils necessary for the stable finely divided dispersion can be achieved by various additives. In a preferred embodiment of the present invention, the preparations 2 comprise one or more viscosity-regulating additives which are selected from

• a) esters or amides of di-, tri-, tetra- or polyols, in particular dextrin one or more times esterified with palmitic acid or N-lauroyl-1-glutamic acid, α, γ-di-n-butylamide,
• b) esters of di- or oligocarboxylic acids, in particular di-phenyl fumaric acid esters,
• c) phyllosilicates, preferably organically modified, in particular hydrophobically modified phyllosilicates,
• d) mono- or diglycerides of C ₁₂ -C ₂₂ fatty acids
• e) alkali, alkaline earth and aluminum salts of fatty acids and / or hydroxycarboxylic acids, in particular the lithium salts of C3-C14-hydroxycarboxylic acids,
• f) pigments from SiO ₂ and / or TiO _2, (Aerosil ^®, Degussa) Particularly preferred are those having an average particle size below 100 micron, in particular below 100 microns,
• g) polyols, preferably polyethylene glycols and / or polypropylene glycols, more preferably polyols having an average molecular weight below 20,000,
• h) dibenzylidene sorbitols and their derivatives,
• i) copolymers with aminodithiazoles,
• j) graft copolymers of polyvinylpyridine with sulfonated polyisobutylene,
• k) Crosslinked polyamines and / or polyimines
• l) polymers selected from i) rubber-based block copolymers, ii) silicone oils having a viscosity above 2000 mPas, iii) microcrystalline waxes and
• m) ethylene-vinyl acetate copolymers.

Particularly preferred as viscosity-regulating additives for the coated, non-aqueous preparations Dibenzylidensorbitole and their derivatives have been found in the US 6,338,841 B1 be described and whose content is included in the application. Further preferred are the copolymers with aminodiazoles, as described in the US 5,472,627 are described and their contents are explicitly referred to. Also preferred are graft copolymers of polyvinylpyridine with sulfonated polyisobutylene as described in US Pat US 5,328,960 are described and their contents are fully incorporated into this application. Further preferred are the crosslinked polyamines and / or polyimines, as disclosed explicitly in WO 01/46373 A1. Also particularly preferred are the esters of di- or oligocarboxylic acids, in particular dibehenyl fumaric acid esters, as disclosed in WO 99/51191. Further preferred viscosity-regulating additives are polymers selected from I) rubber-based block copolymers, II) silicone oils having a viscosity above 2000 mPas, III) microcrystalline waxes, as described in WO 98/30193. The lithium salts of C ₃ -C ₁₄ -hydroxycarboxylic acids, as explicitly described in WO 98/11180, have proven to be particularly advantageous for the formation of viscosity in low-water hair dye systems. Also advantageously usable are ethylene-vinyl acetate copolymers, as described in WO 97/07158, the contents of which are fully incorporated into this application.

The Preparations 1 and 2 can about that addition, other active and auxiliary adjuvants included.

In many cases, the colorants contain at least one surfactant, wherein in principle both anionic as well as zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. It has proven to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

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

Suitable anionic surfactants in preparations are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 or 3 C 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 alkyl group having 10 to 22 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 10 to 18 C atoms in the acyl group,
• Acyltaurides having 10 to 18 C atoms in the acyl group,
• Acyl isethionates having 10 to 18 C atoms in the acyl group,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Linear alkanesulfonates having 12 to 18 C atoms,
• - linear alpha-olefin sulfonates having 12 to 18 C atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in which R is a preferably linear alkyl group having 10 to 18 C atoms and x = 0 or 1 to 12,
• Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
• Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,
• Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
• - esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

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

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

Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

• Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide onto linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids containing 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,
• C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs, and
• - Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil.

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

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

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

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

Particular preference is given to those alkylpolyglycosides in which R ¹

• Consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• Essentially of C ₁₂ and C ₁₄ alkyl groups,
• - Substituted from C ₈ -C ₁₆ alkyl groups or
• - Consists essentially of C ₁₂ -C ₁₆ alkyl groups.

When Sugar component Z can any mono- or oligosaccharides are used. Usually Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Such sugars are, for example, glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, Gulose, idose, talose and sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The usable according to the invention Alkyl polyglycosides contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x 1.1 to 1.4.

The Alkyl glycosides can in addition to their surfactant effect also serve the fixation of fragrance components to improve on the hair. The person skilled in the art will therefore be that one over the effect of the perfume oil beyond the duration of the hair treatment the hair desired is, preferably to this class of substance as a further ingredient the preparations according to the invention To fall back on.

Also The alkoxylated homologs of said alkyl polyglycosides can be used according to the invention become. These homologs can 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 cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^(-) or -SO ₃ ^(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C _12-18 acylsarcosine.

According to the invention as cationic surfactants, especially those of the quaternary ammonium type, the esterquats and amidoamines used.

preferred quaternary Ammonium compounds are ammonium halides, especially chlorides and Bromides such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, Lauryldimethylbenzylammoniumchlorid and tricetylmethylammonium chloride, as well as those under the INCl designations Quaternium-27 and quaternium-83 known imidazolium compounds. The long alkyl chains of the above surfactants are preferred 10 to 18 carbon atoms.

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

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

Further usable according to the invention cationic surfactants are the quaternized protein hydrolysates represents.

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

at it may be the compounds with alkyl groups used as surfactant each are uniform substances. It is, however, in usually preferred in the preparation of these substances by native to go out with vegetable or animal raw materials, so that one Substance mixtures with different, from the respective raw material dependent alkyl chain lengths receives.

at the surfactants, the adducts of ethylene and / or propylene oxide represent fatty alcohols or derivatives of these addition products, can both products with a "normal" homolog distribution as well as those with a narrow homolog distribution become. Under "normal" homolog distribution are understood to mean mixtures of homologs which are used in the Reaction of fatty alcohol and alkylene oxide using alkali metals, Alkali metal hydroxides or alkali metal alcoholates as catalysts receives. Narrowed homolog distributions are obtained when, 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 narrow homolog distribution may be preferred.

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

enthaltenFurthermore, the colorants according to the invention further active ingredients, auxiliaries and additives, such as

• Nonionic polymers such as vinyl pyrrolidone / vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers and polysiloxanes,
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
• 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, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,
• Thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
• - Protein hydrolysates, especially elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
• Fiber-structure-improving active substances, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose,
• Quaternized amines such as methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate
• Defoamers like silicones,
• Dyes for staining the agent,
• Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole,
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, such as, for example, customary acids, in particular edible acids and bases,
• - active substances such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,
• Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ , C, E, F and H,
• - Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime, wheat, Kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root ,.
• - cholesterol,
• Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,
• - fats and waxes such as spermaceti, beeswax, montan wax and paraffins,
• Fatty acid alkanolamides,
• Complexing agents such as EDTA, NTA, β-alaninediacetic acid and phosphonic acids,
• - swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
• Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers
• Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,
• - pigments,
• Stabilizer for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain

Regarding further optional components as well as the amounts of these components used expressly on the specialist manuals known to those skilled in the art, eg. B. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

Of the pH value of the agents according to the invention in the application may be in principle between 2-11, with a preferred pH range is at pH 6 to 9. To adjust the pH can virtually any for cosmetic Purpose usable acid be used. Usually are consumed acids used. Under Be enjoyment acids such acids understood that under the usual Food intake and positive effects to have the human organism. Acetic acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and Gluconic. In the context of the invention is the use of citric acid and lactic acid particularly preferred.

Regarding further Components as well as quantity ranges for the individual ingredients is based on the well-known manuals, z. B. K. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, referenced.

One second object of the invention is the use of an agent of the first subject of the invention for dyeing keratin-containing fibers, especially human hair.

A third object of the invention is finally a process for coloring keratin fibers, in particular human hair, in which the preparations 1 and 2 of an agent of the first subject of the invention are combined and applied the inventive composition after complete mixing of the ingredients applied to the hair and optionally after a Exposure time from 10 seconds to 45 Mi rinsed again.

• a) mindestens eine getrennt konfektionierte, umhüllte, nicht-wässrige Zubereitung, enthaltend mindestens ein Oxofarbstoffvorprodukt, ausgewählt aus reaktiven Carbonylverbindungen (Komponente A) sowie
• b) gegebenenfalls mindestens eine getrennt konfektionierte, umhüllte, nicht-wässrige Zubereitung enthaltend mindestens ein Oxofarbstoffvorprodukt der Komponente B,
• c) mindestens eine getrennt konfektionierte wässrige Zubereitung, enthaltend mindestens ein Oxofarbstoffvorprodukt der Komponente B wobei Komponente B mindestens eine Verbindung, ausgewählt aus der Gruppe, die gebildet wird, aus (a) CH-aciden Verbindungen und (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen, bedeutet.

A fourth object of the invention is a kit of parts for providing the colorant of the first article of the invention in which

• a) at least one separately formulated, coated, nonaqueous preparation containing at least one Oxofarbstoffvorprodukt selected from reactive carbonyl compounds (component A) and
• b) optionally at least one separately formulated, coated, nonaqueous preparation comprising at least one oxo dye precursor of component B,
• c) at least one separately prepared aqueous preparation containing at least one Oxofarbstoffvorprodukt of component B wherein component B at least one compound selected from the group consisting of (a) CH-acidic compounds and (b) compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

• a) mindestens eine getrennt konfektionierte, umhüllte, nicht-wässrige Zubereitung, enthaltend mindestens ein Oxofarbstoffvorprodukt der Komponente B sowie
• b) gegebenenfalls mindestens eine getrennt konfektionierte, umhüllte, nicht-wässrige Zubereitung enthaltend mindestens ein Oxofarbstoffvorprodukt der Komponente A, ausgewählt aus reaktiven Carbonylverbindungen
• c) mindestens eine getrennt konfektionierte wässrige Zubereitung, enthaltend mindestens ein Oxofarbstoffvorprodukt der Komponente A, ausgewählt aus reaktiven Carbonylverbindungen, wobei Komponente B mindestens eine Verbindung, ausgewählt aus der Gruppe, die gebildet wird, aus (a) CH-aciden Verbindungen und (b) Verbindungen mit primärer oder sekundärer Aminogruppe oder Hydroxygruppe, ausgewählt aus primären oder sekundären aromatischen Aminen, stickstoffhaltigen heterozyklischen Verbindungen und aromatischen Hydroxyverbindungen, bedeutet.

Furthermore, the Oxofarbstoffvorprodukte can also be distributed inversely to the preparations, so as to give the following sales unit containing

• a) at least one separately formulated, coated, nonaqueous preparation containing at least one Oxofarbstoffvorprodukt of component B and
• b) optionally at least one separately formulated, coated, nonaqueous preparation containing at least one Oxofarbstoffvorprodukt of component A, selected from reactive carbonyl compounds
• c) at least one separately prepared aqueous preparation comprising at least one oxo dye precursor of component A selected from reactive carbonyl compounds, wherein component B comprises at least one compound selected from the group formed from (a) CH-acidic compounds and (b) Compounds having primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

• a) Behältnis zum Anmischen und Auflösen der umhüllten Zubereitung und/oder
• b) ein oder mehrere Behältnisse) enthaltend mindestens eine weitere kosmetische Zubereitung, vorzugsweise eine Wasserstoffperoxid-Lösung oder Wasserstoffperoxid-Emulsion oder eine Pflegelotion; und/oder
• c) eine Vorrichtung zum Vermischen oder Rühren und/oder
• d) ein oder mehrere Sicherheitsmaterialien zur Vermeidung des unerwünschten Inkontakttretens der kosmetischen Zubereitung mit dem menschlichen Körper, vorzugsweise Handschuhe.

In a further preferred embodiment, the kit according to the invention additionally contains one or more constituents selected from the group

• a) container for mixing and dissolving the coated preparation and / or
• b) one or more containers) containing at least one further cosmetic preparation, preferably a hydrogen peroxide solution or hydrogen peroxide emulsion or a care lotion; and or
• c) a device for mixing or stirring and / or
• d) one or more safety materials to prevent the undesirable contact of the cosmetic preparation with the human body, preferably gloves.

Example 1:

It the following preparations were prepared:

Table 1

Both Preparations were at 80 ° C with stirring heated. At this temperature, in both cases clear, low-viscosity Liquids, when cooling down to room temperature to clear, medium-viscosity gels thickened.

• • 0,75 g Dimethylaminobenzaldehyd
• • 1,2 g Methocel^® E4M und
• • 0,5 g Arginin

in der wässrigen Zubereitung

• • 0,85 g 1,2-Dihydro-1,3,4,6-tetramethyl-2-oxopyridiniumchlorid und
• • 3,6 g eines bei Raumtemperatur (20°C) flüssigen C₈-C₁₀-Fettalkoholgemisches homogen dispergiert.

In the non-aqueous preparations were after cooling

• • 0.75 g of dimethylaminobenzaldehyde
• • 1.2 g Methocel ^® E4M and
• • 0.5 g arginine

in the aqueous preparation

• 0.85 g of 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyridinium chloride and
• • 3.6 g of a liquid at room temperature (20 ° C) C ₈ -C ₁₀ fatty alcohol mixture homogeneously dispersed.

The following raw materials were used: Cremophor ^® RH 40: Castor oil, hydrogenated with 40-45 ethylene oxide units (INCl designation: PEG-40 Hydrogenated Castor Oil) (BASF) Rheopearl ^® KL: Dextrin palmitate (Miyoshi Kasei) Cetiol ^® B: Di-n-butyl Dehydol ^® LS 3: Lauryl Alcohol 3 EO (Cognis Deutschland GmbH) Methocel ^® E4 M: hydroxypropyl methylcellulose

to Preparation of the non-aqueous coated according to the invention Preparations were the non-aqueous Preparations I and II each separately by means of a tubular bag sealing method in a water-soluble PVA polymer film (Solublon, type SA 20 ex Syntana) and then thermally packaged liquid-tight sealed.

The envelope of the tubular bag has the following properties: root mean square roughness: 30 μm average thickness of the film: 20 μm Film material: partially saponified polyvinyl acetate with a saponification degree of 96%; cast; average molecular weight: 36,000 g / mol

Outdoor and inner surfaces the polymer film are three-dimensionally structured with a karoförmigen pattern. The pattern is formed by a grid with square pits, so that the gridlines are formed by the edges of the depressions become.

The Depth of the recess is 0.12 mm.

The impressed Checks have a diameter of 0.6 mm.

bag 1, containing the non-aqueous Preparation I and bag 2 containing the non-aqueous preparation II, were in a watery Preparation stirred in from 80 ml of water at 40 ° C. The result was a good flowable emulsion.

A with this formulation in the weight ratio of 4: 1 30 minutes at 32 ° C be colored strand of hair (Kerling natural white) was intensely nuanced magenta.

Example 2:

It the following preparation were prepared:

Table 2

The following raw materials were used: Dehydol ^® LS 2: Lauryl alcohol-2 EO (Cognis Deutschland GmbH) Eumulgin ^® B2: Cetylstearyl alcohol with 20 moles of ethylene oxide (Cognis Deutschland GmbH) Stenol ^® 1618: C ₁₆ / C ₁₈ fatty alcohol mixture (Cognis Deutschland GmbH) Cutina ^® GMS: Glycerol monostearate (Cognis Deutschland GmbH) Eumulgin ^® B1: Cetylstearyl alcohol with 12 moles of ethylene oxide (Cognis Deutschland GmbH) Cetiol ^® 868:

The Ingredients of non-aqueous Preparation was at 80 ° C heated. In the hot Mixture was dissolved 0.6 g of N-allyl isatin. Subsequently was with stirring cooled to room temperature. The recipe was analogous to Example 1 in a corresponding Packed tubular bag.

To Dissolve the shrouded, non-aqueous Preparation in the aqueous Preparation was the staining a blond strand of hair (Kerling natural white, 30 minutes, 32 ° C). The color of the strand was Titian red.

Claims (11)

Dyeing agent keratinic fibers, which is prepared immediately before use will be out • at least an aqueous Preparation (Preparation 1) and • at least one of them spatially separated and enveloped present non-aqueous Preparation (preparation 2), in which i) an envelope of the non-aqueous Preparation consists of a material that when added to the non-aqueous Preparation to the aqueous Preparation allows mixing of the components of both preparations and ii) one of the preparations as a component A at least one reactive Contains carbonyl compound and another preparation containing no component A, as Component B at least one compound selected from the group formed is made from (a) CH-acidic compounds and (b) compounds with primary or secondary Amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds. Means according to claim 1, characterized in that the envelope a Mixing of the components of both preparations at 38 ° C within of 5 minutes. Agent according to claim 1 or 2, characterized that the wrapping the non-aqueous Preparation is a capsule or sachet. Composition according to claim 3, characterized in that the thickness of the casing is 10 to 30 micrometers is Agent according to one of claims 1 to 4, characterized that the wrapping at least partially made of polyvinyl alcohol. Agent according to one of claims 1 to 5, characterized in that the coated, non-aqueous Preparations at least one liquid oil component contain. Agent according to one of claims 1 to 6, characterized in that the coated, non-aqueous preparations additionally at least one or more viscosity-regulating additives selected from the group consisting of esters or amides of di-, tri-, tetra- or Polyols, esters of dicarboxylic acids, esters of oligocarboxylic acids, phyllosilicates, mono- or diglycerides of C ₁₂ -C ₂₂ fatty acids, alkali, alkaline earth and aluminum salts of fatty acids, alkali, alkaline earth and aluminum salts of hydroxycarboxylic acids, pigments of SiO ₂ , Pigments of TiO ₂ , polyols, dibenzylidene sorbitols and their derivatives, copolymers with aminodithiazoles, graft copolymers of polyvinylpyridine with sulfonated polyisobutylene, crosslinked polyamines and / or polyimines, rubber-based block copolymers, silicone oils with a viscosity above 2000 mPas, microcrystalline waxes and ethylene -Vinylacetat copolymers. Agent according to one of claims 1 to 7, characterized that the non-aqueous Preparation in addition at least one compound with an exothermic solubility behavior at solution in water. Use of an agent according to one of claims 1 to 8 for coloring keratin-containing fibers, especially human hair. Method of coloring keratin-containing fibers, characterized in that the preparations 1 and 2 of a composition according to one of claims 1 to 8 are combined and the resulting agent after complete mixing of the ingredients applied to the hair and optionally after a contact time rinsed off from 10 seconds to 45 minutes. Kit-of-parts, containing a) at least one made-up, wrapped, non-aqueous A preparation containing at least one oxo dye precursor selected from reactive carbonyl compounds (component A) as well b) if applicable at least one separately formulated, coated, non-aqueous preparation containing at least one oxo dye precursor of the component B c) at least one separately prepared aqueous preparation, containing at least one oxo dye precursor of the component B wherein component B at least one compound selected from of the group formed from (a) CH-acidic compounds and (b) compounds with primary or secondary Amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.