DE102006012575A1 - Silazanes or metal-amides, -imides and/or -nitrides are used in agents for dyeing or brightening keratin fibers to reduce or virtually eliminate the need to include ammonia - Google Patents

Abstract

Use is claimed of silazanes or metal-amides, -imides and/or -nitrides in agents for dyeing and/or brightening keratin fibers, especially in ammonia-reduced or -free agents. Use is claimed of silazanes or metal-amides, -imides and/or -nitrides of formula Mn+>(NH2-x)n/x (sic : given as this in claim 14 but as Mn+>(NH3-x)n/x elsewhere in the specification) in agents for dyeing and/or brightening keratin fibers, especially in ammonia-reduced or -free agents. M : a main Group I - IV or sub-Group I - VIII metal; and n, x : 1, 2 or 3. An independent claim is included for a dyeing and/or brightening keratin fiber agent containing by weight: ammonia (no more than 2% calculated as 100% NH3); and (i) a silazane and/or (ii) a metal-amide, -imide and/or -nitride of formula Mn+>(NH3-x)n/x.

Description

The The present invention relates to agents for coloring and / or lightening keratinic Fibers, i. Agent for use on keratin fibers, in particular human hair, and their use.

The change The shape and color of the hair represents an important area of the hair This can change the appearance of the hair both current fashion trends as well as the individual wishes adapted to the individual person become. It can Perming and other hair shape changing procedures almost independent of Type of hair to be treated to be used. In contrast, dyeing and Bleaching procedure limited to certain initial hair colors. The Basics of the Blondierverfahren are known in the art and can in relevant Monographs, e.g. by Kh. Schrader, Foundations and Recipes of Kosmetika, 2nd edition, 1989, Dr. med. Alfred Hüthig Verlag, Heidelberg, or W. Umbach (ed.), Cosmetics, 2nd edition, 1995, Georg Thieme Verlag, Stuttgart, New York, can be read.

simultaneously But there is also often the desire to change the hair color and along with the hair coloring also a whitening of the to be colored To reach hair.

conventional Hair Dye usually consist of at least one developer and at least a coupler substance and optionally contain direct dyes as a nuance. Coupler and developer components are also known as Oxidation dye precursors referred.

In front their application to human hair will be hair dyeing and / or lightening agent in solid or pasty form mixed with dilute aqueous hydrogen peroxide solution. This mixture is then applied to the hair and after a rinsed out certain exposure time again. The exposure time on the Hair to achieve a complete coloration or brightening is between about 30 and 45 minutes. It is obvious, that at There is a need for users of these hair dyes or bleaching agents to do this Reduce exposure time.

Neither the pasty ones still the powdery dyeing and / or bleaching agents that are on the market today can be considered as be optimally viewed. While the dyeing and / or bleaching effect on the hair than on the consumer needs can be called tailored, but there is still a number disadvantages and problems both in manufacture and in the handling of these agents.

So Coloring and bleaching processes usually take place on keratinic fibers at alkaline pH values, in particular between 9.0 and 10.5. These pH values are necessary to an opening of the outer cuticle (cuticle) to ensure and a penetration of the active species (dye precursors and / or Hydrogen peroxide) in the hair. As alkalizing agent is usually ammonia used, however, for the users the disadvantage of intense smell and possible irritation having.

In Market products are used as alternative alkalizing agents to ammonia For example, aminomethylpropanol or monoethanolamine used. However, since they often lag behind ammonia in their performance, they usually become used in admixture with ammonia. But again, the performance of the Ammonia, especially with regard to the parameters gray covering, whitening performance and color result.

It Therefore, there is still a need for active ingredients or drug combinations for lightening and coloring agents with reduced ammonia content. In particular, should be reduced in ammonia or even -free dye and / or hydrogen peroxide-containing Formulations one with conventional ammonia-based funds comparable performance can be achieved.

It it has now been found that certain drug combinations with particular advantage in hair dyeing and incorporate brightening agent and to increase performance lead this means.

• a) maximal 2 Gew.-% Ammoniak (berechnet als 100 %iges NH₃);
• b) 0,01 bis 25 Gew.-% mindestens eines Stoffes aus der Gruppe der b1) Silazane und/oder b2) Metallamide und/oder -imide und/oder -nitride der Formel Mⁿ⁺(NH_3-x)_n/x in der M für ein Metall der I. und/oder II. und/oder III. und/oder IV. Hauptgruppe und/oder der I. und/oder II. und/oder III. und/oder IV. und/oder V. und/oder VI. und/oder VII und/oder VIII. Nebengruppe des Periodensystems steht und n bzw. x für die ganzen Zahlen 1, 2, 3 stehen.

The invention is in a first embodiment, a means for dyeing and / or Aufhel len keratinischer fibers containing - in each case based on its weight -

• a) at most 2% by weight of ammonia (calculated as 100% NH ₃ );
• b) 0.01 to 25 wt .-% of at least one substance from the group of b1) silazanes and / or b2) metal amides and / or imides and / or nitrides of the formula M ^{n +} (NH _{3 -x} ) _{n / x} in the M for a metal of the I. and / or II. and / or III. and / or IV. Main group and / or the I. and / or II. and / or III. and / or IV. and / or V. and / or VI. and / or VII and / or VIII. Subgroup of the Periodic Table and n and x are the integers 1, 2, 3.

The agents according to the invention can as a dyeing agent and / or as a means of lightening keratinischer fibers become. Among keratinic or keratin fibers are in For the purposes of this application, furs, wool, feathers and, in particular, human ones Hair understood.

The agents according to the invention optionally contain ammonia (calculated as 100% NH ₃ ), the amount of which is limited to a maximum of 2% by weight, based on the total agent or, in the case of multi-component agents, of the ready-to-use mixture. Preferred agents or application mixtures according to the invention contain at most 1.8% by weight of ammonia, more preferably at most 1.5% by weight of ammonia, even more preferably not more than 1.25% by weight of ammonia, particularly preferably not more than 1.0% by weight. -% ammonia and in particular at most 0.5 wt .-% ammonia. In a further preferred embodiment of the present invention, the agents are ammonia-free.

As an essential constituent, the compositions according to the invention contain from 0.01 to 25% by weight of at least one substance from the group of the silazanes and / or the metal amides and / or imides and / or nitrides of the formula M ^{n +} (NH ₃ -x) _{n / x} in the M for a metal of the I. and / or II. and / or III. and / or IV. Main group and / or the I. and / or II. and / or III. and / or IV. and / or V. and / or VI. and / or VII and / or VIII. Subgroup of the Periodic Table and n and x are the integers 1, 2, 3.

In a first embodiment contain the agents of the invention 0.01 to 25 wt .-% of at least one substance from the group of silazanes. Silazanes are compounds having at least one Si-N-Si sequence in the skeleton. They arise both through the implementation of lithiated aminosilanes with halosilanes as well as by reaction of ammonia or primary amines or their alkali metal salts with halosilanes. Are at the silicon atoms instead of organic radicals, amino groups or halogens are bonded an extension Silazankette or a ring closure possible.

According to preferred means for dyeing and / or lightening keratinischer fibers are characterized in that they are 0.01 to 25 wt .-%, preferably 0.05 to 20 wt .-%, particularly preferably 0.1 to 15 wt .-% and in particular 0.25 to 10 wt .-% of at least one silazane of the formula X- [SiR ¹ R ² -NH-SiR ³ R ⁴ ] _n -Y in which X or Y are a chemical bond or the radicals R ⁵ and R ⁶ , R ¹ to R ^{6 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , - (CH ₂ ) ₂ CH ₃ , -CH ₂ (CH ₃ ) ₂ , -OH, -NH ₂ and n are the integers 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

If X and Y for are a chemical bond, there is a cyclo-silazane, otherwise a hexasubstituted disalazane (n = 2), an octasubstituted trisilazane (n = 3) or a decasubstituted tetrasilazane, generally a (2n + 2) -substituted n-silazane. Among the silazanes according to the invention are some Representative particularly preferred. Means for dyeing and / or lightening keratinischer Fibers, the 1,1,1,3,3,3-hexamethyldisilazane and / or 1,1,1,3,3,3-hexaethyldisilazane and / or 1,1,1,3,3,3-hexapropyldisilazane and / or 1,1,1,3,3,3-hexaisopropyldisilazane and / or 1,1,1,3,3,5,5,5-octamethyltrisilazane and / or 1,1,1,3,3,5,5,7,7,7-decamethyltetrasilazane and / or 1,1,1,3,3,5,5,7,7,9,9,9-tridecamethylpentasilazane and / or cyclo-1,1,3,3,5,5-hexamethyltrisilazane and / or cyclo-1,1,3,3,5,5,7,7-octamethyltetrasilazane are preferred embodiments of the present invention.

Particularly preferred are agents which are 0.01 to 25 wt .-%, preferably 0.05 to 20 wt .-%, particularly preferably 0.075 to 15 wt .-%, more preferably 0.1 to 10 wt .-% and in particular 0.15 to 5 wt .-% 1,1,1,3,3,3-hexamethyldisilazane and / or 1,1,1,3,3,3-hexaethyldisilazane and / or 1,1,1,3,3,5,5,5-octamethyltrisilazane and / or 1,1,1,3,3,5,5,7,7,7-decamethyltetrasilazane and / or 1,1,1, 3,3,5,5,7,7,9,9,9-Tridecamethylpentasilazane.

In addition to the silazanes or in their place, the agents according to the invention may contain from 0.01 to 25% by weight of metal amides and / or imides and / or nitrides of the formula M ^{n +} (NH ₃ -x) _{n / x} in which M for a metal of I. and / or II. and / or III. and / or IV. Main group and / or the I. and / or II. and / or III. and / or IV. and / or V. and / or VI. and / or VII and / or VIII. Subgroup of the Periodic Table and n and x are the integers 1, 2, 3. In compositions according to the invention which contain both silazanes and also metal amides and / or imides and / or nitrides, the total amount of these substances is from 0.01 to 25% by weight.

Particular preference is given to agents for dyeing and / or lightening keratinic fibers which contain 0.01 to 25% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight and in particular 0, From 25 to 10% by weight of at least one metal amide and / or imide and / or nitride of the formula Mn ⁺ (NH3 _-x ) _{3 / x} in which M is Na, K, Mg, Ca, Si, Al, Zn, Mg, Cu and n and x are the integers 1, 2, 3, the following compounds being particularly preferred: Mg (NH ₂ ) ₂ , Ca (NH ₂ ) ₂ , LiAl (NH ₂ ) ₄ , LiAl (NH) ₂ , Zn (NH ₂ ) ₂ , Mg (NH), Ca (NH), Zn (NH), Mg ₃ N ₂ , Ca ₃ N ₂ , Zn ₃ N ₂ .

As already mentioned, can the agents according to the invention also directly before the application of two or more separately packaged Preparations are prepared. This is particularly suitable to separate incompatible ingredients to a premature one To avoid reaction.

• b1) Silazane und/oder
• b2) Metallamide und/oder -imide und/oder -nitride der Formel Mⁿ⁺(NH_3-x)_n/x in der M für ein Metall der I. und/oder II. und/oder III. und/oder IV. Hauptgruppe und/oder der I. und/oder II. und/oder III. und/oder IV. und/oder V. und/oder VI. und/oder VII und/oder VIII. Nebengruppe des Periodensystems steht und n bzw. x für die ganzen Zahlen 1, 2, 3 stehen, enthält.

Another object of the present invention is therefore an agent for dyeing and / or whitening keratinic fibers, in particular human hair, which immediately before application to the hair from a flowable preparation A, an oxidizing agent preparation B containing at least one oxidizing agent selected from hydrogen peroxide and whose addition compounds to solid carriers and a preparation C, which are mixed together to form a dyeing and / or Aufhellansatz obtained, wherein the composition C - based on their weight - 1 to 100 wt .-% of at least one substance from the group of

• b1) silazanes and / or
• b2) metal amides and / or imides and / or nitrides of the formula M ^{n +} (NH _{3 -x} ) _{n / x} in the M for a metal of the I. and / or II. and / or III. and / or IV. Main group and / or the I. and / or II. and / or III. and / or IV. and / or V. and / or VI. and / or VII and / or VIII. Subgroup of the Periodic Table and n or x are the integers 1, 2, 3 contains.

The Mixture of preparations A, B and C before use leads to a Application mixture, the silazanes and / or metal amides and / or imides and / or nitrides. In addition, preferred application mixtures satisfy the first embodiment of the present invention, i. particularly preferred means of second embodiment are so made up and / or are in such a relationship with each other mixed that the Application mixture 0.01 to 25 wt .-% silazanes and / or metal amides and / or imides and / or nitrides.

Especially the preparations A and B are preferably mixed with one another in one weight ratio from 4: 1 to 1: 4, preferably 3: 1 to 1: 3, more preferably 2: 1 to 1: 2 and especially 1: 2 to 1: 1.5 mixed. Preferred mixing ratios from (A + B) to C are in the range of 120: 1 to 1: 1, preferably from 100: 1 to 1.5: 1, more preferably from 80: 1 to 2: 1, and especially from 50: 1 to 3: 1.

The Ingredients of preparations A, B and C are described below. The following comments on preferred Ingredients, preferred quantities, etc. apply mutatis mutandis also for them Application mixture and therefore for the Einkomponentenmittel disclosed above, which also additionally some or all of the other ingredients listed below can contain.

Preferably are the agents of the invention as brightening agent (hereinafter also referred to as bleaching agent) and / or as a colorant provided. Agents which at the same time have a coloring and lightening effect, are also called lightening colorants designated.

preferred inventive agent are colorants, i.e. Means of change the color of keratinous fibers. Among these are in particular the so-called oxidation colorants prefers. The oxidation colorants of the invention contain at least one coupler and at least one developer component. Coupler and developer components are also known as oxidation dye precursors designated. In addition, you can the oxidation colorants of the invention also contain direct dyes as Nuanceure. According to the invention preferred Dyeing agent and / or lightening keratinic fibers are thus characterized that the flowable preparation A at least one developer-type oxidation dye precursor and / or coupler type.

When Developer components are usually primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, Diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

Specific Representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxamido-4-amino-pyrazol-5-one, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-4-hydroxypyrimidine.

When Coupler components are usually m-phenylenediamine derivatives, Naphthols, resorcinol and resorcinol derivatives, pyrazolones, m-aminophenols and substituted pyridine derivatives. As coupler substances Particularly suitable are α-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4- (2-hydroxyethylamino) -anisole (Lehmann's Blue), 1-phenyl-3-methyl-pyrazol-5-one, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl, 5-methylresorcinol, 3-amino-6-methoxy-2-methylaminopyridine and 3,5-diamino-2,6-dimethoxypyridine.

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

sowie Mischungen von Vertretern dieser Gruppen enthalten.With regard to the further dyestuff precursors which can be used in the dyestuffs according to the invention, the present invention is not subject to any restrictions. The colorants according to the invention can be used as further dye precursors

• - Developer and / or coupler type oxidation dye precursors, and
• Precursors of nature-analogous dyes, such as indole and indoline derivatives,

and mixtures of representatives of these groups.

In a first preferred embodiment contains the colorant at least one developer component. As developer components become common primary aromatic amines with another, in para or ortho position free or substituted hydroxy or amino group, Diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used.

wobei

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

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

in which

• G ¹ represents a hydrogen atom, a C ₁ to C ₄ alkyl radical, a C ₁ to C ₄ monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl radical, a C ₁ to C ₄ alkoxy radical (C ₁ - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C ₁ - to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• G ² represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ to C ₄ polyhydroxyalkyl, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl or a C ₁ to C ₄ alkyl substituted with a nitrogen containing group;
• G ³ represents a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₁ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ -acetylaminoalkoxy radical, a C ₁ - to C ₄ -mesylaminoalkoxy radical or a C ₁ - to C ₄ -carbamoylaminoalkoxy radical;
• - G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or
• When G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C ₁ - to C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (E1) are, in particular, the amino groups, C ₁ - to C ₄ -monoalkylamino groups, C ₁ - to C ₄ -dialkylamino groups, C ₁ - to C ₄ -trialkylammonium groups, C ₁ - to C ₄ -monohydroxyalkylamino groups, Imidazolinium and ammonium.

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

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

It can continue according to the invention be preferred to use as a developer component compounds, which contain at least two aromatic nuclei which are reactive with amino and / or hydroxyl groups are substituted.

wobei:

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

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

in which:

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

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

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

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

wobei:

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

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

in which:

• - G ¹³ is a hydrogen atom, a halogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ Alkoxy (C ₁ to C ₄ ) alkyl, C ₁ to C ₄ aminoalkyl, hydroxy (C ₁ to C ₄ ) alkylamino, C ₁ to C ₄ hydroxyalkoxy, C ₁ - to C ₄ -hydroxyalkyl- (C ₁ - to C ₄ ) -aminoalkyl or a (di-C ₁ - to C ₄ -alkylamino) - (C ₁ - to C ₄ ) -alkyl, and
• - G ¹⁴ represents a hydrogen or halogen atom, a C ₁ - to C ₄ alkyl, C ₁ - to C ₄ monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ Alkoxy (C ₁ to C ₄ ) alkyl, C ₁ to C ₄ aminoalkyl or C ₁ to C ₄ cyanoalkyl,
• G ¹⁵ is hydrogen, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a phenyl radical or a benzyl radical, and
• - G ¹⁶ is hydrogen or a halogen atom.

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

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

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

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

Farther For example, the developer component may be selected from heterocyclic Developer components, such as the pyridine, pyrimidine, Pyrazole, pyrazole pyrimidine derivatives and their physiologically tolerable Salt.

preferred Pyridine derivatives are in particular the compounds 2,5-diamino-pyridine, 2- (4'-Methoxyphenyl) amino-3-amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

preferred Pyrimidine derivatives are in particular 2,4,5,6-tetraaminopyrimidine, 4-Hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

preferred Pyrazole derivatives are in particular 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) -pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-Methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

wobei:

• – G¹⁷, G¹⁸, G¹⁹ und G²⁰ unabhängig voneinander stehen für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest einen (C₁- bis C₄)-Alkoxy-(C₁- bis C₄)-alkylrest, einen C₁- bis C₄-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)-alkyl]-(C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄)-[Hydroxyalkyl]-(C₁- bis C₄)-aminoalkylrest,
• – die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen C₁- bis C₄-Alkylrest, einen Aryl-Rest, einen C₁- bis C₄-Hydroxyalkylrest, einen C₂- bis C₄-Polyhydroxyalkylrest, einen C₁- bis C₄-Aminoalkylrest, einen (C₁- bis C₄)-Alkylamino-(C₁- bis C₄)-alkylrest, einen Di-[(C₁- bis C₄)alkyl]- (C₁- bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen C₁- bis C₄-Hydroxyalkyl- oder einen Di-(C₁- bis C₄-hydroxyalkyl)aminoalkylrest, einen Aminorest, einen C₁- bis C₄-Alkyl- oder Di-(C₁- bis C₄-hydroxyalkyl)aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• – i hat den Wert 0, 1, 2 oder 3,
• – p hat den Wert 0 oder 1,
• – q hat den Wert 0 oder 1 und
• – n hat den Wert 0 oder 1, mit der Maßgabe, dass
• – die Summe aus p + q ungleich 0 ist,
• – wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG¹⁷G¹⁸ und NG¹⁹G²⁰ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• – wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG¹⁷G¹⁸ (oder NG¹⁹G²⁰) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

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

in which:

• - G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -Polyhydroxyalkylrest a (C ₁ - to C ₄ ) alkoxy- (C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -Aminoalkylrest, optionally protected by an acetyl-ureide or a sulfonyl radical may be a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle with 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl- or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to C ₄ ) aminoalkyl radical,
• - The X radicals independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a C ₁ - to C ₄ -aminoalkyl, a (C ₁ - to C ₄ ) -alkylamino- (C ₁ - to C ₄ ) -alkyl, a di - [(C ₁ - to C ₄ ) alkyl] - (C ₁ - bis C ₄ ) aminoalkyl radical, wherein the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) amino alkyl radical, an amino radical, a C ₁ - to C ₄ -alkyl or di- (C ₁ - to C ₄ -hydroxyalkyl) amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1, with the proviso that
• The sum of p + q is not equal to 0,
• If p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);
• When p + q is 1, n is 1, and the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the group OH occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7);

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

Unter den Pyrazolo[1,5-a]pyrimidinen der obenstehenden Formel (E4) kann man insbesondere nennen:

• – Pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,5-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – Pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 2,7-Dimethyl-pyrazolo[1,5-a]pyrimidin-3,5-diamin;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-7-ol;
• – 3-Aminopyrazolo[1,5-a]pyrimidin-5-ol;
• – 2-(3-Aminopyrazolo[1,5-a]pyrimidin-7-ylamino)-ethanol;
• – 2-(7-Aminopyrazolo[1,5-a]pyrimidin-3-ylamino)-ethanol;
• – 2-[(3-Aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxy-ethyl)amino]-ethanol;
• – 2-[(7-Aminopyrazolo(1,5-a]pyrimidin-3-yl)-(2-hydroxy-ethyl)amino]-ethanol;
• – 5,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 2,6-Dimethylpyrazolo[1,5-a]pyrimidin-3,7-diamin;
• – 3-Amino-7-dimethylamino-2,5-dimethylpyrazolo[1,5-a]pyrimidin;

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.When the pyrazolo [1,5-a] pyrimidine of the above formula (E4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium represented, for example, in the following scheme:

In particular, among the pyrazolo [1,5-a] pyrimidines of the above formula (E4):

• - pyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 2,5-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - pyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 2,7-dimethylpyrazolo [1,5-a] pyrimidine-3,5-diamine;
• 3-aminopyrazolo [1,5-a] pyrimidin-7-ol;
• 3-aminopyrazolo [1,5-a] pyrimidin-5-ol;
• 2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;
• - 2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;
• - 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol;
• - 2 - [(7-aminopyrazolo (1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) amino] -ethanol;
• 5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• - 2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;
• 3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine;

and their physiologically acceptable salts and their tautomeric forms when a tautomeric equilibrium is present.

The Pyrazolo [1,5-a] pyrimidines of the above formula (E4) can be used as described in the literature by cyclization starting from a Aminopyrazole or produced from hydrazine.

Particularly according to the invention preferred oxidation colorants are characterized in that the developer component selected is from 3-methyl-1,4-diaminobenzene, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, 2- (2,5-diaminophenoxy) ethanol, N, N-bis (2'-hydroxyethyl) -1,4-diaminobenzene, 3-methyl-4-aminophenol and 2-methylamino-4-aminophenol, p-phenylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) -methane, N, N'-bis (4'-aminophenyl) -1,4-diazacycloheptane, 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-fluorophenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ((diethylamino) methyl) phenol, o-aminophenol, 2-amino-4-methylphenol, 2-amino-5-methylphenol, 2-amino-4-chlorophenol, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6- triaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, 1- (2'-hydroxy-5'-aminobenzyl) -imidazolidin-2-one, 4,5-diamino-1- (2'-hydroxyethyl) pyrazole and N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine trihydrochloride.

According to the invention preferred Dyeing agent and / or lightening keratinic fibers are characterized that she as oxidation dye precursor at least one developer component containing preferred developer components are selected p-phenylenediamine, p-toluenediamine, N, N-bis (2-hydroxyethyl) amino-p-phenylenediamine, 1,3-bis - [(2-hydroxyethyl-4'-aminophenyl) amino] propane-2-ol, 1,10-bis (2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane, 4-aminophenol, 4-amino-3-methylphenol, bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole.

in the Case of the multi-component agent according to the second embodiment The present invention provides the oxidation dye precursors of the developer type preferably contained in the preparation A.

The Colorants according to the invention can furthermore contain at least one coupler component.

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

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

sowie deren physiologisch verträglichen Salze.According to preferred coupler components are

• - M-aminophenol and its derivatives such as 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl 3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'-hydroxyethyl) - amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4-dichloro 3-aminophenol,
• O-aminophenol and its derivatives,
• - M-Diaminobenzene and its derivatives such as 2,4-diaminophenoxy-ethanol, 1,3-bis (2 ', 4'-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2'-hydroxyethylamino ) benzene, 1,3-bis (2 ', 4'-diaminophenyl) -propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [( 2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1 amino-3-bis- (2'-hydroxyethyl) aminobenzene,
• O-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,
• Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene,
• Pyridine derivatives such as 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3, 4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,
• Naphthalene derivatives such as, for example, 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,
• Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,
• Pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole,
• Pyrimidine derivatives such as 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino 4-hydroxy-6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or
• Methylene dioxybenzene derivatives such as, for example, 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1- (2'-hydroxyethyl) amino-3,4-methylenedioxybenzene,

and their physiologically acceptable salts.

Particularly according to the invention preferred coupler components are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine.

When Precursors of naturally-analogous dyes are preferably those indoles and indolines containing at least one hydroxy or amino group, preferably as a substituent on the six-membered ring. These groups can carry further substituents, e.g. in the form of etherification or Esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

in der unabhängig voneinander

• – R¹ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine C₁-C₄-Hydroxy-alkylgruppe,
• – R² steht für Wasserstoff oder eine -COOH-Gruppe, wobei die -COOH-Gruppe auch als Salz mit einem physiologisch verträglichen Kation vorliegen kann,
• – R³ steht für Wasserstoff oder eine C₁-C₄-Alkylgruppe,
• – R⁴ steht für Wasserstoff, eine C₁-C₄-Alkylgruppe oder eine Gruppe -CO-R⁶, in der R⁶ steht für eine C₁-C₄-Alkylgruppe, und
• – R⁵ steht für eine der unter R⁴ genannten Gruppen,

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Particularly suitable precursors of natural-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (Ia),

in the independently of each other

• R ¹ is hydrogen, a C ₁ -C ₄ -alkyl group or a C ₁ -C ₄ -hydroxy-alkyl group,
• R ² is hydrogen or a -COOH group, where the -COOH group may also be present as a salt with a physiologically compatible cation,
• R ³ is hydrogen or a C ₁ -C ₄ -alkyl group,
• R ⁴ is hydrogen, a C ₁ -C ₄ -alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -alkyl group, and
• R ⁵ is one of the groups mentioned under R ⁴ ,

and physiologically acceptable salts of these compounds with an organic or inorganic acid.

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

Especially noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and in particular the 5,6-dihydroxyindoline.

in der unabhängig voneinander

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

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

in the independently of each other

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

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

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

The Indoline and indole derivatives can in the used in the context of the method according to the invention coloring both as free bases and in the form of their physiologically acceptable Salts with inorganic or organic acids, e.g. the hydrochlorides, the sulfates and hydrobromides used. The indole or Indoline derivatives are common in these in amounts of 0.05-10 wt .-%, preferably 0.2-5 wt .-%.

In a further embodiment it may be preferred according to the invention be the indoline or Indolderivat in hair dyes in combination with at least one amino acid or an oligopeptide. The amino acid is advantageous an α-amino acid; all particularly preferred α-amino acids Arginine, ornithine, lysine, serine and histidine, especially arginine.

Particularly according to the invention preferred oxidation colorants are characterized in that the coupler component selected is from m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, Pyrazolones, m-aminophenols and substituted pyridine derivatives, preferred agents resorcinol, 3-amino-2-methylamino-6-methoxypyridine, 3-amino-6-methylphenol, 3-amino-2-hydroxypyridine, 1,3-bis (2,4-diaminophenoxy) propane, 2,7-dihydroxynaphthalene, 2-methylresorcinol, 5-methyl resorcinol, 2,5-dimethylresorcinol and 4-chlororesorcinol 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, Resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxy-3,4-dimethylpyridine, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-Hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and / or 2 - [(3-morpholin-4-yl-phenyl) -amino] -ethanol dihydrochloride.

According to the invention preferred Dyeing agent and / or lightening keratinic fibers are characterized that she as oxidation dye precursor at least one coupler component containing preferred coupler components are selected from resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3-amino-4-chloro-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-Amino-2,4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2'-hydroxyethyl) amino-anisole sulfate, 1,3-bis (2,4-diaminophenoxy) propane, 2-amino-3-hydroxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-phenyl-3-methylpyrazol-5-one, 2,6-bis - [(2'-hydroxyethyl) amino] -toluene, 4-hydroxyindole, 6-hydroxyindole, 6-hydroxybenzomorpholine.

in the Case of the multi-component agent according to the second embodiment The present invention provides the oxidation dye precursors of the coupler type preferably contained in the preparation A.

Preferably become coupler and developer components in a certain ratio to each other used. Here are oxidation colorants according to the invention preferably, the coupler component (s) in an amount of 0.01 to 20 wt .-%, preferably from 0.5 to 5 wt .-%, and the developer component (s) in from 0.01 to 20% by weight, preferably from 0.5 to 5% by weight, each based on the total oxidation colorant included.

Additionally, the colorants may contain one or more substantive dyes for shade. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis ( β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2'-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4 -methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene , 4-Amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro 4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

According to the invention preferred An oxidation are characterized in that they at least one substantive dye-containing is selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of international Names or trade names of known dyes HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 Compounds and 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) -aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-Amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

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

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

• (a) cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,
• (b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as
• (c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned, for example, in EP-A2-998 908, which is incorporated herein by reference, in claims 6 to 11.

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

The Compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also available under the terms Basic Yellow 87, Basic Orange 31 and Basic Red 51 are very particularly preferred cationic substantive Dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^®, according to the invention are also very particularly preferred cationic direct dyes.

The agents according to the invention according to this embodiment contain the substantive dyes preferably in an amount from 0.01 to 20 wt .-%, based on the total colorant.

Farther can the preparations according to the invention also occurring in nature dyes such as, for example in henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, Sedre and alkano root are included.

In summary, agents according to the invention for dyeing and / or brightening keratinic fibers are preferred which comprise at least one substantive dye selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of dyes HC known under the international names or trade names HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1 , HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis- (β-) hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4- methyl 2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-ureidoethyl) amino-4-nitrobenzene, 4 -Amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4 nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

It it is not necessary that the oxidation dye precursors or the direct dyes in each case uniform compounds represent. Rather, you can in the hair colorants according to the invention by the manufacturing processes for the individual dyes, be contained in minor amounts still other components as far as these are not the dyeing result adversely affect or for other reasons, e.g. toxicological, must be excluded.

Regarding the in the hair dyeing and -tönungsmitteln applicable dyes is still expressly on the monograph Ch. Zviak, The Science of Hair Care, Chapter 7 (pp. 248-250; Dyes) and chapter 8, pages 264-267; Oxidation dye precursors) appeared as volume 7 of the series "Dermatology" (ed. Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, as well as the "European Inventory of cosmetic raw materials ", issued by the European Community, available in diskette form from the German Association of Industrial and Trade Companies for Medicines, Health food and personal care products e.V., Mannheim.

A coloring Keratinic fibers can also be made by means of dyes which in an oxidatively catalyzed reaction of C, H-acidic compounds be formed with reactive carbonyl compounds.

• 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.

In a further embodiment, the agent according to the invention therefore contains 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.

• a) Aminen und deren Derivate unter Bildung von Iminen oder Oximen als Kondensationsverbindung
• b) von Alkoholen unter Bildung von Acetalen oder Ketalen als Kondensationsverbindung
• c) von Wasser unter Bildung von Hydraten als Additionsverbindung.

Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component A) have at least one carbonyl group as reactive group which reacts with the compounds of component B to form a chemical bond linking both components. Furthermore, those compounds according to the invention are also included as component A in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to component B is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with

• a) amines and derivatives thereof to form imines or oximes as a condensation compound
• b) of alcohols to form acetals or ketals as a condensation compound
• c) of water to form hydrates as addition compound.

Component A is 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 diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4-aminoacetophenone, 4- Dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-S-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-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8-dihydroxyanthrone, vanillin, coniferylaldehyde, 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-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxybenzaldehyde 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-trimetho xybenzaldehyde, 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, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 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, 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-naphthaldeh yd, 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-methoxy-cinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 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, piperonal, 2,3, 6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1H, 5H-benzo [ij] quinolizine-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, chromone-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'-dimethylaminobenzylidene) -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-diene-2-o n, 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-nitrobenzaldehyde, 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-fo methylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitro cinnamaldehyde, 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-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquinoline um, 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-methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-ethylquinolinium, 5-Acetyl-1-benzyl-quinolinium, 6-acetyl-1-benzyl-quinolinium, 7-acetyl-1-benzyl-quinolinium, 8-acetyl-1-benzyl-quinolinium, 5-acetyl-1-allyl-quinolinium, 6-acetyl-1 allylquinolinium, 7-acetyl-1-allylquinolinium and 8-acetyl-1-allylquinolinium, 9-formyl-10-methylacridinium, 4- (2'-formylvinyl) -1-methylpyridinium, 1,3-dimethyl-2 - (4'-formyl-phenyl) -benzimidazolium, 1,3-dimethyl-2- (4'-formyl-phenyl) -imidazolium, 2- (4'-formyl-phenyl) -3-methyl-benzothiazolium-2- (4'-acetyl-phenyl) 3-methylbenzothiazolium, 2- (4'-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-dimethylbenzothiazolium 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-nitroisatin, 6- Nitro-isatin, 5-sulfoisatin, 5-carboxyisatin, quinisatin, 1-methylquinisatin, and any mixtures of the above compounds.

worin

• • R^1*, R^2* und R^3* stehen unabhängig voneinander für ein Wasserstoffatom, ein Halogenatom, eine C₁-C₆-Alkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, 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 Carboxygruppe, eine Sulfonsäuregruppe, eine Sulfonamidogruppe, eine Sulfonamidgruppe, eine Carbamoylgruppe, eine C₂-C₆-Acylgruppe oder eine Nitrogruppe,
• • Z' steht für eine direkte Bindung oder eine Vinylengruppe,
• • R^4* und R^5* stehen für ein Wasserstoffatom oder bilden gemeinsam, zusammen mit dem Restmolekül einen 5- oder 6-gliederigen aromatischen oder aliphatischen Ring.

Benzaldehyde, cinnamic aldehyde and naphthaldehyde and their derivatives, in particular having one or more hydroxyl, alkoxy or amino substituents, are very particularly preferably used as the reactive carbonyl compound in the agents according to the invention. Again, the compounds according to formula (Ca-1) are preferred,

wherein

• R ^{1 *} , R ^{2 *} and R ^{3 *} 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, a C ₁ -C ₆ - Dialkylamino group, di (C ₂ -C ₆ hydroxyalkyl) amino group, di (C ₁ -C ₆ alkoxy-C ₁ -C ₆ alkyl) amino group, C ₁ -C ₆ hydroxyalkyloxy group, sulfonyl group, carboxy group , a sulfonic acid group, a sulfonamido group, a sulfonamide group, a carbamoyl group, a C ₂ -C ₆ acyl group or a nitro group,
• Z 'is a direct bond or a vinylene group,
• • R ^{4 *} and R ^{5 *} represent a hydrogen atom or together form, together with the remainder of the molecule, a 5- or 6-membered aromatic or aliphatic ring.

The derivatives of the benzaldehydes, naphthaldehydes or cinnamaldehydes of the reactive carbonyl compound according to component C are particularly preferably selected from certain aldehydes. Preferred herein are agents which additionally contain at least one reactive carbonyl compound selected from the group consisting of 4-hydroxy-3-methoxybenzaldehyde, 3,5-dimethoxy-4-hydroxybenzaldehyde, 4-hydroxy-1-naphthaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 3,4-dihydroxy-5-methoxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3,5-dibromo-4-hydroxybenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 3-bromo-4- hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde, Coniferyl aldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimetho xy-benzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5-dimethylbenzaldehyde, 4-hydroxy-2,6-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-meth yl-benzaldehyde, 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-methylbenzaldehyde, 3,4-dihydroxy-2-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, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4-morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 3,5-dichloro-4-hydroxybenzaldehyde, 4-hydroxy-3,5-diiodobenzaldehyde, 3-chloro-4-hydroxybenzaldehyde, 5-chloro-3,4-dihydroxybenzaldehyde, 5-bromo-3, 4-dihydroxybenzaldehyde, 3-chloro-4-hydroxy-5-methoxybenzaldehyde, 4-hydroxy-3-iodo 5-methoxybenzaldehyde, 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-dimethylamino-1 -naphthaldehyde, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3-nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy 3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde, 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, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-Ni troccimaldehyde, 4-nitrocinnamaldehyde, 4-dimethylaminocinnamic aldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4- (1-imidazolyl) benzaldehyde and piperonal.

According to the invention preferred Agents are characterized in that they act as hair dyes formulated, based on their weight 0.01 to 20 wt .-%, preferably 0.05 to 15% by weight, particularly preferably 0.1 to 12.5% by weight and in particular 0.2 to 10 wt .-% of one or more reactive carbonyl compound (s).

When CH-Acids are generally considered to be compounds which a hydrogen atom bonded to an aliphatic carbon atom carry, due to electron-withdrawing substituents one Activation of the corresponding carbon-hydrogen bond causes becomes. According to the invention, CH-acidic compounds also include enamines. by alkaline treatment of quaternized N-heterocycles with a conjugated to quaternary nitrogen CH-acid Alkyl group arise.

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-dimethylnaphtho [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-coumaranone, 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-methylquinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3-trimethylquinoxalinium iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methyl-benzothiazolium-p-toluenesulfonate, 1-ethyl-4-methyl-quinolinium-p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium-p-toluenesulfonate, and 1,2,3-trimethylquinoxaluminum p-toluenesulfonate.

worin

• • R⁸ und R⁹ stehen unabhängig voneinander für eine lineare oder cyclische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine gegebenenfalls substituierte Heteroarylgruppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₁-C₆-alkylgruppe, eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6,
• • R¹⁰ und R¹² stehen unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe, wobei mindestens einer der Reste R¹⁰ und R¹² eine C₁-C₆-Alkylgruppe bedeutet,
• • R¹¹ steht für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Hydroxyalkoxygruppe, eine Gruppe R^IIIR^IVN-(CH₂)_q-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe und q steht für eine Zahl 1, 2, 3, 4, 5 oder 6, wobei der Rest R¹¹ zusammen mit einem der Reste R¹⁰ oder R¹² einen 5- oder 6-gliedrigen aromatischen Ring bilden kann, der gegebenenfalls mit einem Halogenatom, einer C₁-C₆-Alkylgruppe, einer C₁-C₆-Hydroxyalkylgruppe, einer C₂-C₆-Polyhydroxyalkylgruppe, einer C₁-C₆-Alkoxygruppe, einer C₁-C₆-Hydroxyalkoxygruppe, einer Nitrogruppe, einer Hydroxygruppe, einer Gruppe R^VR^VIN-(CH₂)_s-, worin R^V und R^VI stehen unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe und s steht für eine Zahl 0, 1, 2, 3, 4, 5 oder 6 substituiert sein kann,
• • R¹³ und R¹⁴ bilden entweder zusammen mit dem Stickstoffatom einen gesättigten oder ungesättigten 5- oder 6-gliedrigen Ring oder stehen unabhängig voneinander für eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine Arylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine (C₂-C₆)-Hydroxyalkylgruppe, eine (C₂-C₆)-Polyhydroxyalkylgruppe oder eine Gruppe R^IR^IIN-(CH₂)_m-, worin R^I und R^II stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, eine (C₁-C₆)-Alkenylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^I und R^II gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 2, 3, 4, 5 oder 6, und
• • R¹⁵ ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine Arylgruppe, eine Aryl-(C₁-C₆)-alkylgruppe, eine (C₂-C₆)-Hydroxyalkylgruppe, eine (C₂-C₆)-Polyhydroxyalkylgruppe oder eine Gruppe R^IIIR^IVN-(CH₂)_n-, worin R^III und R^IV stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁-C₆)-Alkylgruppe, eine (C₁-C₆)-Alkenylgruppe oder eine Aryl-C₁-C₆-alkylgruppe, wobei R^III und R^IV gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und n steht für eine Zahl 2, 3, 4, 5 oder 6
• • Y steht für ein Sauerstoffatom, ein Schwefelatom oder eine Gruppe NR^VII, worin R^VII steht für ein Wasserstoffatom, eine Arylgruppe, eine Heteroarylgruppe, eine C₁-C₆-Alkylgruppe oder eine C₁-C₆-Arylalkylgruppe,
• • X^– steht für ein physiologisch verträgliches Anion,
• • Het steht für einen gegebenenfalls substituierten Heteroaromaten,
• • X¹ steht für eine direkte Bindung oder eine Carbonylgruppe.

The CH-acidic compounds are preferably selected from the formulas (II) and / or (III) and / or (IV)

wherein

• R ⁸ and R ⁹ independently of one another represent a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-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, a group R ^I R ^II N- (CH ₂ ) _m in which R ^I and R ^II independently of one another represent a hydrogen atom, a C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group, where R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6,
• R ¹⁰ and R ¹² independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, where at least one of the radicals R ¹⁰ and R ¹² denotes a C ₁ -C ₆ -alkyl group,
• R ¹¹ is hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ hydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ -Hydroxyalkoxygruppe, a group R ^III R ^IV N- (CH ₂ ) _q -, wherein R ^III and R ^IV independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group or a Aryl-C ₁ -C ₆ -alkyl group and q is a number 1, 2, 3, 4, 5 or 6, wherein the radical R ¹¹ together with one of the radicals R ¹⁰ or R ^{12 is} a 5- or 6-membered aromatic Ring optionally containing a halogen atom, 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 group, a C ₁ - C ₆ -hydroxyalkoxy group, a nitro group, a hydroxy group, a group R ^V R ^VI N- (CH ₂ ) _s -, wherein R ^V and R ^VI independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₆ -alkyl group and s is a number 0, 1, 2, 3, 4, 5 or 6 may be substituted,
• R ¹³ and R ¹⁴ either together with the nitrogen atom form a saturated or unsaturated 5- or 6-membered ring or independently of one another represent a (C ₁ -C ₆ ) -alkyl group, a (C ₂ -C ₆ ) -alkenyl group, an aryl group, an aryl (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) hydroxyalkyl group, a (C ₂ -C ₆ ) polyhydroxyalkyl group or a group R ^I R ^II N- (CH ₂ ) _m -, wherein R ^I and R ^II independently represent a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkenyl group or an aryl-C ₁ -C ₆ alkyl group, wherein R ^I and R ^II together with the nitrogen atom can form a 5-, 6- or 7-membered ring and m is a number 2, 3, 4, 5 or 6, and
• • R ^{15 is} a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) alkenyl group, an aryl group, an aryl (C ₁ -C ₆ ) alkyl group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group or a group R ^III R ^IV N- (CH ₂ ) _n -, wherein R ^III and R ^IV independently of one another represent a hydrogen atom, a (C ₁ -C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkenyl group or an aryl-C ₁ -C ₆ alkyl group, wherein R ^III and R ^IV together with the nitrogen atom can form a 5-, 6- or 7-membered ring and n is a number 2, 3, 4, 5 or 6
• Y is an oxygen atom, a sulfur atom or a group NR ^VII , in which R ^VII represents a hydrogen atom, an aryl group, a heteroaryl group, a C ₁ -C ₆ -alkyl group or a C ₁ -C ₆ -arylalkyl group,
• • X ^- is a physiologically acceptable anion,
• Het is an optionally substituted heteroaromatic,
• • X ¹ represents a direct bond or a carbonyl group.

With the same effect the compounds of formula II are their enamine forms. It will here explicitly the document WO-A1-2004 / 022016, to the full extent Reference is made.

At least one group R ¹⁰ or R ¹² according to formula II is necessarily a C ₁ -C ₆ -alkyl group. This alkyl group preferably carries at least two hydrogen atoms on its alpha carbon atom. Particularly preferred alkyl groups are the methyl, ethyl, propyl, n-butyl, iso-butyl, n-pentyl, neo-pentyl, n-hexyl group. Most preferably, R ¹⁰ and R ¹² are each independently hydrogen or a methyl group, wherein at least one group R ¹⁰ or R ^{12 is} a methyl group.

In a preferred embodiment Y stands according to formula (II) for an oxygen or sulfur atom, more preferably an oxygen atom.

The radical R ^{8 of} the formula (II) is preferably selected from a (C ₁ -C ₆ ) -alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ -alkenyl group (in particular an allyl group), a hydroxy (C ₂ - to C ₆ ) alkyl group, in particular a 2-hydroxyethyl group, or an optionally substituted benzyl group.

R ^{11 of} the formula (II) preferably represents a hydrogen atom.

Particularly preferred in formula (II) are the radicals R ⁹ , R ¹⁰ and R ^{12 is} a methyl group, the radical R ^{11 is} a hydrogen atom, Y is an oxygen or sulfur atom and the radical R ⁸ is selected from a (C ₁ C ₆ ) alkyl group (particularly preferably a methyl group), a C ₂ -C ₆ alkenyl group (in particular an allyl group), a hydroxy (C ₂ to C ₆ ) alkyl group, in particular a 2-hydroxyethyl group, or optionally substituted benzyl group.

Preferably, the compounds according to formula II are selected from one or more compounds of the group of salts with physiologically compatible counterion X ^- , which is formed from salts of
1,2-dihydro-1,3,4,6-tetramethyl-2-oxo-pyrimidinium, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-oxo-pyrimidinium, 1,2- Dihydro-1,3-dipropyl-4,6-dimethyl-2-oxopyrimidinium, 1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-oxopyrimidinium, 1 , 2-Dihydro-1,3-diphenyl-4,6-dimethyl-2-oxopyrimidinium, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium, 1,2-dihydro-1 , 3-diethyl-4-methyl-2-oxopyrimidinium, 1,2-dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium, 1,2-dihydro-1,3-di (2 -hydroxyethyl) -4-methyl-2-oxopyrimidinium, 1,2-dihydro-1,3-diphenyl-4-methyl-2-oxopyrimidinium, 1-allyl-1,2-dihydro-3,4, 6-trimethyl-2-oxo-pyrimidinium, 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxo-pyrimidinium, 1,2-dihydro-1,3,4, 6-tetramethyl-2-thioxo-pyrimidinium, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-dihydro-1,3-dipropyl-4,6- dimethyl-2-thioxopyrimidinium, 1,2-dihydro-1,3-di (2-hydroxyethyl) -4,6-dimethyl-2-thioxo-pyrimidinium, 1,2-dihydro-1,3-diphenyl-4 , 6-dimethyl-2-thioxo-p yrimidiniums, 1,2-dihydro-1,3,4-trimethyl-2-thioxo-pyrimidiniums, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxo-pyrimidiniums, 1,2-dihydro- 1,3-dipropyl-4-methyl-2-thioxo-pyrimidinium, 1,2-dihydro-1,3-di (2-hydroxyethyl) -4-methyl-2-thioxo-pyrimidinium, 1,2-dihydro-1 , 3-diphenyl-4-methyl-2-thioxopyrimidinium, 1,2-dihydro-3,4-dimethyl-2-oxo-quinazolinium and 1,2-dihydro-3,4-dimethyl-2-thioxo-quinazolinium ,

Very particularly preferred agents according to the invention are characterized in that they are as CH-acidic compound
Salts of 1,2-dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium,
Salts of 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium,
Salts of 1,2-dihydro-1,3,4,6-tetramethyl-2-thioxopyrimidinium,
Salts of 1-allyl-1,2-dihydro-3,4,6-trimethyl-2-oxopyrimidinium,
Salts of 1,2-dihydro-1- (2-hydroxyethyl) -3,4,6-trimethyl-2-oxopyrimidinium, 2- (cyanomethyl) benzimidazole,
4,5-dihydro-4-imino-2- (1-piperidinyl) thiazole and / or its hydrochloride,
4,5-dihydro-4-imino-2- (4-morpholinyl) thiazole and / or its hydrochloride,
4,5-dihydro-4-imino-2- (1-pyrrolidinyl) thiazole and / or its hydrochloride
contain.

X ^- in formula (II) and in the above lists is preferably halide, benzenesulfonate, p-toluenesulfonate, C ₁ -C ₄ -alkanesulfonate, trifluoromethanesulfonate, perchlorate, 0.5 sulfate, hydrogensulfate, tetrafluoroborate, hexafluorophosphate or tetrachlorozincate. The anions chloride, bromide, iodide, hydrogensulfate or p-toluenesulfonate are particularly preferably used as X ^- .

worin

• • R¹⁶ und R¹⁷ stehen unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, ein Halogenatom, eine Nitrogruppe, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Cyanmethylgruppe, eine Cyanmethylcarbonylgruppe, eine gegebenenfalls substituierte Heteroarylguppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Alkoxycarbonylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine C₁-C₆-Sulfoalkylgruppe, eine C₁-C₆-Carboxyalkylgruppe, eine Gruppe R^VIIIR^IXN-(CH₂)_m-, worin R^VIII und R^IX stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₄-alkylgruppe, wobei R^VIII und R^IX gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und m steht für eine Zahl 0, 1, 2, 3 oder 4, wobei R¹⁶ und/oder R¹⁷ einen an den Ring des Restmoleküls ankondensierten, gegebenenfalls substituierten aromatischen oder heteroaromatischen, 5- oder 6-Ring bilden können
• • X² und X³ stehen unabhängig voneinander für ein Stickstoffatom oder eine Gruppe CR¹⁵, wobei R¹⁵ steht für ein Wasserstoffatom, eine Hydroxygruppe, ein Halogenatom, eine Nitrogruppe, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine gegebenenfalls substituierte Arylgruppe, eine Cyanmethylgruppe, eine Cyanmethylcarbonylgruppe, eine gegebenenfalls substituierte Heteroarylguppe, eine Aryl-C₁-C₆-alkylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe, eine C₁-C₆-Alkoxycarbonylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine C₁-C₆-Sulfoalkylgruppe, eine C₁-C₆-Carboxyalkylgruppe und eine Gruppe R^XR^XIN-(CH₂)_n-, worin R^X und R^XI stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₄-alkylgruppe, wobei R^X und R^XI gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und n steht für eine Zahl 0, 1, 2, 3 oder 4, wobei mindestens einer der Substituenten X² und X³ zusammen mit dem Restmolekül einen ankondensierten gegebenenfalls substituierten aromatischen 5- oder 6-Ring bilden kann,
• • X⁴ steht für ein Sauerstoffatom, ein Schwefelatom, einer Vinylengruppe oder eine Gruppe N-H, wobei die beiden letztgenannten Gruppen unabhängig voneinander gegebenenfalls mit einer linearen oder zyklischen C₁-C₆-Alkylgruppe, einer C₂-C₆-Alkenylgruppe, einer gegebenenfalls substituierten Arylgruppe, einer gegebenenfalls substituierten Heteroarylguppe, einer Aryl-C₁-C₆-alkylgruppe, einer C₂-C₆-Hydroxyalkylgruppe, einer C₂-C₆-Polyhydroxyalkylgruppe, einer C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, einer C₁-C₆-Sulfoalkylgruppe, einer C₁-C₆-Carboxyalkylgruppe, einer Gruppe R^XIIR^XIIIN-(CH₂)_p- steht, worin R^XII und R^XIII stehen unabhängig voneinander für ein Wasserstoffatom, eine lineare oder zyklische C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe oder eine Aryl-C₁-C₄-alkylgruppe, wobei R^XII und R^XIII gemeinsam mit dem Stickstoffatom einen 5-, 6- oder 7-gliedrigen Ring bilden können und p steht für eine Zahl 0, 1, 2, 3 oder 4, substituiert sein können,

mit der Maßgabe, daß, wenn X⁴ für eine Vinylengruppe steht, mindestens eine der Gruppen X² oder X³ ein Stickstoffatom bedeutet.The radical Het according to formula (III) preferably represents the molecule fragment of the formula (V),

wherein

• R ¹⁶ and R ¹⁷ are each independently hydrogen, hydroxy, halogen, nitro, C ₁ -C ₆ linear or cyclic, C ₂ -C ₆ alkenyl, optionally substituted aryl, cyanomethyl , a cyanomethylcarbonyl group, an optionally substituted heteroaryl group, an aryl-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 group, a C ₁ -C ₆ alkoxycarbonyl group, a C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl group, a C ₁ -C ₆ sulfoalkyl group, a C ₁ -C ₆ carboxyalkyl group, a group R ^VIII R ^IX N- CH ₂ ) _m -, wherein R ^VIII and R ^IX are each independently a hydrogen atom, a linear or cyclic C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₁ -C ₆ hydroxyalkyl group or a Aryl-C ₁ -C ₄ -alkyl group, wherein R ^VIII and R ^IX together with the nitrogen atom, a 5-, 6- or 7-membered can form ring and m is a number 0, 1, 2, 3 or 4, wherein R ¹⁶ and / or R ^{17 can form} a fused to the ring of the remainder of the molecule, optionally substituted aromatic or heteroaromatic, 5- or 6-ring
• X ² and X ³ independently represent a nitrogen atom or a group CR ¹⁵ , wherein R ¹⁵ represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a linear or cyclic C ₁ -C ₆ alkyl group, a C ₂ C ₆ alkenyl group, an optionally substituted aryl group, a cyanomethyl group, a cyanomethylcarbonyl group, an optionally substituted heteroaryl group, an aryl-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 group, a C ₁ -C ₆ alkoxycarbonyl group, a C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl group, a C ₁ -C ₆ sulfoalkyl group, a C ₁ -C _6- carboxyalkyl group and a group R ^X R ^XI N- (CH ₂ ) _n -, wherein R ^X and R ^XI independently represent a hydrogen atom, a linear or cyclic C ₁ -C ₆ alkyl group, a C ₂ -C ₆ Alkenyl group, a C ₁ -C ₆ hydroxyalkyl group or an aryl C ₁ -C ₄ alkyl group, wherein R ^X and R ^XI g together with the nitrogen atom may form a 5-, 6- or 7-membered ring and n is a number 0, 1, 2, 3 or 4, wherein at least one of the substituents X ² and X ³ together with the remainder of the molecule is a fused-together optionally can form substituted aromatic 5- or 6-ring,
• X ⁴ represents an oxygen atom, a sulfur atom, a vinylene group or a group NH, the last two groups independently of one another optionally with a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an aryl-C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy-C ₂ -C _6- alkyl group, a C ₁ -C ₆ sulfoalkyl group, a C ₁ -C ₆ carboxyalkyl group, a group R ^XII R ^XIII N- (CH ₂ ) _p -, wherein R ^XII and R ^XIII independently represent a hydrogen atom , a linear or cyclic C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group or an aryl-C ₁ -C ₄ -alkyl group, wherein R ^XII and R ^XIII together with the nitrogen atom can form a 5-, 6- or 7-membered ring and p is one e number 0, 1, 2, 3 or 4, may be substituted,

with the proviso that when X ^{4 is} a vinylene group, at least one of X ² or X ^{3 represents} a nitrogen atom.

The bond of the heterocyclic ring according to formula (V) to the molecule fragment -X ¹ -CH ₂ -C≡N to give the compound according to formula (III) according to the invention takes place at the ring of the heterocycle and replaces a hydrogen atom bound to this ring. Consequently, it is imperative that the substituents R ¹⁶ , R ¹⁷ , X ² , X ³ and X ⁴ must be chosen such that at least one of these substituents allows a corresponding bond formation. Consequently, it is compulsory that at least one of R ¹⁶ or R ^{17 forms} the bond to the molecular fragment -X ¹ -CH ₂ -C≡N when X ^{4 is} an oxygen atom or a sulfur atom and X ² and X ^{3 represent} a nitrogen atom.

The radical Het according to formula (III) is particularly preferably derived from the heteroaromatics furan, thiophene, pyrrole, isoxazole, isothiazole, imidazole, oxazole, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, 1,2,3-triazine, 1,2 , 4-triazine, 1,3,5-triazine, benzopyrrole, benzofuran, benzothiophene, benzimidazole, benzoxazole, indazole, benzoisoxazole, benzoisothiazole, indole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, acridine, benzoquinoline, benzoisoquinoline, benzothiazole , Phenazine, benzocinnoline, benzoquinazoline, benzoquinoxaline, phenoxazine, phenothiazine, nephthyridine, phenanthroline, indolizine, quinolizine, carboline, Purine, pteridine and coumarin, wherein the aforementioned heteroaromatics have at least one group selected from a halogen atom, a nitro group, a thio group, a thio (C ₁ -C ₆ ) alkyl group, a heteroaryl group, an aryl group, a (C ₁ -C ₆ ) -alkyl group, a (C ₁ -C ₆ ) -alkoxy group, a hydroxy group, a (C ₂ -C ₆ ) -hydroxyalkyl group, a (C ₂ -C ₆ ) -polyhydroxyalkyl group, a (C ₁ -C ₆ ) - Alkoxyl (C ₁ -C ₆ ) -alkyl group, an aryl (C ₁ -C ₆ ) -alkyl group, an amino group, a (C ₁ -C ₆ ) -monoalkylamino group, a (C ₁ -C ₆ ) -dialkylamino group, a dialkylaminoalkyl group - (CH ₂ ) _n -NR'R ", wherein n is an integer of 2 and 6 and R 'and R" independently represent a linear or branched alkyl group which may optionally together form a ring could be.

Preferably are the compounds according to formula (III) selected from the group consisting of 2- (2-furoyl) -acetonitrile, 2- (5-bromo-2-furoyl) -acetonitrile, 2- (5-methyl-2-trifluoromethyl-3-furoyl) -acetonitrile, 3- (2,5-dimethyl-3-furyl) -3-oxopropanitrile, 2- (2-thenoyl) -acetonitrile, 2- (3-thenoyl) -acetonitrile, 2- (5-fluoro-2-thenoyl) -acetonitrile, 2- (5-chloro-2-thenoyl) -acetonitrile, 2- (5-bromo-2-thenoyl) -acetonitrile, 2- (5-methyl-2-thenoyl) -acetonitrile, 2- (2,5-dimethylpyrrol-3-oyl) -acetonitrile, 2- (1,2,5-trimethylpyrrol-3-oyl) -acetonitrile, 1H-benzimidazol-2-ylacetonitrile, 1H-benzothiazol-2-ylacetonitrile, 2- (pyrid-2-yl) -acetonitrile, 2,6-bis (cyanomethyl) -pyridine, 2- (indol-3-oyl) -acetonitrile, 2- (2-methyl-indol-3-oyl) -acetonitrile, 8-cyanoacetyl-7-methoxy-4-methylcoumarin, 2- (2-isopropyl-5,6-benzoquinolin-4-oyl) -acetonitrile, 2- (2-phenyl-5,6-benzoquinolin-4-oyl) - acetonitrile, 2- (Quinoxalin-2-yl) -acetonitrile, 2- (Cumaron-2-yl) -acetonitrile, 6,7-dichloro-5- (cyanoacetyl) -2,3-dihydro-1-benzofuran-2-carboxylic acid. butyl, 2- (6-Hydroxy-4,7-dimethoxy-1-benzofuran-5-oyl) -acetonitrile and 2- (1-phenyl-1,4-dihydrothiochromeno [4,3-c] pyrazol-3-oyl) - acetonitrile. Particularly preferred is 1H-benzimidazol-2-ylacetonitrile [2- (cyanomethyl) benzimidazole].

Compositions according to the invention, containing CH-acidic compounds are characterized that she as hair dye which are in addition to at least one reactive carbonyl compound additionally preferred based on the weight of the ready-to-use agent 0.01 to 20 wt .-%, preferably 0.05 to 15 wt .-%, particularly preferably 0.1 to 12.5 wt .-% and in particular 0.2 to 10 wt .-% of one or more Containing CH-acidic compound (s).

in der

• • R⁷ für eine Hydroxy- oder eine Aminogruppe, die durch C_1-4-Alkyl-, C_1-4-Hydroxyalkyl-, C_1-4-Alkoxy- oder C_1-4-Alkoxy-C_1-4-alkylgruppen substituiert sein kann, steht,
• • R⁸, R⁹, R¹⁰, R¹¹ und R¹² unabhängig voneinander für ein Wasserstoffatom, eine Hydroxy- oder eine Aminogruppe, die durch C₁-C₄-Alkyl-, C₁-C₄-Hydroxyalkyl, C₁-C₄-Alkoxy-, C₁-C₄-Aminoalkyl- oder C₁-C₄-Alkoxy-C₁-C₄-alkylgruppen substituiert sein kann, stehen, und
• • P für eine direkte Bindung, eine gesättigte oder ungesättigte, ggf. durch Hydroxygruppen substituierte Kohlenstoffkette mit 1 bis 4 Kohlenstoffatomen, eine Carbonyl-, Sulfoxy-, Sulfonyl- oder Iminogruppe, ein Sauerstoff- oder Schwefelatom, oder eine Gruppe mit der Formel VII -Q'-(CH₂-Q-CH₂-Q'')_o- (VII) in der
• • Q eine direkte Bindung, eine CH₂- oder CHOH-Gruppe bedeutet,
• • Q' und Q'' unabhängig voneinander für ein Sauerstoffatom, eine NR¹³-Gruppe, worin R¹³ ein Wasserstoffatom, eine C_1-4-Alkyl- oder eine Hydroxy-C_1-4-alkylgruppe, 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 beispielsweise 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.Preferred primary or secondary aromatic amines of component B are selected from 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-methylphenol, 2- 2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) 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) -phen ol, 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- (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-diaminobenzene benzoic 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-hydroxy-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-h ydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, amino groups containing nitro groups, such as 3-amino-6-methylamino-2-nitro-pyridine, picric acid, [8 - [(4-amino -2-nitrophenyl) azo] -7-hydro xy-naphth-2-yl] -trimethylammonium chloride, [8 - ((4-amino-3-nitrophenyl) azo) -7-hydroxy-naphth-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-aminobenzene (HC Red # 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-disulfonic acid disodium salt (Palatinch rome green), 1-amino-2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (gallium), 4-amino-4'-nitrostilbene-2,2 'disulfonic acid disodium salt, 2,4-diamino-3', 5'-dinitro-2'-hydroxy-5-methylazobenzene (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, aniline, 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, ar omatic anilines or phenols with a further aromatic radical, as shown in the formula VI

in the

• R ^{7 represents} a hydroxy or amino group represented by C _1-4 alkyl, C _1-4 hydroxyalkyl, C _1-4 alkoxy or C _1-4 alkoxy C _1-4 alkyl groups may be substituted,
• • R ^8, R ^9, R ^10, R ¹¹ and R ¹² independently represent a hydrogen atom, a hydroxy or an amino group by C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, C ₁ - C ₄ alkoxy, C ₁ -C ₄ aminoalkyl or C ₁ -C ₄ alkoxy C ₁ -C ₄ alkyl groups may be substituted, and
• P is a direct bond, a saturated or unsaturated, optionally substituted by hydroxy groups carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group of formula VII -Q '- (CH ₂ -Q-CH ₂ -Q'') _o - (VII) in the
• Q signifies a direct bond, a CH ₂ or CHOH group,
• • Q 'and Q''independently represent an oxygen atom, an NR ¹³ group, wherein R ^{13 represents} a hydrogen atom, a C _1-4 alkyl or a hydroxy C _1-4 alkyl group, both of which together with represents a 5-, 6- or 7-membered ring for the remainder of the molecule, the group O- (CH ₂ ) _p -NH or NH- (CH ₂ ) _{p '} -O, where p and p' are 2 or 3, stand and
• O is a number from 1 to 4,

such as 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'-tetraamino-benzophenone, 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 the aforementioned compounds both in free form and in the form of their physiologically acceptable Salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid, can be used.

suitable nitrogen-containing heterocyclic compounds are e.g. 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-amino-pyridine, 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. Furthermore, 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. used as salts of inorganic acids, such as hydrochloric or sulfuric acid become.

suitable Aromatic hydroxy compounds are e.g. 2-methylresorcinol, 4-methylresorcinol, 5-methyl, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, catechol, Hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3-dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxy-phenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoic acid, 2,4,6-trihydroxyacetophenone, 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.

The oxidizing agent preparation B contains at least one oxidizing agent selected from hydrogen peroxide and its addition compounds to solid supports. As the oxidant of the present invention, hydrogen peroxide itself is preferably used. The hydrogen peroxide is used as a solution or in the form of a solid addition compound of hydrogen peroxide to inorganic or organic compounds, such as sodium perborate, sodium percarbonate, magnesium percarbonate, sodium percarbamide, polyvinylpyrrolidone n H ₂ O ₂ (n is a positive greater than 0), urea peroxide and melamine peroxide.

Very particularly preferred according to the invention are aqueous hydrogen peroxide solutions. The concentration of a hydrogen peroxide solution is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6-12% solutions in water are used. According to preferred means for dyeing and / or lightening keratinischer fibers are characterized in that the oxidizing agent preparation B - based on their weight - 0.5 to 10 wt .-%, preferably 0.75 to 9.0 wt .-%, particularly preferably 1 to 8.0 wt .-%, more preferably 1.25 to 7.0 wt .-% and in particular 1.5 to 6.0 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ).

The Oxidizer formulation B is preferably an aqueous, flowable oxidizer formulation. Accordingly, preferred means for dyeing and / or Whitening keratinic fibers, characterized in that the flowable oxidizing agent preparation B - related on her weight - 40 to 99% by weight, preferably 50 to 95% by weight, more preferably 55 to 90 wt .-%, water.

Preferably becomes the flowable oxidizer formulation B an emulsifier or a surfactant added, wherein surface-active Depending on the field of application substances are known as surfactants or as emulsifiers and anionic, cationic, zwitterionic, ampholytic and nonionic surfactants and emulsifiers. These substances are described in detail below.

The choice of this further peroxo compound is subject in principle to no restrictions, and customary peroxo compounds known to the person skilled in the art are, for example, ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, percarbonates, such as magnesium percarbonate, Peroxides such as barium peroxide and perborates, urea peroxide and melamine peroxide are among these peroxo compounds which can also be used in combination According to the invention, the inorganic compounds are preferred. Particularly preferred are the peroxydisulfates, in particular combinations of at least two peroxydisulfates. Here, agents according to the invention for dyeing and / or brightening keratinic fibers are preferred, which additionally contains at least one peroxo compound, which is preferably selected from ammonium and alkali metal persulfates and peroxydisulfates, preferred agents containing at least 2 different peroxydisulfates.

The Peroxo compound is preferably separated from the preparation A, the oxidation preparation B and the preparation C as preferred anhydrous (i.e., a maximum of 3% by weight of water), particularly preferably pasty or powdery, Preparation D stored.

Short before use, preparations A, B C and optionally D to obtain the agent according to the invention mixed. The preferred order of mixing these preparations is that starting from the oxidation preparation B, the other Preparations are added in the following order: A + C, C + A, A + C + D, A + C + D, C + A + D or D + A + C

The agents according to the invention to dye and / or lightening of keratinic fibers may continue all for such Preparations known active ingredients, additives and excipients. In the case of multicomponent agents, these ingredients can both in the preparation A as well as in the preparation B as well as in the preparation C or only in individual of these preparations.

In many cases entle the colorants at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases However, it proved to be advantageous, the surfactants from anionic, select zwitterionic or nonionic surfactants.

• – lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_x-CH₂-COOH, in der R eine lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acyltauride mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 8 bis 24 C-Atomen in der Acylgruppe,
• – lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 8 bis 24 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• – Acylglutamate der Formel (1),
  
  in der R¹CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen und X für Wasserstoff, ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht, beispielsweise Acylglutamate, die sich von Fettsäuren mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen ableiten, wie beispielsweise C_12/14- bzw. C_12/18-Kokosfettsäure, Laurinsäure, Myristinsäure, Palmitinsäure und/oder Stearinsäure, insbesondere Natrium-N-cocoyl- und Natrium-N-stearoyl-L-glutamat,
• – Ester einer hydroxysubstituierten Di- oder Tricarbonsäure der allgemeinen Formel (2),
  
  
  in der X=H oder eine -CH₂COOR-Gruppe ist, Y=H oder -OH ist unter der Bedingung, dass Y=H ist, wenn X=-CH₂COOR ist, R, R¹ und R² unabhängig voneinander ein Wasserstoffatom, ein Alkali- oder Erdalkalimetallkation, eine Ammoniumgruppe, das Kation einer ammonium-organischen Base oder einen Rest Z bedeuten, der von einer polyhydroxylierten organischen Verbindung stammt, die aus der Gruppe der veretherten (C₆-C₁₈)-Alkylpolysaccharide mit 1 bis 6 monomeren Saccharideinheiten und/oder der veretherten aliphatischen (C₆-C₁₆)-Hydroxyalkylpolyole mit 2 bis 16 Hydroxylresten ausgewählt sind, unter der Maßgabe, dass wenigstens eine der Gruppen R, R¹ oder R² ein Rest Z ist,
• – Ester der Sulfobernsteinsäure oder der Sulfosuccinate der allgemeinen Formel (3),
  
  in der M^(n+/n) für n = 1 ein Wasserstoffatom, ein Alkalimetallkation, eine Ammoniumgruppe oder das Kation einer ammonium-organischen Base und für n = 2 ein Erdalkalimetallkation darstellt und R¹ und R² unabhängig voneinander ein Wasserstoffatom, ein Alkali- oder Erdalkalimetallkation, eine Ammoniumgruppe, das Kation einer ammonium-organischen Base oder einen Rest Z bedeuten, der von einer polyhydroxylierten organischen Verbindung stammt, die aus der Gruppe der veretherten (C₆-C₁₆)-Alkylpolysaccharide mit 1 bis 6 monomeren Saccharideinheiten und/oder der veretherten aliphatischen (C₆-C₁₆)-Hydroxyalkylpolyole mit 2 bis 16 Hydroxylresten ausgewählt ist, unter der Maßgabe, dass wenigstens eine der Gruppen R¹ oder R² ein Rest Z ist,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremonoalkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – Alkylsulfate und Alkylpolyglycolethersulfate der Formel R-(O-CH₂-CH₂)_x-OSO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 – 12 ist,
• – gemischte oberflächenaktive Hydroxysulfonate gemäß DE-A-37 25 030,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2-15 Molekülen Ethylenoxid und/oder Propylenoxid an C_8-22-Fettalkohole darstellen,
• – Alkyl- und/oder Alkenyletherphosphate,
• – sulfatierte Fettsäurealkylenglycolester,
• – Monoglyceridsulfate und Monoglyceridethersulfate.

Suitable anionic surfactants and emulsifiers for the compositions according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 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 and emulsifiers are, in each case in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts having 2 to 4 C atoms in the alkanol group,

• - linear and branched fatty acids with 8 to 30 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 8 to 30 C atoms and x = 0 or 1 to 16,
• Acylsarcosides having 8 to 24 C atoms in the acyl group,
• Acyltaurides having 8 to 24 carbon atoms in the acyl group,
• Acyl isethionates having 8 to 24 C atoms in the acyl group,
• - linear alkanesulfonates having 8 to 24 carbon atoms,
• - linear alpha-olefin sulfonates having 8 to 24 carbon atoms,
• Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 C atoms,
• Acylglutamates of the formula (1),
  
  in which R ¹ CO is a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X is hydrogen, an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium, for example acylglutamates, which are derived from fatty acids having 6 to 22, preferably 12 to 18 carbon atoms, such as, for example, C _12/14 or C _12/18 coconut fatty acid, lauric acid, myristic acid, palmitic acid and / or stearic acid, in particular sodium N-cocoyl and sodium N-stearoyl-L-glutamate,
• Esters of a hydroxy-substituted di- or tricarboxylic acid of the general formula (2),
  
  
  in which X = H or a -CH ₂ COOR group, Y = H or -OH, on condition that Y = H when X is -CH ₂ COOR =, R, R ¹ and R ^{2 are} independently a hydrogen atom, an alkali or alkaline earth metal cation, an ammonium group, the cation of an ammonium organic base or a radical Z derived from a polyhydroxylated organic compound selected from the group of etherified (C ₆ -C ₁₈ ) alkyl polysaccharides with 1 to 6 monomeric saccharide units and / or the etherified aliphatic (C ₆ -C ₁₆ ) -hydroxyalkylpolyols having 2 to 16 hydroxyl radicals, with the proviso that at least one of the groups R, R ¹ or R ^{2 is} a radical Z,
• Esters of sulfosuccinic acid or sulfosuccinates of general formula (3),
  
  in which M ^{(n + / n)} for n = 1 represents a hydrogen atom, an alkali metal cation, an ammonium group or the cation of an ammonium organic base and for n = 2 an alkaline earth metal cation and R ¹ and R ² independently of one another represent a hydrogen atom, an alkali metal cation or alkaline earth metal cation, an ammonium group, the cation of an ammonium organic base or a radical Z derived from a polyhydroxylated organic compound selected from the group of etherified (C ₆ -C ₁₆ ) -alkyl polysaccharides having 1 to 6 monomeric saccharide units and / or the etherified aliphatic (C ₆ -C ₁₆ ) -hydroxyalkylpolyols having 2 to 16 hydroxyl radicals, with the proviso that at least one of the groups R ¹ or R ^{2 is} a radical Z,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R- (O-CH ₂ -CH ₂ ) _x -OSO ₃ H, in which R is a preferably linear alkyl group with 8 to 30 C atoms and x = 0 or 1-12,
• Mixed surface-active hydroxysulfonates according to DE-A-37 25 030,
• 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 C _8-22 fatty alcohols,
• Alkyl and / or alkenyl ether phosphates,
• - sulfated fatty acid alkylene glycol esters,
• Monoglyceride sulfates and monoglyceride ether sulfates.

preferred anionic surfactants and emulsifiers are acyl glutamates, acyl isethionates, Acyl sarcosinates and acyl taurates, each with a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, in particularly preferred embodiments from an octanoyl, decanoyl, lauroyl, myristoyl, palmitoyl and stearoyl radical selected is, esters of tartaric acid, Citric acid or Succinic acid or the salts of these acids with alkylated glucose, in particular the products with the INCI name Disodium Coco-Glucoside Citrate, Sodium Coco-Glucoside Tartrate and disodium coco-glucoside sulfosuccinates, alkyl polyglycol ether sulfates and ether carboxylic acids with 8 to 18 C atoms in the alkyl group and up to 12 ethoxy groups in the molecule, sulfosuccinic and -dialkylester having 8 to 18 C-atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 ethoxy groups.

Zwitterionic surfactants and emulsifiers are those 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 and emulsifiers are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl 3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants and emulsifiers are understood to mean those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming internal salts , Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylaminopropionic 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 24 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

• – Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – C₁₂-C₃₀-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Polyole mit 3 bis 6 Kohlenstoffatomen, insbesondere an Glycerin,
• Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Polyolfettsäure(partial)ester, wie Hydagen^® HSP (Cognis) oder Sovermol^® – Typen (Cognis), insbesondere von gesättigten C_8-30-Fettsäuren,
• – alkoxylierte Triglyceride,
• – alkoxylierte Fettsäurealkylester,
• – Aminoxide,
• – Fettsäurealkanolamide, Fettsäure-N-alkylglucamide und Fettamine sowie deren Ethylenoxid- oder Polyglycerin-Anlagerungsprodukte,
• – Sorbitanfettsäureester und Anlagerungsprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate,
• – Zuckerfettsäureester und Methylglucosid-Fettsäureester sowie deren Ethylenoxid- oder Polyglycerin-Anlagerungsprodukte,
• – Alkylpolyglycoside entsprechend der allgemeinen Formel RO-(Z)_x wobei R für Alkyl, Z für Zucker sowie x für die Anzahl der Zuckereinheiten steht. Besonders bevorzugt sind solche Alkylpolyglycoside, bei denen R
• – im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• – im wesentlichen aus C₈- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₆ bis C₁₈-Alkylgruppen

besteht.Nonionic surfactants and emulsifiers contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group as the hydrophilic group. Such compounds are, for example

• - Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• C ₁₂ -C ₃₀ -fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol,
• Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• - polyol fatty (partial) ester as Hydagen ^® HSP (Cognis) or Sovermol ^® - types (Cognis), especially of saturated C _8-30 fatty acids,
• - alkoxylated triglycerides,
• - alkoxylated fatty acid alkyl esters,
• - amine oxides,
• Fatty acid alkanolamides, fatty acid N-alkylglucamides and fatty amines and their ethylene oxide or polyglycerol addition products,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,
• Sugar fatty acid esters and methyl glucoside fatty acid esters and their ethylene oxide or polyglycerol addition products,
• - Alkylpolyglycoside according to the general formula RO- (Z) _x wherein R is alkyl, Z is sugar and x is the number of sugar units. Particular preference is given to those alkylpolyglycosides in which R
• Consisting essentially of C ₈ and C ₁₀ -alkyl groups,
• Essentially of C ₁₂ and C ₁₄ alkyl groups,
• - Essentially from C ₈ - to C ₁₆ alkyl groups or
• - Essentially from C ₁₂ - to C ₁₆ alkyl groups or
• - Substituted from C ₁₆ to C ₁₈ alkyl groups

consists.

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.

• – Gemische aus Alkyl-(oligo)-glucosiden und Fettalkoholen, z.B. Montanov^®68,
• – Sterine, z.B. Ergosterin, Stigmasterin, Sitosterin und Mykosterine,
• – Phospholipide, z.B. Lecithine bzw. Phosphatidylcholine,
• – Polyglycerine und Polyglycerinderivate wie beispielsweise Polyglycerinpoly-12-hydroxystearat (Dehymuls^® PGPH) oder Triglycerindüsosteara4 (Lameform^® TGI),
• – alkoxylierte Polydialkylsiloxane (INCI-Bezeichnung: Dimethicone Copolyol).

The alkylpolyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 2.0 are preferred. Very particular preference is given to alkyl glycosides in which x is 1.1 to 1.8.

• Glucosides mixtures of alkyl (oligo) and fatty alcohols, such as Montanov ^® 68, -
• - sterols, eg ergosterol, stigmasterol, sitosterol and mycosterols,
• Phospholipids, eg lecithins or phosphatidylcholines,
• - polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate (Dehymuls ^® PGPH) or Triglycerindüsosteara4 (Lameform ^® TGI),
• - alkoxylated polydialkylsiloxanes (INCI name: Dimethicone Copolyol).

When preferred nonionic surfactant Substances have the alkyl polyglycosides, optionally in Mixture with fatty alcohols, alkoxylated polydialkylsiloxanes, alkylene oxide Anla tion products saturated linear fatty alcohols and fatty acids with in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid.

Also usable according to the invention are cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides. The long alkyl chains of these surfactants have preferably 10 to 18 carbon atoms, such as in cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further preferred cationic surfactants are the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83.

Very particular preference is given to compositions according to the invention for dyeing and / or lightening keratinic fibers which additionally contain fatty alcohol (s) and / or fatty alcohol alkoxylate (s), preferably C _12-22 fatty alcohol (s) and / or. Preferably in the free-flowing oxidizing agent preparation B C _12-22 fatty alcohol ethoxylate (s) having 10 to 30 EO units, more preferably C _16-18 fatty alcohol (s) and / or C _16-18 fatty alcohol ethoxylate (s) having 12 to 20 EO units, preferably in Amounts of from 5 to 20 wt .-%, preferably from 7.5 to 17.5 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of the application mixture containing.

• – Anlagerungsprodukte von 4 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 Polyole mit 3 bis 6 Kohlenstoffatomen, insbesondere an Glycerin,
• – Ethylenoxid- und Polyglycerin-Anlagerungsprodukte an Methylglucosid-Fettsäureester, Fettsäurealkanolamide und Fettsäureglucamide,
• – C₈-C₂₂-Alkylmono- und -oligoglycoside und deren ethoxylierte Analoga, wobei Oligomerisierungsgrade von 1,1 bis 5, insbesondere 1,2 bis 2,0, und Glucose als Zuckerkomponente bevorzugt sind,
• – Gemische aus Alkyl-(oligo)-glucosiden und Fettalkoholen zum Beispiel das im Handel erhältliche Produkt Montanov^®68,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Partialester von Polyolen mit 3-6 Kohlenstoffatomen mit gesättigten Fettsäuren mit 8 bis 22 C-Atomen,
• – Sterine. Als Sterine wird eine Gruppe von Steroiden verstanden, die am C-Atom 3 des Steroid-Gerüstes eine Hydroxylgruppe tragen und sowohl aus tierischem Gewebe (Zoosterine) wie auch aus pflanzlichen Fetten (Phytosterine) isoliert werden. Beispiele für Zoosterine sind das Cholesterin und das Lanosterin. Beispiele geeigneter Phytosterine sind Ergosterin, Stigmasterin und Sitosterin. Auch aus Pilzen und Hefen werden Sterine, die sogenannten Mykosterine, isoliert.
• – Phospholipide. Hierunter werden vor allem die Glucose-Phospolipide, die z.B. als Lecithine bzw. Phospahtidylcholine aus z.B. Eidotter oder Pflanzensamen (z.B. Sojabohnen) gewonnen werden, verstanden.
• – Fettsäureester von Zuckern und Zuckeralkoholen, wie Sorbit,
• – Polyglycerine und Polyglycerinderivate wie beispielsweise Polyglycerinpoly-12-hydroxystearat (Handelsprodukt Dehymuls^® PGPH),
• – Lineare und verzweigte Fettsäuren mit 8 bis 30 C -Atomen und deren Na-, K-, Ammonium-, Ca-, Mg- und Zn – Salze.

In a further preferred embodiment, the agents according to the invention may contain emulsifiers (F). Emulsifiers effect at the phase interface the formation of water- or oil-stable adsorption layers, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Emulsifiers are therefore constructed like surfactants from a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. An emulsion is to be understood as meaning a droplet-like distribution (dispersion) of a liquid in another liquid under the expense of energy in order to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers depends on the substances to be dispersed and the respective outer phase and the fineness of the emulsion. Emulsifiers which can be used according to the invention are, for example

• Addition products of from 4 to 30 mol of ethylene oxide and / or from 0 to 5 mol of propylene oxide onto linear fatty alcohols having from 8 to 22 carbon atoms, to fatty acids containing from 12 to 22 carbon atoms and to alkylphenols having from 8 to 15 carbon atoms in the alkyl group,
• C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol,
• Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,
• C ₈ -C ₂₂ -alkylmono- and -oligoglycosides and their ethoxylated analogues, preference being given to degrees of oligomerization of from 1.1 to 5, in particular from 1.2 to 2.0, and glucose as the sugar component,
• Glucosides mixtures of alkyl (oligo) and fatty alcohols, for example, the commercially available product ^® Montanov 68, -
• Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,
• Partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 C atoms,
• - sterols. Sterols are understood to mean a group of steroids which have a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.
• - Phospholipids. These include, in particular, the glucose phospholipids which are obtained, for example, as lecithins or phosphatidylcholines from, for example, egg yolks or plant seeds (for example soybeans).
• Fatty acid esters of sugars and sugar alcohols, such as sorbitol,
• - polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hydroxystearate (commercial product Dehymuls ^® PGPH),
• - Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The agents according to the invention contain the emulsifiers preferably in amounts of 0.1 to 25 wt .-%, in particular 0.5 to 15 wt .-%, based on the total mean.

Prefers can the compositions of the invention at least one nonionic emulsifier having an HLB value of 8 to 18 included. Nonionic emulsifiers with an HLB value from 10 - 15 can particularly according to the invention be preferred.

When It has furthermore been shown to be advantageous if polymers (G) are available in the agents according to the invention are included. In a preferred embodiment, the agents according to the invention therefore polymers are added, both cationic, anionic, amphoteric and nonionic polymers have been found to be effective.

Usable according to the invention are preferably cationic or amphoteric polymers. Under cationic or amphoteric polymers are to be understood as meaning polymers which are available in the main and / or Side chain have a group which may be "temporary" or "permanent" cationic. As "permanently cationic" according to the invention such Polymers referred to independently have a cationic group from the pH of the agent. This are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic Groups are quaternary Ammonium groups. In particular, such polymers in which the quaternary ammonium group over a C1-4 hydrocarbon group to one of acrylic acid, methacrylic acid or whose derivatives are attached to a polymer backbone, have proven to be particularly suitable.

in der R¹= -H oder -CH₃ ist, R², R³ und R⁴ unabhängig voneinander ausgewählt sind aus C1-4-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen, m = 1, 2, 3 oder 4, n eine natürliche Zahl und X- ein physiologisch verträgliches organisches oder anorganisches Anion ist, sowie Copolymere, bestehend im wesentlichen aus den in Formel (G1-I) aufgeführten Monomereinheiten sowie nichtionogenen Monomereinheiten, sind besonders bevorzugte kationische Polymere. Im Rahmen dieser Polymere sind diejenigen erfindungsgemäß bevorzugt, für die mindestens eine der folgenden Bedingungen gilt:

• – R¹ steht für eine Methylgruppe
• – R², R³ und R⁴ stehen für Methylgruppen
• – m hat den Wert 2.

Homopolymers of the general formula (G1-I),

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from C 1-4 -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X- is a physiologically acceptable organic or inorganic anion, as well as copolymers consisting essentially of the monomer units listed in formula (G1-I) and nonionic monomer units, are particularly preferred cationic polymers. In the context of these polymers, preference is given to those according to the invention for which at least one of the following conditions applies:

• - R ¹ is a methyl group
• - R ² , R ³ and R ⁴ are methyl groups
• - m has the value 2.

Suitable physiologically tolerated counterions X ^- include, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions. Preference is given to halide ions, in particular chloride.

A particularly suitable homopolymer is, if desired, crosslinked, poly (methacryloyloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. Such products are available, for example under the names Rheocare ^® CTH (Cosmetic Rheologies) and Synthalen® ^® CR (Ethnichem) in trade. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are (under the names Salcare ^® SC 95 about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1 trideceth-6) ) and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol (with a mixture of caprylic and capric acid INCI name: propylene glycol Dicaprylate / Dicaprate) and Tridecylpolyoxypropylen polyoxyethylene ether (INCI name : PPG-1-trideceth-6)) are commercially available.

Copolymers having monomer units of the formula (G1-I) contain as nonionic monomer units preferably acrylamide, methacrylamide, acrylic acid-C _1-4 -alkyl esters and methacrylic acid-C _1-4 -alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A copolymer preferred according to the invention is the crosslinked acrylamide-methacryloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, are commercially available as approximately 50% non-aqueous polymer dispersion 92 under the name Salcare ^® SC.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate,
• – kationische Alkylpolyglycoside gemäß der DE-PS 44 13 686,
• – kationisierter Honig, beispielsweise das Handelsprodukt Honeyquat^® 50,
• – kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®Guar und Jaguar^® vertriebenen Produkte,
• – polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere,
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoalkylacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminoethylmethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich,
• – Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat^® FC 370, FC 550, FC 905 und HM 552 angeboten werden,
• – quaternierter Polyvinylalkohol,
• – sowie die unter den Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

Further preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® commercially are available. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives
• Cationic alkyl polyglycosides according to DE-PS 44 13 686,
• - cationized honey, for instance, the commercial product Honeyquat ^® 50,
• - cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia® ^® Guar and Jaguar ^®,
• - Dimethyldiallylammoniumsalze polymeric and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers,
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,
• - vinylpyrrolidone vinylimidazoliummethochloride copolymers, such as those offered under the names Luviquat.RTM ^® FC 370, FC 550, FC 905 and HM 552,
• - quaternized polyvinyl alcohol,
• - as well as the polymers known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 with quaternary nitrogen atoms in the polymer main chain.

Likewise, as cationic polymers can be used under the names Polyquaternium-24 (commercial product eg Quatrisoft ^® LM 200), known polymers. , Gaffix ^® VC 713 (manufactured by ISP): Also according to the invention can be used the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (ISP manufacturer) are Gafquat ^® ASCP 1011, Gafquat ^® HS 110, Luviquat ^® 8155 and Luviquat ^® MS 370 available are.

• A) Monomeren mit quartären Ammoniumgruppen der allgemeinen Formel (Z-I), R¹-CH=CR²-CO-Z-(C_nH_2n)-N⁽⁺⁾R³R⁴R⁵ A^(-) (Z-I)In der R¹ und R² unabhängig voneinander stehen für Wasserstoff oder eine Methylgruppe und R³, R⁴ und R⁵ unabhängig voneinander für Alkylgruppen mit 1 bis 4 Kohlenstoff-Atomen, Z eine NH-Gruppe oder ein Sauerstoffatom, n eine ganze Zahl von 2 bis 5 und A^(–) das Anion einer organischen oder anorganischen Säure ist und
• B) monomeren Carbonsäuren der allgemeinen Formel (Z-II), R⁶-CH=CR⁷-COOH (Z-II) in denen R⁶ und R⁷ unabhängig voneinander Wasserstoff oder Methylgruppen sind.

In addition to cationic polymers or in their place, the agents according to the invention can also contain amphoteric polymers. These additionally have at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers. In the context of the present invention, preferably usable zwitterionic polymers are composed essentially together

• A) monomers having quaternary ammonium groups of the general formula (ZI), R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ³ R ⁴ R ⁵ A ^(-) (ZI) In the R ¹ and R ² independently of one another are hydrogen or a methyl group and R ³ , R ⁴ and R ^{5 are} independently alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer of 2 to 5 and A ^{(-) is} the anion of an organic or inorganic acid and
• B) monomeric carboxylic acids of the general formula (Z-II), R ⁶ -CH = CR ⁷ -COOH (Z-II) in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

suitable Starting monomers are e.g. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, Dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide and Diethylaminoethylacrylamid, if Z is an NH group or Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate, when Z is an oxygen atom.

The a tertiary Amino-containing monomers are then in a known manner quaternized, wherein as alkylating reagents methyl chloride, dimethyl sulfate or diethyl sulfate are particularly suitable. The quaternization reaction can in aqueous solution or in the solvent respectively.

Advantageously, such monomers of formula (ZI), which are derivatives of acrylamide or methacrylamide. Preference is furthermore given to those monomers which contain halide, methoxysulfate or ethoxysulfate ions as counterions. Also preferred are those monomers of the formula (ZI) in which R ³ , R ⁴ and R ^{5 are} methyl groups.

The Acrylamidopropyltrimethylammonium chloride is a very special one preferred monomer of the formula (Z-I).

When monomeric carboxylic acids of the formula (Z-II) are acrylic acid, methacrylic acid, crotonic acid and 2-methyl-crotonic acid. Preference is given to using acrylic or methacrylic acid, in particular acrylic acid.

The can be used according to the invention zwitterionic polymers are prepared from monomers of the formulas (Z-I) and (Z-II) according to known polymerization. The polymerization can be carried out either in aqueous or aqueous-alcoholic solution respectively. Alcohols are alcohols having 1 to 4 carbon atoms, preferably isopropanol, used simultaneously as a polymerization regulator serve. The monomer solution can but other components may also be added as regulators, e.g. Formic acid or Mercaptans, such as thioethanol and thioglycolic acid. The initiation of the polymerization takes place with the help of radical-forming substances. For this purpose, redox systems and / or thermally decomposing radical formers of the azo compound type, such as. azoisobutyronitrile, Azobis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride be used. Suitable redox systems are e.g. Combinations Hydrogen peroxide, potassium or ammonium peroxodisulfate and tertiary butyl hydroperoxide with sodium sulfite, sodium dithionite or hydroxylamine hydrochloride as a reduction component.

The Polymerization may be isothermal or under adiabatic conditions carried out be, depending on from the concentration ratios by the released heat of polymerization of the temperature range for the process the reaction between 20 and 200 ° C may vary, and the reaction optionally under the autogenous overpressure carried out must become. Preferably, the reaction temperature is between 20 and 100 ° C.

Of the pH during The copolymerization can vary within a wide range. advantageously, is polymerized at low pHs; however, pH values are also possible above the neutral point. After the polymerization is with a aqueous base, e.g. Sodium hydroxide solution, potassium hydroxide solution or ammonia, to a pH between 5 and 10, preferably 6 to 8, set. Details of the polymerization process can taken from the examples.

When Such polymers have proven particularly effective in which the monomers of the formula (Z-I) over the monomers of the formula (Z-II) in excess. It is therefore preferred according to the invention to use those polymers which consist of monomers of the formula (Z-I) and the monomers of the formula (Z-II) in a molar ratio of 60:40 to 95: 5, especially from 75:25 to 95: 5 exist.

The cationic or amphoteric polymers are in the inventive compositions preferably in amounts of 0.05 to 10 wt .-%, based on the total Means, included. Amounts of 0.1 to 5 wt .-% are particularly preferred.

at the anionic polymers (G2) are anionic polymers, which carboxylate and / or Have sulfonate groups. Examples of anionic monomers, from such polymers may be acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The can acidic groups in whole or in part as sodium, potassium, ammonium, Mono- or triethanolammonium salt present. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

When anionic polymers have proven to be particularly effective containing as sole or co-monomer 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group wholly or partly as sodium, potassium, ammonium, mono- or Triethanolammonium salt may be present.

More preferably, the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid, which is available for example under the name Rheothik ^® 11-80 is commercially.

Within this embodiment For example, it may be preferable to use copolymers of at least one anionic Use monomer and at least one nonionic monomer. In terms of The anionic monomers are based on the substances listed above directed. Preferred nonionic monomers are acrylamide, methacrylamide, acrylate, methacrylates, Vinyl pyrrolidone, vinyl ethers and vinyl esters.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group wholly or partly as sodium, potassium, ammonium, mono- or Triethanolammonium salt is present. This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylene-bisacrylamide are used. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound, which in addition to the polymer component contains a hydrocarbon mixture (C ₁₃ -C ₁₄ isoparaffin) and a nonionic emulsifier (laureth-7), has proved to be particularly advantageous within the scope of the teaching according to the invention.

Also sold under the name Simulgel ^® 600 as a compound with isohexadecane and polysorbate-80 Natriumacryloyldimethyltaurat copolymers have proved to be particularly effective according to the invention.

Likewise preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trademark Carbopol ^® commercially.

Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-retaining polymers. A 1.9-decadienes crosslinked maleic acid-methyl copolymer available under the name Stabileze® ^® QM.

The agents according to the invention can in a further embodiment non-ionic polymers (G4).

• – Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind ebenfalls bevorzugte nichtionische Polymere.
• – Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) und Natrosol^®-Typen (Hercules) vertrieben werden.
• – Stärke und deren Derivate, insbesondere Stärkeether, beispielsweise Structure^® XL (National Starch), eine multifunktionelle, salztolerante Stärke;
• – Schellack
• – Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol^® (BASF) vertrieben werden.
• – Siloxane. Diese Siloxane können sowohl wasserlöslich als auch wasserunlöslich sein. Geeignet sind sowohl flüchtige als auch nichtflüchtige Siloxane, wobei als nichtflüchtige Siloxane solche Verbindungen verstanden werden, deren Siedepunkt bei Normaldruck oberhalb von 200 °C liegt. Bevorzugte Siloxane sind Polydialkylsiloxane, wie beispielsweise Polydimethylsiloxan, Polyalkylarylsiloxane, wie beispielsweise Polyphenylmethylsiloxan, ethoxylierte Polydialkylsiloxane sowie Polydialkylsiloxane, die Amin- und/oder Hydroxy-Gruppen enthalten.
• – Glycosidisch substituierte Silicone.

Suitable nonionic polymers are, for example:

• - Vinylpyrrolidone / vinyl ester copolymers, such as those sold under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are also preferred nonionic polymers.
• - cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as for example under the trademark Culminal® ^® and Benecel ^® (AQUALON) and Natrosol ^® grades (Hercules) are distributed.
• - starch and its derivatives, in particular starch, such as Structure XL ^® (National Starch), a multifunctional, salt-tolerant starch;
• - shellac
• - polyvinylpyrrolidones, as for example under the name Luviskol ^® (BASF).
• - siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, nonvolatile siloxanes being understood as meaning those compounds whose boiling point is above 200 ° C. under normal pressure. Preferred siloxanes are polydialkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups.
• - Glycosidically substituted silicones.

It It is also possible according to the invention that the preparations several, in particular two different polymers of the same charge and / or in each case an ionic and an amphoteric and / or not contain ionic polymer.

The Polymers (G) are preferred in amounts in the agents according to the invention from 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5, in particular from 0.1 to 3 wt .-%, are particularly prefers.

Farther can in a preferred embodiment the invention also an agent according to the invention UV filter (I) included. The invention to be used UV filters are subject to structural and physical considerations Features no general restrictions. Rather, they are suitable all UV filters that can be used in the cosmetics sector, their absorption maximum in the UVA (315-400 nm), in the UVB (280-315 nm) or in the UVC (<280 nm) range lies. UV filter with an absorption maximum in the UVB range, in particular in the range of about 280 to about 300 nm, are particularly preferred.

The used according to the invention UV filters can for example, selected are substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylates, cinnamic, salicylates, Benzimidazoles and o-aminobenzoic acid esters.

Examples of UV filters which can be used according to the invention are 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline-methylsulfate, 3,3,5-trimethyl-cyclohexylsalicylate (homosalates), 2-hydroxy-4-methoxy-benzophenone (benzophenone-3; Uvinul ^® M 40, Uvasorb MET ^{®, ®} Neo Heliopan BB, Eusolex ^® 4360), 2-phenylbenzimidazole-5-sulfonic acid and potassium, sodium and triethanolamine salts ( Phenylbenzimidazole Sulfonic Acid; Parsol ^® HS; Neo Heliopan Hydro ^®), 3,3 '- (1,4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo-bicyclo [2.2.1] hept-1- yl-methane sulfonic acid) and salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1,3-dione (butyl methoxydi benzoylmethane; Parsol ^® 1789 Eusolex ^® 9020), α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul ^® P 25), 4-dimethylaminobenzoic acid 2-ethylhexyl (octyl dimethyl PABA ; Uvasorb ^® DMO, Escalol ^® 507, Eusolex ^® 6007), salicylic acid-2-ethylhex ylester (octyl salicylate; Escalol ^® 587, Neo Heliopan ^® OS, Uvinul ^® O18), 4-methoxycinnamic acid isopentyl (isoamyl p-methoxycinnamate; Neo Heliopan ^® E 1000), 4-methoxycinnamic acid 2-ethylhexyl ester (Octyl Methoxycinnamate; Parsol ^® MCX, Escalol ^® 557, Neo Heliopan AV ^®), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (Benzophenone-4; Uvinul ^® MS 40; Uvasorb S 5 ^®), 3- (4'-methylbenzylidene) -D, L-camphor (4-methylbenzylidene camphor; Parsol ^® 5000, Eusolex ^® 6300), 3-benzylidene camphor (3-benzylidene camphor), 4-isopropylbenzyl, 2,4,6-trianilino- (p-carbo-2'- ethylhexyl-1'-oxi) -1,3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N - {(2 and 4) - [2-oxoborn-3-ylidenemethyl] benzyl } -acrylamids, 2,4-dihydroxy (benzophenone-1; Uvasorb ^® 20 H, Uvinul ^® 400), 1,1'-Diphenylacrylonitrilsäure-2-ethylhexyl ester (Octocrylene; Eusolex ^® OCR, Neo Heliopan ^® Type 303, Uvinul ^® N 539 SG), o-aminobenzoic acid menthyl ester (Menthyl Anthranilate; Neo He liopan ^® MA), 2,2 ', 4,4'-tetrahydroxy benzophenone (benzophenone-2; Uvinul ^® D-50), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Benzophenone-6), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate, and 2-cyano-3, 3-diphenylacrylate 2'-ethylhexyl acrylate. Preference is given to 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methylsulfate, 3,3,5-trimethylcyclohexylsalicylate, 2-hydroxy-4-methoxybenzophenone, 2 Phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3 '- (1,4-phenylenedimethylene) -bis (7,7-dimethyl-2-oxo-bicyclo- [2.2.1] hept- 1-yl-methanesulfonic acid) and its salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione, α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid and its salts, ethoxylated 4-aminobenzoic acid ethyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl salicylate, isopentyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, 2-hydroxy- 4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3- (4'-methylbenzylidene) -D, L-camphor, 3-benzylidene-camphor, 4-isopropylbenzyl salicylate, 2,4,6-trianilino- (p-carbo-2 '-ethylhexyl-1'-oxi) -1,3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N - {(2 and 4) - [2-ox Oborn-3-ylidenemethyl] benzyl} acrylamide. Very particularly preferred according to the invention are 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione, 4-methoxycinnamic acid 2-ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor.

Prefers are those UV filters whose molar extinction coefficient at the absorption maximum above 15,000, especially above 20,000.

Farther was found that at structurally similar UV filters in many cases the water-insoluble Compound in the context of the teaching of the invention, the higher effect across from such water-soluble Compounds that are distinguished from it by one or more additionally distinguish ionic groups. As water-insoluble are within the scope of the invention to understand those UV filters which at 20 ° C to not more than 1 wt .-%, in particular not more than 0.1% by weight, dissolve in water. Farther should these compounds in usual cosmetic oil components at room temperature to at least 0.1, in particular at least 1% by weight soluble be). The use of water-insoluble UV filter may therefore be preferred according to the invention.

According to one another embodiment the invention, those UV filters are preferred which are cationic Group, in particular a quaternary Ammonium group.

These UV filters have the general structure U - Q.

• – substituierte Benzophenone,
• – p-Aminobenzoesäureester,
• – Diphenylacrylsäureester,
• – Zimtsäureester,
• – Salicylsäureester,
• – Benzimidazole und
• – o-Aminobenzoesäureester.

The structural part U stands for a UV-absorbing group. This group can in principle be derived from the known UV filters which can be used in the cosmetics sector, in which a group, generally a hydrogen atom, of the UV filter is replaced by a cationic group Q, in particular having a quaternary amino function , Compounds from which the structural part U can derive are, for example

• Substituted benzophenones,
• P-aminobenzoic acid ester,
• - diphenylacrylic acid ester,
• - cinnamic acid ester,
• Salicylic acid ester,
• Benzimidazoles and
• O-aminobenzoic acid ester.

structural parts U, derived from cinnamamide or derive from N, N-dimethylamino-benzoic acid amide are preferred according to the invention.

The Structural parts U can chosen in principle be that Absorption maximum of the UV filter both in the UVA (315-400 nm), as well as in the UVB (280-315 nm) or in the UVC (<280 nm) range can lie. UV filter with an absorption maximum in the UVB range, especially in the range of about 280 to about 300 nm, are particularly prefers.

Farther is the structural part U, also in dependence on structural part Q, preferably chosen that the molar extinction coefficient of the UV filter at the absorption maximum above 15,000, especially above 20,000.

Of the Structure part Q contains as a cationic group, a quaternary ammonium group is preferred. This quaternary ammonium group can in principle be connected directly to the structural part U, so that the Structural part U one of the four substituents of the positively charged Represents nitrogen atom. However, one of the four is preferred Substituents on the positively charged nitrogen atom is a group, in particular an alkylene group having 2 to 6 carbon atoms, which as a compound between the structural part U and the positively charged nitrogen atom acts.

Advantageously, the group Q has the general structure - (CH ₂ ) _x -N ⁺ R ¹ R ² R ³ X ^- , in which x is an integer from 1 to 4, R ¹ and R ² independently of one another are C _{1 -4} alkyl groups, R ³ is a C _1-22 alkyl group or a benzyl group and X ^{- is} a physiologically acceptable anion. In the context of this general structure, x preferably represents the number 3, R ¹ and R ² each represent a methyl group and R ^{3 represents} either a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain having 8 to 22, in particular 10 to 18, carbon atoms.

physiological compatible Anions are, for example, inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.

Two preferred UV filters with cationic groups are the commercially available compounds cinnamic acid trimethyl ammonium chloride (Incroquat ^® UV-283) and Dodecyldimethylaminobenzamidopropyl-tosylate (Escalol ^® HP 610).

Of course, the teaching of the invention includes also the use of a combination of several UV filters. in the Frame of this embodiment is the combination of at least one water-insoluble UV filter with at least a UV filter with a cationic group is preferred.

The UV filters (I) are customary in the compositions according to the invention in amounts 0.1-5 wt .-%, based on the total agent included. Levels of 0.4-2.5 wt .-% are preferred.

The compositions of the invention may further contain a 2-pyrrolidinone-5-carboxylic acid and its derivatives (J). Preference is given to the sodium, potassium, calcium, magnesium or ammonium salts in which the ammonium ion carries, in addition to hydrogen, one to three C ₁ - to C ₄ -alkyl groups. The sodium salt is most preferred. The amounts used in the compositions according to the invention are preferably from 0.05 to 10% by weight, based on the total composition, particularly preferably from 0.1 to 5, and in particular from 0.1 to 3,% by weight.

Finally, the agents according to the invention also contain plant extracts (L).

Usually These extracts are produced by extraction of the whole plant. It may, however, in individual cases also be preferred, the extracts exclusively from flowers and / or Scroll to produce the plant.

Regarding the invention usable Plant extracts are particularly pointed to the extracts, in the on page 44 of the 3rd edition of the Guidance on the declaration of ingredients Cosmetic agent, published by the Industrieverband Körperpflege- and Detergents e.V. (IKW), Frankfurt, beginning table are listed.

According to the invention are available especially the extracts of green Tea, Oak bark, Stinging nettle, Hamamelis, Hops, Henna, Chamomile, Burdock root, horsetail, hawthorn, lime blossom, almond, Aloe vera, spruce needle, horse chestnut, Sandalwood, juniper, coconut, Mango, Apricot, Lime, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Rosemary, Birch, Mallow, Meadowfoam, Quendel, Yarrow, Thyme, melissa, hominy, coltsfoot, marshmallow, meristem, ginseng and ginger root preferred.

Especially preferred are the extracts of green tea, oak bark, stinging nettle, Witch hazel, hops, chamomile, burdock root, horsetail, lime blossom, almond, Aloe vera, coconut, Mango, Apricot, Lime, Wheat, Kiwi, Melon, Orange, Grapefruit, Sage, Rosemary, Birch, Meadowfoam, Quendel, Yarrow, Homeselps, meristem, ginseng and ginger root.

All especially for the use according to the invention suitable are the extracts of green tea, almond, aloe vera, Coconut, Mango, apricot, lime, wheat, kiwi and melon.

When Extraction agent for the preparation of said plant extracts can Water, alcohols and mixtures thereof are used. Under the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant and in mixture with Water, preferably. Plant extracts based on water / propylene glycol in relation to 1:10 to 10: 1 have proven to be particularly suitable.

The Plant extracts can according to the invention both in pure as well as in diluted Form are used. If used in dilute form, they usually contain about 2 - 80 Wt .-% of active substance and as a solvent the extractant or extractant mixture used in their extraction.

Farther it may be preferred in the inventive compositions of several, especially from two, different plant extracts use.

In addition, can it prove to be advantageous when in the inventive compositions Penetrants and / or swelling agents (M) are included. These include, for example, to count Urea and urea derivatives, guanidine and its derivatives, arginine and its derivatives, water glass, imidazole and its derivatives, histidine and its derivatives, benzyl alcohol, glycerol, glycol and glycol ether, Propylene glycol and propylene glycol ether, for example propylene glycol monoethyl ether, Carbonates, bicarbonates, diols and triols, and in particular 1,2-diols and 1,3-diols such as 1,2-propanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-dodecanediol, 1,3-propanediol, 1,6-hexanediol, 1,5-pentanediol, 1,4-butanediol.

A particularly preferred group of ingredients are the silicones represents.

• (i) Polyalkylsiloxanen, Polyarylsiloxanen, Polyalkylarylsiloxanen, die flüchtig oder nicht flüchtig, geradkettig, verzweigt oder cyclisch, vernetzt oder nicht vernetzt sind;
• (ii) Polysiloxanen, die in ihrer allgemeinen Struktur eine oder mehrere organofunktionelle Gruppen enthalten, die ausgewählt sind unter:
• a) substituierten oder unsubstituierten aminierten Gruppen;
• b) (per)fluorierten Gruppen;
• c) Thiolgruppen;
• d) Carboxylatgruppen;
• e) hydroxylierten Gruppen;
• f) alkoxylierten Gruppen;
• g) Acyloxyalkylgruppen;
• h) amphoteren Gruppen;
• i) Bisulfitgruppen;
• j) Hydroxyacylaminogruppen;
• k) Carboxygruppen;
• l) Sulfonsäuregruppen; und
• m) Sulfat- oder Thiosulfatgruppen;
• (iii) linearen Polysiloxan(A)- Polyoxyalkylen(B)- Blockcopoylmeren vom Typ (A-B)_n mit n > 3;
• (iv) gepfropften Siliconpolymeren mit nicht siliconhaltigem, organischen Grundgerüst, die aus einer organischen Hauptkette bestehen, welche aus organischen Monomeren gebildet wird, die kein Silicon enthalten, auf die in der Kette sowie gegebenenfalls an mindestens einem Kettenende mindestens ein Polysiloxanmakromer gepfropft wurde;
• (v) gepfropften Siliconpolymeren mit Polysiloxan-Grundgerüst, auf das nicht siliconhaltige, organische Monomere gepfropft wurden, die eine Polysiloxan-Hauptkette aufweisen, auf die in der Kette sowie gegebenenfalls an mindestens einem ihrer Enden mindestens ein organisches Makromer gepfropft wurde, das kein Silicon enthält; oder deren Gemischen.

Preferred agents according to the invention are characterized in that they comprise at least one silicone, preferably a silicone, selected from:

• (i) polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes which are volatile or nonvolatile, straight chain, branched or cyclic, crosslinked or uncrosslinked;
• (ii) Polysiloxanes containing in their general structure one or more organofunctional groups selected from:
• a) substituted or unsubstituted aminated groups;
• b) (per) fluorinated groups;
• c) thiol groups;
• d) carboxylate groups;
• e) hydroxylated groups;
• f) alkoxylated groups;
• g) acyloxyalkyl groups;
• h) amphoteric groups;
• i) bisulfite groups;
• j) hydroxyacylamino groups;
• k) carboxy groups;
• l) sulfonic acid groups; and
• m) sulphate or thiosulphate groups;
• (iii) linear polysiloxane (A) - polyoxyalkylene (B) - block copolymers of the type (AB) _n with n>3;
• (iv) grafted silicone polymers having a non-silicone organic backbone consisting of an organic backbone formed from organic monomers containing no silicone grafted with at least one polysiloxane macromer in the chain and optionally at least one chain end;
• (v) grafted polysiloxane backbone silicone polymers having grafted thereto non-silicone organic monomers having a polysiloxane backbone to which at least one organic macromer not containing silicone has been grafted in the chain, and optionally at least at one of its ends ; or their mixtures.

Particularly according to the invention preferred colorants contain the silicone (s) preferably in amounts of 0.1 to 10 wt .-%, preferably from 0.25 to 7 wt .-% and in particular from 0.5 to 5 wt .-%, each based on the total agent.

preferred Silicones are described below.

Particularly preferred oxidation colorants according to the invention are characterized in that they contain at least one silicone of the formula Si-I (CH ₃ ) ₃ Si- [O-Si (CH ₃ ) ₂ ] _x -O-Si (CH ₃ ) ₃ (Si-I), in which x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.

These silicones are called DIMETHICONE according to the INCI nomenclature. In the context of the present invention, as the silicone of the formula Si-1, the compounds are preferably:
(CH ₃ ) ₃ Si-O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si (O- (CH ₃ ) ₂ Si] ₂ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₃ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₄ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₅ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₆ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₇ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₈ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₉ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₀ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₁ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₂ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₃ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₄ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₅ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) Si] ₁₆ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₇ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₈ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₉ -O-Si (CH ₃ ) ₃
(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₂₀ -O-Si (CH ₃ ) ₃
where (CH ₃ ) ₃ Si-O-Si (CH ₃ ) ₃ , (CH ₃ ) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) ₃ and / or (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₂ -O-Si (CH ₃ ) _{3 are} particularly preferred.

Of course you can too Mixtures of the above Silicones in the compositions according to the invention be included.

Preferred silicones which can be used according to the invention have viscosities of from 0.2 to 2 mm ² s ^-1 at 20 ° C., silicones having viscosities of from 0.5 to 1 mm ² s ^{-1 being} particularly preferred.

Particularly preferred agents according to the invention contain one or more amino-functional silicones. Such silicones may, for example, be represented by the formula M (R _a Q _b SiO _{(4-ab) / 2) x} (R _c SiO _{(4-c) / 2y} M) wherein R in the above formula is a hydrocarbon or a hydrocarbon group of 1 to about 6 carbon atoms, Q is a polar group of the general formula -R ¹ HZ wherein R ^{1 is} a divalent linking group attached to hydrogen and the group Z is an organic, amino-functional radical containing at least one amino-functional group, carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms; "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range from about 1 to about 3, and x is a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and y is a number ranging from about 20 to about 10,000 , preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy. Non-limiting examples of the groups represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R ¹ include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH ₂ CH (CH ₃ ) CH ₂ -, phenylene, naphthylene, -CH ₂ CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ - , -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) C (O) OCH ₂ -, - (CH ₂ ) ₃ CC (O) OCH ₂ CH ₂ -, C ₆ H ₄ C ₆ N ₄ -, -C ₆ H ₄ CH ₂ C ₆ H ₄ -; and - (CH ₂ ) ₃ C (O) SCH ₂ CH ₂ -.

Z is an organic, amino-functional radical containing at least one functional amino group. A possible formula for Z is NH (CH ₂ ) _z NH ₂ , wherein z is 1 or more. Another possible formula for Z is -NH (CH ₂ ) _z (CH ₂ ) _zz NH, wherein both z and zz are independently 1 or more, which structure includes diamino ring structures, such as piperazinyl. Z is most preferably a -NHCH ₂ CH ₂ NH ₂ radical. Another possible formula for Z is -N (CH ₂ ) _z (CH ₂ ) _zz NX ₂ or -NX ₂ , wherein each X of X _{2 is} independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar, amine functional group of formula -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH z. In the formulas, "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 2 to about 3, "a" + "b" is less than or equal to 3, and "c "is a number in the range of about 1 to about 3. The molar ratio of the R _a Q _b SiO _{(4-ab) / 2} units to the R _c SiO _{(4-c) / 2} units is in the range of about From 1: 2 to 1:65, preferably from about 1: 5 to about 1: 65, and most preferably from about 1: 15 to about 1: 20. When one or more silicones of the above formula are employed then the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.

• – G ist -H, eine Phenylgruppe, -OH, -O-CH₃, -CH₃, -O-CH₂CH₃, -CH₂CH₃, -O-CH₂CH₂CH₃,-CH₂CH₂CH₃, -O-CH(CH₃)₂, -CH(CH₃)₂, -O-CH₂CH₂CH₂CH₃, -CH₂CH₂CH₂CH₃, -O-CH₂CH(CH₃)₂, -CH₂CH(CH₃)₂, -O-CH(CH₃)CH₂CH₃, -CH(CH₃)CH₂CH₃, -O-C(CH₃)₃, -C(CH₃)₃;
• – a steht für eine Zahl zwischen 0 und 3, insbesondere 0;
• – b steht für eine Zahl zwischen 0 und 1, insbesondere 1,
• – m und n sind Zahlen, deren Summe (m + n) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei n vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt,
• – R' ist ein monovalenter Rest ausgewählt aus – -Q-N(R'')-CH₂-CH₂-N(R'')₂ – -Q-N(R'')₂ – -Q-N⁺(R'')₃A^– – -Q-N⁺H(R'')₂A^– – -Q-N⁺H₂(R'')A^– – -Q-N(R'')-CH₂-CH₂-N⁺R''H₂A^–, wobei jedes Q für eine chemische Bindung, -CH₂-, -CH₂-CH₂-, -CH₂CH₂CH₂-, -C(CH₃)₂-, -CH₂CH₂CH₂CH₂-, -CH₂C(CH₃)₂-, -CH(CH₃)CH₂CH₂- steht, R'' für gleiche oder verschiedene Reste aus der Gruppe -H, -Phenyl, -Benzyl, -CH₂-CH(CH₃)Ph, der C_1-20-Alkylreste, vorzugsweise -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂, -CH₂CH₂CH₂H₃, -CH₂CH(CH₃)₂, -CH(CH₃)CH₂CH₃, -C(CH₃)₃, steht und A ein Anion repräsentiert, welches vorzugsweise ausgewählt ist aus Chlorid, Bromid, Iodid oder Methosulfat.

Preferred oxidation colorants according to the invention are characterized in that they contain an amino-functional silicone of the formula (Si-II) R ' _a G _3-a Si (OSiG ₂ ) _n - (OSiG _b R' _2-b ) _m -O-SiG _3-a R ' _a (Si-II), contain, in which means:

• G is -H, a phenyl group, -OH, -O-CH ₃ , -CH ₃ , -O-CH ₂ CH ₃ , -CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -O-CH (CH ₃ ) ₂ , -CH (CH ₃ ) ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -O-CH ₂ CH (CH ₃ ) ₂ , -CH ₂ CH (CH ₃ ) ₂ , -O-CH (CH ₃ ) CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , -C (CH ₃ ) ₃ ;
• A is a number between 0 and 3, in particular 0;
• B is a number between 0 and 1, in particular 1,
• M and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10,
• R 'is a monovalent radical selected from --QN (R'') - CH ₂ -CH ₂ -N (R'') ₂ - -QN (R'') ₂ - -QN ⁺ (R'') ₃ A ^- - -QN ⁺ H (R '') ₂ A ^- - -QN ⁺ H ₂ (R '') A ^- - -QN (R '') - CH ₂ -CH ₂ -N ⁺ R''H ₂ A ^- , wherein each Q is a chemical bond, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C (CH ₃ ) ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ C (CH ₃ ) ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -, R '' represents identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH ( CH ₃ ) Ph, the C _1-20 -alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , and A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.

enthalten, worin m und n Zahlen sind, deren Summe (m + n) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei n vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt.Particularly preferred agents according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (Si-IIa)

in which m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes.

These Silicones are classified as trimethylsilylamodimethicones according to the INCI declaration designated.

enthalten, worin R für -OH, -O-CH₃ oder eine -CH₃-Gruppe steht und m, n1 und n2 Zahlen sind, deren Summe (m + n1 + n2) zwischen 1 und 2000, vorzugsweise zwischen 50 und 150 beträgt, wobei die Summe (n1 + n2) vorzugsweise Werte von 0 bis 1999 und insbesondere von 49 bis 149 und m vorzugsweise Werte von 1 bis 2000, insbesondere von 1 bis 10 annimmt.Also particularly preferred are agents according to the invention which are an amino-functional silicone of the formula (Si-IIb)

in which R is -OH, -O-CH ₃ or a -CH ₃ group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and 150 , where the sum (n1 + n2) preferably assumes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10.

These Silicones are called amodimethicones according to the INCI declaration.

Independently of, which amino-functional silicones are used are agents according to the invention preferably containing an amino-functional silicone whose amine number above 0.25 meq / g, preferably above 0.3 meq / g and especially above 0.4 meq / g. The amine number stands for the milliequivalents Amine per gram of amino-functional silicone. It can be done by titration determined and also in the unit mg KOH / g.

According to the invention preferred dye are characterized in that they based on their weight, 0.01 to 10 wt.%, Preferably 0.1 to 8 wt.%, Particularly preferably 0.25 to 7.5 wt.% And in particular 0.5 to 5 wt.% Amino-functional silicone (s) included.

enthalten, in der x für eine Zahl von 0 bis 200, vorzugsweise von 0 bis 10, weiter bevorzugt von 0 bis 7 und insbesondere 0, 1, 2, 3, 4, 5 oder 6, steht.The INCI CYCLOMETHICONE designated cyclic dimethicones are inventively used with preference. Here, coloring agents according to the invention are preferred for keratinic fibers which contain at least one silicone of the formula Si-III

in which x is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6 stands.

The silicones described above have a backbone consisting of -Si-O-Si units is constructed. Of course can these Si-O-Si units may also be interrupted by carbon chains. Appropriate molecules are by chain extension reactions accessible and preferably come in the form of silicone-in-water emulsions for use.

The silicone-in-water emulsions which can be used according to the invention can be prepared by known processes, as described, for example, in US Pat US 5,998,537 and EP 0 874 017 A1 are disclosed.

In summary comprises this manufacturing process the emulsifying mixture of components, one of which contains at least one polysiloxane, the other at least contains an organosilicone material, which reacts with the polysiloxane in a chain extension reaction, wherein at least one metal ion-containing catalyst for the chain extension reaction, at least one surfactant and water are present.

Chain extension reactions with polysiloxanes are known and may include, for example, the hydrosilylation reaction in which an Si-H group having an aliphatically unsaturated group in the presence of a platinum / rhodium catalyst to form polysiloxanes having some Si (C) _p Si bonds (p = 1-6), the polysiloxanes also being referred to as polysiloxanes-polysilalkylenes copolymers.

The Chain extension reaction can also be the reaction of an Si-OH group (for example, a hydroxy-terminated Polysiloxane) having an alkoxy group (for example, alkoxysilanes, Silicates or alkoxysiloxanes) in the presence of a metal-containing Catalyst to form polysiloxanes include.

The polysiloxanes used in the chain extension reaction comprise a substantially linear polymer of the following structure: R-Si (R ₂ ) - [- O-Si (R ₂ ) -] _n -O-SiR ₃

In this structure, each R independently represents a hydrocarbon radical having up to 20 carbon atoms, preferably having 1 to 6 carbon atoms, such as an alkyl group (for example, methyl, ethyl, propyl or butyl), an aryl group (for example, phenyl), or group required for the chain extension reaction ("reactive group", for example, Si-bonded H atoms, aliphatically unsaturated groups such as vinyl, allyl or hexenyl, hydroxy, alkoxy such as methoxy, ethoxy or propoxy, alkoxy-alkoxy, acetoxy, amino, etc.), with the proviso that on average one to two reactive groups are present per polymer, n is a positive number> 1. Preferably, a plurality of the reactive groups, more preferably> 90%, and especially> 98% of the reactive groups, at the terminal Si -Atomen bound in siloxane. Preferably, n is numbers describing polysiloxanes having viscosities between 1 and 1,000,000 mm ² / s, more preferably viscosities between 1,000 and 100,000 mm ² / s.

The Polysiloxanes can branched to a low degree (for example <2 mol% of the siloxane units), but preferably the polymers are substantially linear, especially preferably completely linear. In addition, you can the substituents R in turn be substituted, for example with N-containing groups (for example amino groups), epoxy groups, S-containing groups, Si-containing groups, O-containing groups, etc. Preferably At least 80% of the radicals R are alkyl radicals, particularly preferably methyl groups.

The Organosilicone material that reacts with the polysiloxane in the chain extension reaction can either be a second polysiloxane, or a molecule known as chain acts. When the organosilicone material is a polysiloxane it the above-mentioned general structure. In these cases has a polysiloxane in the reaction (at least) a reactive Group, and a second polysiloxane has (at least) a second one reactive group that reacts with the first one.

If the organosilicone material comprises a chain extending agent this may be a material such as a silane, a siloxane (For example, disiloxanes or trisiloxane) or a silazane. So For example, a composition comprising a polysiloxane according to the above described general structure, which comprises at least one Si-OH group can be chain extended by reacting with an alkoxysilane (For example, a dialkoxysilane or trialkoxysilane) in the presence is reacted by tin or titanium-containing catalysts.

The metal-containing catalysts in the chain extension reaction are usually specific for a particular reaction. Such catalysts are known in the art and include, for example, metals such as platinum, rhodium, tin, titanium, copper, lead, etc. In a preferred chain extension reaction, a polysiloxane having at least one aliphatically unsaturated group, preferably an end group, is reacted with an organosilicone material Presence of a hydrosilylation catalyst which is a siloxane or polysiloxane having at least one (preferably terminal) Si-H group. The polysiloxane has at least one aliphatically unsaturated group and satisfies the general formula given above in which R and n are as defined above, with an average of between 1 and 2 groups R having one aliphatically unsaturated group per polymer. Representative aliphatically unsaturated groups are, for example, vinyl, allyl, hexenyl and cyclohexenyl or a group R ² CH = CHR ³ , in which R ^{2 is} a divalent aliphatic silicon-bonded chain and R ^{3 represents} a hydrogen atom or an alkyl group. The organosilicone material having at least one Si-H group preferably has the above-mentioned structure, wherein R and n are as defined above and wherein, on average, between 1 and 2 groups R is hydrogen and n is 0 or a positive integer.

This Material may be a polymer or a low molecular weight material such as a siloxane (for example, a disiloxane or a trisiloxane).

The Polysiloxane with at least one aliphatic unsaturated Group and the organosilicone material having at least one Si-H group react in the presence of a hydrosilation catalyst. Such Catalysts are known in the art and include For example, platinum and rhodium-containing materials. The Catalysts can take any known form, for example on support materials (such as silica gel or activated carbon) applied platinum or rhodium or other suitable compounds such as platinum chloride, Salts of platinum or chloroplatinic acids. One because of the good dispersibility in organosilicon systems and the slight color change preferred catalyst is chloroplatinic acid either as commercial available Hexahydrate or in anhydrous form.

at Another preferred chain extension reaction is a polysiloxane with at least one Si-OH group, preferably an end group, reacted with an organosilicone material which is at least has an alkoxy group, preferably a siloxane having at least a Si-OR group or an alkoxysilane having at least two alkoxy groups. In this case, the catalyst again is a metal-containing catalyst used.

For the reaction an Si-OH group with an Si-OR group, many known in the literature exist Catalysts, for example organometallic compounds such as organotin salts, Titanates or titanium chelates or complexes. Examples include tin octoate, Dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, Dibutyltin dimethoxide, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin dineodecanoate, triethyltin tartrate, Tin oleate, tin naphthenate, tin butyrate, tin acetate, tin benzoate, Tin sebacate, tin succinate, tetrabutyl titanate, tetraisopropyl titanate, Tetraphenyl titanate, tetraoctadecyl titanate, titanium naphthanate, ethyl triethanolamine titanate, Titani-diisopropyl-diethyl acetoacetate, Titanium diisopropoxy-diacetyl-acetonate and titanium tetra-alkoxides, where the alkoxide is butoxy or propoxy.

Colorants which are likewise preferred according to the invention are characterized in that they contain at least one silicone of the formula Si-IV R ₃ Si [O-SiR ₂ ] _x - (CH ₂ ) _n - [O-SiR ₂ ] _y -O-SiR ₃ (Si-IV), in which R is identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph, the C _1-20 -alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , - C (CH ₃ ) ₃ , x and y are a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and especially 0, 1, 2, 3, 4, 5 or 6, stand and n is a number from 0 to 10, preferably from 1 to 8 and in particular from 2, 3, 4, 5, 6.

With The silicones are preferably water-soluble. According to the invention preferred dye are characterized in that they at least one water-soluble Silicone included.

at An application of oxidants becomes the actual colorant as mentioned above, expediently immediately before use by mixing the preparation of the Oxidizing agent B with the preparation containing the dye precursors, produced. The resulting ready-to-use hair dye preparation should preferably have a pH in the range of 6 to 12. Especially Preferably, the application of the hair dye in a weak alkaline environment. The application temperatures can be in a range between 15 and 40 ° C lie. After an exposure time of 5 to 45 minutes, the Hair Dye by rinsing of which to be colored Hair removed. The washing with a shampoo is eliminated, if a strong surfactant-containing carrier, e.g. a dyeing shampoo, has been used.

In particular, in the case of hair that is difficult to dye, an agent according to the invention may optionally be applied to the hair with additional dye precursors but also without prior mixing with the oxidation component. After an exposure time of 20 to 30 minutes, the oxidation component is then applied, if appropriate after an intermediate rinse. After a further exposure time of 10 to 20 minutes is then rinsed and ge wished if nachshampooniert. In this embodiment According to a first variant, in which the previous application of the dye precursors is to bring about a better penetration into the hair, the corresponding agent is adjusted to a pH of about 4 to 7. According to a second variant, an air oxidation is initially desired, wherein the applied agent preferably has a pH of 7 to 10. In the subsequent accelerated post-oxidation, the use of acidified peroxydisulfate solutions may be preferred as the oxidizing agent.

In addition, the agents according to the invention contain additional ingredients. A use of certain metal ions For example, or complexes may be preferred to be intense colorations to obtain. Here, agents according to the invention are preferred which additionally contain Cu, Fe, Mn, Ru ions or complexes of these ions.

Preferred hair coloring and lightening agents according to the invention contain from 0.0001 to 2.5% by weight, preferably from 0.001 to 1% by weight, based on the total composition of the composition, of at least one compound from the group consisting of copper chloride (CuCl ₂ ), copper sulfate ( CuSO ₄ ), iron (II) sulfate, manganese (II) sulfate, manganese (II) chloride, cobalt (II) chloride, cerium sulfate, cerium chloride, vanadium sulfate, potassium iodide, sodium iodide, lithium chloride, potassium dichromate, magnesium acetate, calcium chloride, calcium nitrate, barium nitrate, Manganese dioxide (MnO ₂ ) and / or hydroquinone.

When further ingredient can the compositions of the invention at least one ammonium compound from the group ammonium chloride, Ammonium carbonate, ammonium bicarbonate, ammonium sulfate and / or ammonium carbamate in an amount of 0.5 to 10, preferably 1 to 5 wt .-%, based on contain the total composition of the agent.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidon/Vinylacrylat-Copolymere, Polyvinylpyrrolidon und Vinylpyrrolidon/Vinylacetat-Copolymere und Polysiloxane,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-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 Wasserstoffperoxid und andere Oxidationsmittel,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂ und Luft,
• – Antioxidantien,

enthaltenFurthermore, the agents according to the invention may contain 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,
• 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 such as methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such as bentonite or fully synthetic hydrocolloids such as polyvinyl alcohol,
• - structurants such as maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,
• Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and quaternized protein hydrolysates,
• Perfume oils, dimethylisosorbide and cyclodextrins,
• 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, melissa, 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,
• Stabilizing agent for hydrogen peroxide and other oxidizing agents,
• Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,
• - antioxidants,

contain

When another optional ingredient may be the agents of the invention 0.01 to 10 wt .-% chitosan and / or chitosan derivative (s) included.

chitosan is the deacetylation product of chitin, with a defined transition between chitosan and chitin does not exist. In the context of the present Invention is spoken of chitosan when the degree of deacetylation of chitin is at least 20%. Preferred agents according to the invention contain chitosans (or derivatives thereof) whose degree of deacetylation is> 30%, in particular> 40-50%. Further preferred are chitosans and derivatives thereof which are soluble in organic acids.

preferred used according to the invention Chitosans or derivatives thereof have molecular weights of 100,000 to 500,000 Dalton on. Chitosan consists of chains of beta-1,4-glycosidic linked N-acetyl-D-glucosamine (NAG) residues.

preferred inventive agent to dye and / or lightening keratinic fibers are characterized that they - related on her weight - 0.05 to 7.5% by weight, preferably 0.1 to 5% by weight, more preferably 0.2 to 3.5 wt .-% and in particular 0.25 to 1.5 wt .-% chitosan and / or chitosan derivative (s).

Preferably are those in the inventive compositions used chitosans or their derivatives are water-soluble. preferred inventive agent to dye and / or lightening keratinic fibers are characterized that she Chitosan derivative (s) containing a water solubility in distilled Water above 1 g / l (20 ° C, 1013 mbar).

Prefers Chitosan derivatives to be used are derivatized at the amino group. Particularly preferred chitosan derivatives have one to the nitrogen atom the amino group bonded acid radical, preferably the residue of an organic acid. Especially preferred Chitoanderivate have at least one of the nitrogen atom of Amino group bonded acid radical following acids on: formic acid, Acetic acid, propionic acid, butyric acid, Valeric acid, caproic, heptanoic, caprylic, Pelargonic, capric, undecanoic, lauric, tridecanoic, tetradecanoic, pentadecanoic, palmitic, margaric, stearic, nonadecanoic, arachidic, behenic, lignoceric, cerotic, melissic, isobutyric, isovaleric, tubercolostearic, acrylic, crotonic, palmitoleic, oleic, erucic, sorbic, Linoleic, linolenic, elaeostearic, arachidonic, clupanodonic, docosahexaenoic, oxalic, malonic, succinic, glutaric, adipic, pimelic, azelaic, sebacic, maleic, fumaric, muconic, phthalic, terephthalic.

• – Chitosanglycolat
• – N-Acetyl-Chitosan (Chitosanacetat)
• – N-Propionyl-Chitosan (Chitosanpropionat)
• – N-Butanoyl-Chitosan (Chitosanbutanoat)
• – N-Malonyl-Chitosan (Chitosanmalonat)
• – N-Succinyl-Chitosan (Chitosansuccinat)
• – N-Adipyl-Chitosan (Chitosanadipat).

Particularly preferred agents according to the invention for dyeing and / or lightening keratinic fibers are characterized in that the chitosan derivative (s) contained in them is / are selected

• - chitosan glycolate
• - N-acetyl-chitosan (chitosan acetate)
• N-propionyl chitosan (chitosan propionate)
• - N-butanoyl-chitosan (chitosan-butanoate)
• - N-malonyl chitosan (chitosan malonate)
• N-succinyl chitosan (chitosan succinate)
• - N-adipyl-chitosan (chitosan adipate).

Another preferred group of ingredients of the compositions of the invention are vitamins, provitamins or vitamin precursors. These are described below:
The group of substances called vitamin A includes retinol (vitamin A ₁ ) and 3,4-didehydroretinol (vitamin A ₂ ). The β-carotene is the provitamin of retinol. As vitamin A component according to the invention, for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as the palmitate and the acetate into consideration. The agents according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the total preparation.

• – Vitamin B₁ (Thiamin)
• – Vitamin B₂ (Riboflavin)
• – Vitamin B₃. Unter dieser Bezeichnung werden häufig die Verbindungen Nicotinsäure und Nicotinsäureamid (Niacinamid) geführt. Erfindungsgemäß bevorzugt ist das Nicotinsäureamid, das in den erfindungsgemäß verwendeten Mitteln bevorzugt in Mengen von 0,05 bis 1 Gew.-%, bezogen auf das gesamte Mittel, enthalten ist.
• – Vitamin B₅ (Pantothensäure, Panthenol und Pantolacton). Im Rahmen dieser Gruppe wird bevorzugt das Panthenol und/oder Pantolacton eingesetzt. Erfindungsgemäß einsetzbare Derivate des Panthenols sind insbesondere die Ester und Ether des Panthenols sowie kationisch derivatisierte Panthenole. Einzelne Vertreter sind beispielsweise das Panthenoltriacetat, der Panthenolmonoethylether und dessen Monoacetat sowie die in der WO 92/13829 offenbarten kationischen Panthenolderivate. Die genannten Verbindungen des Vitamin B₅-Typs sind in den erfindungsgemäßen Mitteln bevorzugt in Mengen von 0,05 – 10 Gew.-%, bezogen auf das gesamte Mittel, enthalten. Mengen von 0,1 – 5 Gew.-% sind besonders bevorzugt.
• – Vitamin B₆ (Pyridoxin sowie Pyridoxamin und Pyridoxal).

The vitamin B group or the vitamin B complex include, among others

• - Vitamin B ₁ (thiamine)
• - Vitamin B ₂ (riboflavin)
• - Vitamin B ₃ . Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. Preferred according to the invention is the nicotinic acid amide which is contained in the agents used according to the invention preferably in amounts of from 0.05 to 1% by weight, based on the total agent.
• - Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Panthenol and / or pantolactone are preferably used in the context of this group. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and also cationically derivatized panthenols. Individual representatives are, for example, the panthenol triacetate, the panthenol monoethyl ether and its monoacetate and also the cationic panthenol derivatives disclosed in WO 92/13829. The said compounds of the vitamin B ₅ type are preferably contained in the agents according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5 wt .-% are particularly preferred.
• - Vitamin B ₆ (pyridoxine and pyridoxamine and pyridoxal).

vitamin C (ascorbic acid). Vitamin C is preferably used in amounts of 0.1 to 3 wt .-%, based on the total agent used. The Use in the form of palmitic acid ester, the glucoside or phosphates may be preferred. The usage in combination with tocopherols may also be preferred.

vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, including in particular the esters such as the acetate, the nicotinate, the phosphate and the succinate fall, are in the inventive compositions preferably in amounts of 0.05-1% by weight, based on the total agent, contain.

vitamin F. By the term "vitamin F "are usually essential fatty acids, especially linoleic acid, linolenic and arachidonic acid, Understood.

vitamin H. The vitamin H is the compound (3aS, 4S, 6aR) -2-oxohexahydrothienol [3,4-d] imidazole-4-valeric acid, for the But in the meantime, the trivial name Biotin has prevailed. biotin is in the inventive compositions preferably in amounts of 0.0001 to 1.0 wt .-%, in particular in amounts of 0.001 to 0.01 wt .-%.

In summary are agents according to the invention to dye and / or lightening keratinic fibers which additionally contain vitamins and / or pro-vitamins and / or vitamin precursors, preferably the groups A, B, C, E, F and H are assigned, preferred The compounds mentioned being used in amounts of from 0.1 to 5% by weight, preferably from 0.25 to 4 wt .-% and in particular from 0.5 to 2.5 wt .-%, each based on the total agent included.

in welchen die Reste R¹ bis R¹⁰ unabhängig voneinander stehen für:

• – Wasserstoff, -OH, einen Methyl-, Methoxy-, Aminomethyl- oder Hydroxymethylrest,
• – -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest,
• – -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -OR¹¹, mit R¹¹ als einem -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -NR¹²R¹³, wobei R¹² und R¹³ jeweils unabhängig voneinander stehen für Wasserstoff, einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -COOR¹⁴, wobei R¹⁴ steht für Wasserstoff, einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -CONR¹⁵R¹⁶, wobei R¹⁵ und R¹⁶ jeweils stehen für Wasserstoff, Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -COR¹⁶, wobei R¹⁶ steht für einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -OCOR¹⁷, wobei R¹⁷ steht für einen Methyl-, einen -C₂-C₃₀-gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Mono-, Di-, Tri- oder Polyhydroxykohlenwasserstoffrest, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Mono-, Di-, Tri- oder Polyaminokohlenwasserstoffrest,

mit der Maßgabe, daß für den Fall, wenn R⁷ und R⁸ für -OH und gleichzeitig R⁹ oder R¹⁰ für Wasserstoff stehen, die verbleibende Gruppe R⁹ oder R¹⁰ nicht für einen Dihydroxyethylrest steht.Agents preferred according to the invention additionally comprise at least one 2-furanone derivative of the formula (VIII) and / or of the formula (IX.

in which the radicals R ¹ to R ^{10 are} independently of one another

• Hydrogen, -OH, a methyl, methoxy, aminomethyl or hydroxymethyl radical,
• --C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical,
• - C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or Trihydroxykohlenwasserstoffrest,
• --C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• - a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbyl radical,
• - a group -NR ¹² R ¹³ , wherein R ¹² and R ¹³ each independently represent hydrogen, a methyl, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,
• A group -COOR ¹⁴ , where R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated hydrocarbon radical, or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbyl radical,
• - a group -CONR ¹⁵ R ¹⁶ , wherein R ¹⁵ and R ¹⁶ each represent hydrogen, methyl, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ - saturated mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbon hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• A group -COR ¹⁶ , where R ¹⁶ is a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or -or- or di-unsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• - a group -OCOR ^17, wherein R ¹⁷ is a methyl, a C ₂ -C ₃₀ saturated or mono- or polyunsaturated branched, or linear hydrocarbon group, a -C ₂ -C ₃₀ - saturated or mono- or polyunsaturated, branched or linear mono-, di-, tri- or polyhydroxy hydrocarbon radical, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear mono-, di-, tri- or polyamino hydrocarbon radical,

with the proviso that when R ⁷ and R ^{8 are} -OH and at the same time R ⁹ or R ^{10 is} hydrogen, the remaining group R ⁹ or R ¹⁰ does not represent a dihydroxyethyl radical.

2-furanones are known compounds and are described, for example, in "Rompps Lexikon der Chemie, Interactive CD-Rom Version 2.0, for the keyword" dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone "and in"Ullmann's Encyclopedia , sixth edition 1999, electronic release "in Sections 2.4, 2.7, 3.2, 3.4, 4.3, 6, 11 and 15. and the references cited therein relating to their manufacture and use The compounds of the formulas (VIII) and (IX) are employed as intermediates in the synthesis of natural products and in the preparation of medicaments and vitamins The preparation of the active compounds according to formulas (VIII) and (IX) can be carried out, for example, by reaction of primary Furthermore, compounds of the formula (VIII) are obtained by reactions starting from hydroxypivaldehyde, and carbonylations of alkynes lead to substituted 2-furanones Formula (VIII) or (IX). Finally, the compounds of the formula (VIII) or of the formula (IX) can be obtained by intramolecular esterification of the corresponding hydroxycarboxylic acids. For example, the following compounds are on any of the previously indicated Synthesis routes obtained: 2,5-dihydro-5-methoxy-2-furanone, tetrahydro-5-oxo-2-furancarboxylic acid, dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone, or 3,4 Dimethyl 5-pentylidenedihydro-2 (5H) -furanone or 4-hydroxy-2,5-dimethyl-3 (2H) -furanone. Of course, the 2-furanones according to the invention include all possible stereoisomers as well as their mixtures. By the 2-furanones according to the invention, the odor of the cosmetic agent is not permanently affected, so that a perfuming of the agent must be done separately.

• – Wasserstoff, einen -OH-, einen Methyl-, Methoxy-, Aminomethyl-, Hydroxymethylrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -OR¹¹, mit R¹¹ als einem -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -NR¹²R¹³, wobei R¹² und R¹³ jeweils unabhängig voneinander stehen für Wasserstoff, einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -COOR¹⁴, wobei R¹⁴ steht für Wasserstoff, einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -COR¹⁶, wobei R¹⁶ steht für einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -OCOR¹⁷, wobei R¹⁷ steht für einen Methyl-, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Mono-, Di-, Tri- oder Polyhydroxyalkylrest, oder einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Mono-, Di-, Tri- oder Polyaminokohlenwasserstoffrest.

Preferred compounds of the formula (VIII) and / or of the formula (IX) may be compounds in which the substituents R ¹ , R ² and R ⁷ independently of one another represent:

• Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,
• A C ₂ -C ₄ saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical,
• A C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• - a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbyl radical,
• - a group -NR ¹² R ¹³ , wherein R ¹² and R ¹³ each independently represent hydrogen, a methyl, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,
• A group -COOR ¹⁴ , wherein R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or - or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• A group -COR ¹⁶ , where R ¹⁶ is a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or -or- or di-unsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• - a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₃₀ -saturated or one or polyunsaturated, branched or linear mono-, di-, tri- or polyhydroxyalkyl radical, or a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear mono-, di-, tri- or polyamino hydrocarbon radical.

• – Wasserstoff, einen -OH-, einen Methyl-, Methoxy-, Aminomethyl-, Hydroxymethylrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest oder
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest. Weiterhin kann es bevorzugt sein, wenn in dem erfindungsgemäßen Wirkstoff gemäß der Formel (VIII) und/oder der Formel (II) für die Reste R⁵, R⁶, R⁹ und R¹⁰ unabhängig voneinander stehen für:
• – Wasserstoff, einen -OH-, einen Methyl-, Methoxy-, Aminomethyl-, Hydroxymethylrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest oder
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest.

In a further embodiment of the teaching according to the invention, it has been found that, in the case of the compounds of the formula (VIII) or of the formula (IX), the radicals R ³ , R ⁴ and R ^{8 are} preferably, independently of one another,

• Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,
• A C ₂ -C ₄ saturated or mono- or diunsaturated, branched or linear hydrocarbon radical,
• - a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical or
• - a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon. Furthermore, it may be preferred for the radicals R ⁵ , R ⁶ , R ⁹ and R ¹⁰ in the active ingredient according to the formula (VIII) and / or formula (II) according to the invention to be independently of one another
• Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,
• A C ₂ -C ₄ saturated or mono- or diunsaturated, branched or linear hydrocarbon radical,
• - a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical or
• - a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon.

• – Wasserstoff, einen -OH-, einen Methyl-, Methoxy-, Aminomethyl-, Hydroxymethylrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -OR¹¹, mit R¹¹ als einem -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -COOR¹⁴, wobei R¹⁴ steht für Wasserstoff, einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -COR¹⁶, wobei R¹⁶ steht für einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -OCOR¹⁷, wobei R¹⁷ steht für einen Methyl-, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Mono-, Di-, Tri- oder Polyhydroxykohlenwasserstoffrest.

In a particularly preferred embodiment of the teaching according to the invention, a compound of the formula (VIII) is used. In this case, it may be preferred that in a compound of the formula (IX) the radicals R ¹ and R ² independently of one another represent:

• Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,
• A C ₂ -C ₄ saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical,
• - a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbyl radical,
• A group -COOR ¹⁴ , where R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated hydrocarbon radical, or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,
• A group -COR ¹⁶ , where R ¹⁶ is a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or -or- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,
• - a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₃₀ -saturated or one or polyunsaturated, branched or linear mono-, di-, tri- or Polyhydroxykohlenwasserstoffrest.

• – Wasserstoff, einen -OH-, einen Methyl-, Methoxy-, Aminomethyl-, Hydroxymethylrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -OR¹¹, mit R¹¹ als einem -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -COOR¹⁴, wobei R¹⁴ steht für Wasserstoff, einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -OCOR¹⁷, wobei R¹⁷ steht für einen Methyl-, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Mono-, Di-, Tri- und/oder Polyhydroxykohlenwasserstoffrest.

Furthermore, in this particularly preferred embodiment of the teaching according to the invention, it may be advantageous if, in the compounds of the formula (VIII), the radicals R ³ and R ⁴ independently of one another represent:

• Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,
• A C ₂ -C ₄ saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical,
• - a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbyl radical,
• A group -COOR ¹⁴ , where R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated hydrocarbon radical, or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,
• - a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₃₀ -saturated or one or polyunsaturated, branched or linear mono-, di-, tri- and / or polyhydroxy hydrocarbon radical.

• – Wasserstoff, einen -OH-, einen Methyl-, Methoxy-, Aminomethyl-, Hydroxymethylrest,
• – einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -OR¹¹, mit R¹¹ als einem -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest.

In this preferred embodiment, it may furthermore be advantageous for the compounds of the formula (VIII) for the radicals R5 and R6 to stand independently of one another

• Hydrogen, an -OH, a methyl, methoxy, aminomethyl, hydroxymethyl radical,
• A C ₂ -C ₄ saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical,
• - a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbon radical.

• – (R)-(–)-4-Hydroxymethyl-γ-butyrolacton und/oder
• – D,L-4-Hydroxymethyl-γ-butyrolacton und/oder
• – (S)-(+)-4-Hydroxymethyl-γ-butyrolacton und/oder
• – R-(–)-2-Hydroxy-3,3-dimethyl-γ-butyrolacton und/oder
• – D,L-2-Hydroxy-3,3-dimethyl-γ-butyrolacton und/oder
• – S(+)-2-Hydroxy-3,3-dimethyl-γ-butyrolacton und/oder
• – 4-Hydroxy-2,5-dimethyl-3(2H)-furanon und/oder
• – Tetrahydro-5-oxo-2-furancarbonsäure und/oder
• – Tetrahydro-5-oxo-2-furancarbonsäure, Na-Salz und/oder
• – Tetrahydro-5-oxo-2-furancarbonsäure, K-Salz und/oder
• – 2,5-Dihydro-5-methoxy-2-furanon und/oder
• – Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanon

eingesetzt. In einer ganz besonders bevorzugten Ausführungsform der erfindungsgemäßen Lehre wird als Verbindung entsprechend der Formel (VIII) Dihydro-3-hydroxy-4,4-dimethyl-2(3H)-furanon eingesetzt.In a particularly preferred embodiment of the teaching according to the invention, the compound corresponding to the formula (VIII)

• - (R) - (-) - 4-hydroxymethyl-γ-butyrolactone and / or
• - D, L-4-hydroxymethyl-γ-butyrolactone and / or
• - (S) - (+) - 4-hydroxymethyl-γ-butyrolactone and / or
• - R - (-) - 2-hydroxy-3,3-dimethyl-γ-butyrolactone and / or
• - D, L-2-hydroxy-3,3-dimethyl-γ-butyrolactone and / or
• - S (+) - 2-hydroxy-3,3-dimethyl-γ-butyrolactone and / or
• 4-hydroxy-2,5-dimethyl-3 (2H) -furanone and / or
• - Tetrahydro-5-oxo-2-furancarbonsäure and / or
• - Tetrahydro-5-oxo-2-furancarbonsäure, Na salt and / or
• Tetrahydro-5-oxo-2-furancarboxylic acid, K salt and / or
• 2,5-dihydro-5-methoxy-2-furanone and / or
• Dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone

used. In a very particularly preferred embodiment of the teaching according to the invention is as Compound according to the formula (VIII) dihydro-3-hydroxy-4,4-dimethyl-2 (3H) -furanone used.

enthalten, in welchen die Reste R¹ bis R¹⁰ unabhängig voneinander stehen für:

• – Wasserstoff, -OH, einen Methyl-, Methoxy-, Aminomethyl- oder Hydroxymethylrest,
• – -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest,
• – -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -OR¹¹, mit R¹¹ als einem -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -NR¹²R¹³, wobei R¹² und R¹³ jeweils unabhängig voneinander stehen für Wasserstoff, einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest,
• – eine Gruppe -COOR¹⁴, wobei R¹⁴ steht für Wasserstoff, einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -CONR¹⁵R¹⁶, wobei R¹⁵ und R¹⁶ jeweils stehen für Wasserstoff, Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -COR¹⁶, wobei R¹⁶ steht für einen Methyl-, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Trihydroxykohlenwasserstoffrest, einen -C₂-C₄- gesättigten oder ein- oder zweifach ungesättigten, verzweigten oder linearen Mono-, Di- oder Triaminokohlenwasserstoffrest,
• – eine Gruppe -OCOR¹⁷, wobei R¹⁷ steht für einen Methyl-, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Kohlenwasserstoffrest, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Mono-, Di-, Tri- oder Polyhydroxykohlenwasserstoffrest, einen -C₂-C₃₀- gesättigten oder ein- oder mehrfach ungesättigten, verzweigten oder linearen Mono-, Di-, Tri- oder Polyaminokohlenwasserstoffrest,

mit der Maßgabe, daß für den Fall, wenn R⁷ und R⁸ für -OH und gleichzeitig R⁹ oder R¹⁰ für Wasserstoff stehen, die verbleibende Gruppe R⁹ oder R¹⁰ nicht für einen Dihydroxyethylrest steht.In summary, agents according to the invention for dyeing and / or lightening keratinic fibers are preferably characterized in that they additionally contain 0.05 to 15% by weight of at least one 2-furanone derivative of the formula (VIII) and / or of the formula (IX)

in which the radicals R ¹ to R ^{10 are} independently of one another

• Hydrogen, -OH, a methyl, methoxy, aminomethyl or hydroxymethyl radical,
• --C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical,
• - C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or Trihydroxykohlenwasserstoffrest,
• --C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• - a group -OR ¹¹ , with R ¹¹ as a -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, -C ₂ -C ₄ - saturated or mono- or diunsaturated, branched or linear Mono-, di- or trihydroxyhydrocarbyl radical,
• - a group -NR ¹² R ¹³ , wherein R ¹² and R ¹³ each independently represent hydrogen, a methyl, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical,
• A group -COOR ¹⁴ , where R ¹⁴ is hydrogen, a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated hydrocarbon radical, or diunsaturated, branched or linear mono-, di- or trihydroxy hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbyl radical,
• - a group -CONR ¹⁵ R ¹⁶ , wherein R ¹⁵ and R ¹⁶ each represent hydrogen, methyl, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ - saturated mono- or diunsaturated, branched or linear mono-, di- or trihydroxyhydrocarbon hydrocarbon radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• A group -COR ¹⁶ , where R ¹⁶ is a methyl, a C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₄ -saturated or -or- or di-unsaturated, branched or linear mono-, di- or trihydroxyhydrocarbyl radical, a -C ₂ -C ₄ -saturated or mono- or diunsaturated, branched or linear mono-, di- or triaminocarbon radical,
• - a group -OCOR ¹⁷ , wherein R ¹⁷ is a methyl, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear hydrocarbon radical, a -C ₂ -C ₃₀ -saturated or one or polyunsaturated, branched or linear mono-, di-, tri- or polyhydroxy hydrocarbon radical, a -C ₂ -C ₃₀ -saturated or mono- or polyunsaturated, branched or linear mono-, di-, tri- or polyamino hydrocarbon radical,

with the proviso that when R ⁷ and R ^{8 are} -OH and at the same time R ⁹ or R ^{10 is} hydrogen, the remaining group R ⁹ or R ¹⁰ does not represent a dihydroxyethyl radical.

enthalten.Preference is also given to the additional use of bisabolol and / or bisabolol oxides in the agents according to the invention. Here, agents according to the invention for dyeing and / or brightening keratinic fibers are preferred, which additionally contain 0.001 to 5 wt.%, Preferably 0.01 to 4 wt.%, Particularly preferably 0.02 to 2.5 wt.% And in particular 0.1 to 1.5% by weight of bisabolol and / or oxides of bisabolol, preferably (-) - alpha-bisabolol

contain.

Regarding further optional components as well as the amounts of these components used expressly to the relevant manuals known to those skilled in the art, e.g. Kh. Schrader, Basics and formulations of cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989, as well as the comments below.

A oxidative staining The fibers may be in the presence of oxidation dye precursors in principle done with atmospheric oxygen. However, preference is given to a chemical Oxidizing agent used, especially if in addition to the staining a Whitening effect on human hair is desired. This whitening effect can be independent from the staining method required be. The presence of oxidation dye precursors is accordingly no mandatory requirement for an employment of oxidizing agents in the agents according to the invention. The oxidizing agents are persulfates, chlorites and in particular Hydrogen peroxide or its addition products to urea, Melamine and sodium borate in question.

However, according to the invention the oxidation colorant also be applied to the hair together with a catalyst, the oxidation of the dye precursors, e.g. by atmospheric oxygen, activated. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ³⁺ , Fe ²⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of the dyeing can be accelerated and the color shade can be specifically influenced.

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

Suitable enzymes include peroxidases, which can significantly enhance the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention which directly oxidize the oxidation dye precursors with the aid of atmospheric oxygen, such as, for example, the laccases, or generate small amounts of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, eg

• Pyranose oxidase and eg D-glucose or galactose,
• Glucose oxidase and D-glucose,
• - glycerol oxidase and glycerin,
• Pyruvate oxidase and pyruvic acid or its salts,
• Alcohol oxidase and alcohol (MeOH, EtOH),
• Lactate oxidase and lactic acid and their salts,
• Tyrosinase oxidase and tyrosine,
• Uricase and uric acid or their salts,
• - choline oxidase and choline,
• - amino acid oxidase and amino acids.

As already mentioned, Multi-component agent make a preferred embodiment of the present invention. In these multi-component agents are the inventively used Silazanes and / or matlamides and / or imides and / or nitriles preferably. in the form of a separately packaged preparation C. This preparation may optionally have the optional ones mentioned above Contain ingredients. Preferably, the composition C contains at least a non-aqueous, hydrophobic oil.

• – der Nuß- und/oder Mandelöle, vorzugsweise Mandelöl und/oder Macadamiaöl und/oder
• – der Silikonöle und/oder
• – der gehärteten Rizinusöle und ihrer Kondensate mit PEG, vorzugsweise PEG-40-Castor Oil und/oder PEG-60-Castor Oil und/oder
• – der Ether mit C_6-22-Alkylresten, vorzugsweise Di-n-Octylether und/oder Di-n-Decylether

bevorzugt sind.Preferred agents according to the invention for dyeing and / or lightening keratinic fibers are characterized in that composition C additionally contains 1 to 99% by weight, preferably 5 to 95% by weight, particularly preferably 10 to 90% by weight, based on their weight. and in particular from 25 to 85 wt .-% of at least one non-aqueous hydrophobic oil containing oils from the groups

• - The nut and / or almond oils, preferably almond oil and / or macadamia oil and / or
• - the silicone oils and / or
• The hardened castor oils and their condensates with PEG, preferably PEG-40 Castor Oil and / or PEG-60 Castor Oil and / or
• The ether with C _6-22 alkyl radicals, preferably di-n-octyl ether and / or di-n-decyl ether

are preferred.

• – gewünschtenfalls ein Vorbehandlungsmittel M1 auf die Faser aufgebracht wird, dann
• – ein Tönungs- oder Färbemittel M2 auf der Faser zur Anwendung kommt, wobei gewünschtenfalls dem Mittel M2 vor der Anwendung ein weiteres Mittel M3 zugegeben wird,
• – dieses Färbemittel M2 nach einer Zeit von 5-45 Minuten von der Faser abgespült wird
• – und nach der Behandlung gegebenenfalls ein Nachbehandlungsmittel M4 auf die Faser aufgetragen und nach einer Einwirkzeit von einigen Minuten wieder abgespült wird,

dadurch gekennzeichnet, daß mindestens eines der Mittel M1, M2 oder M3 ein erfindungsgemäßes Mittel ist.Another object of the present invention is a process for dyeing and / or lightening keratinischer fibers, wherein

• - If desired, a pretreatment agent M1 is applied to the fiber, then
• A tinting or dyeing agent M2 is applied to the fiber, wherein, if desired, an additional agent M3 is added to the agent M2 before use,
• - This colorant M2 is rinsed from the fiber after a period of 5-45 minutes
• - and after the treatment optionally a post-treatment agent M4 applied to the fiber and rinsed again after a contact time of a few minutes,

characterized in that at least one of the means M1, M2 or M3 is an agent according to the invention.

In preferred according to the invention Procedure is the hair following the application of the first remedy rinsed, and particularly preferred methods are characterized that the Application of hair dye (s) done on damp hair or damp hair contours. "Wet" in the sense of the present Registration is also towel-dry.

With regard to more preferred embodiments the method according to the invention Mutatis mutandis applies to the means of the invention carried out. Especially are methods according to the invention preferred in which the hair dye contains at least one substantive dye.

Also inventive method, where the hair dye at least one aromatic or heteroaromatic activated carbonyl compound and / or contains a CH-acidic compound are preferred embodiments of the present invention.

Another object of the present invention is the use of silazanes and / or metal amides and / or imides and / or nitrides of the formula M ^{n +} (NH _{3 -x} ) _{n / x} in the M for a metal of the I. and / or II. and / or III. and / or IV. Main group and / or the I. and / or II. and / or III. and / or IV. and / or V. and / or VI. and / or VII and / or VIII. Subgroup of the Periodic Table and n and x are the integers 1, 2, 3, in means for dyeing and / or lightening keratinic fibers, in particular in ammonia-reduced and / or ammonia-free dyeing and / or lightening keratinic fibers.

• – Grauabdeckung und/oder
• – Aufhellleistung und/oder
• – Farbergebnis.

The use according to the invention is preferred for improving at least one of the properties

• - Gray cover and / or
• - Brightening performance and / or
• - Color result.

Also in terms of preferred embodiments the uses of the invention Mutatis mutandis applies to the means of the invention carried out.

• * Alkyl(C12/14)-polyglycolether (2EO)-sulfat, Na-Salz 28 Gew.% AS in Wasser) (Cognis)
• ** (INCI: Sodium Lauryl Glucose Carboxylate and Lauryl Glucoside) (Cognis)
• *** Cetylstearylalkohol mit ca. 12 EO-Einheiten (INCI-Bezeichnung: Ceteareth-12) (Cognis)
• **** Cetylstearylalkohol mit ca. 20 EO-Einheiten (INCI-Bezeichnung: Ceteareth-20) (Cognis)
• # 1-Hydroxyethan-1,1-diphosphonsäure (60 % Aktivsubstanz; INCI – Bezeichnung: Etidronic Acid) (COGNIS)

A dye cream of the following composition (in% by weight) was prepared: C _16-18 fatty alcohol 8.1 C _12-18 coconut fatty alcohol 2.7 Texapon NSO * 5.0 Plantapon LGC ** 5.0 Eumulgin ^® B1 *** 0.5 Eumulgin ^® B2 **** 0.5 isostearic 2.0 myristic 0.5 KOH, 50% 1.2 dye precursors 2.2 Ammonia, 25% 7.2 sodium 0.5 ascorbic acid 0.4 Turpinal® ^® SL ^# 0.2 Natronwasserglas 0.5 perfume oil 0.5 propylene glycol 0.4 ammonium sulfate 0.5 water ad 100

• * Alkyl (C12 / 14) polyglycol ether (2EO) sulfate, Na salt 28 wt% AS in water) (Cognis)
• ** (INCI: Sodium Lauryl Glucose Carboxylate and Lauryl Glucoside) (Cognis)
• *** Cetylstearyl alcohol with approx. 12 EO units (INCI name: Ceteareth-12) (Cognis)
• **** Cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)
• # 1-Hydroxyethane-1,1-diphosphonic acid (60% active ingredient, INCI name: Etidronic Acid) (COGNIS)

Furthermore, a blonding cream of the following composition (in% by weight) was prepared: C _16-18 fatty alcohol 12.0 C _12-18 coconut fatty alcohol 2.4 Texapon NSO * 13.0 Plantapon LGC ** 13.0 Ammonia, 25% 7.6 sodium 0.5 ascorbic acid 0.4 Turpinal® ^® SL ^# 0.2 Natronwasserglas 0.5 perfume oil 0.5 ammonium sulfate 0.5 water ad 100

• Mit Ammoniaklösung 25% auf pH = 3,8 – 4,2
• ## Säure-enthaltendes, vernetztes Acrylsäurecopolymer (INCI-Bezeichnung: Acrylates Copolymer, ca. 28% Aktivsubstanz) (Rohm&Haas)

In addition, a developer emulsion (composition B) of the following composition (in% by weight) was prepared: Ammonia, 25% 0.62 Dpicolinsäure 0.1 sodium pyrophosphate 0.03 Turpinal® ^® SL ^# 1.5 Texapon NSO * 2.0 Aculyn ^® 33 A ^## 12.0 Hydrogen peroxide, 30% 12.0 water ad 100

• With ammonia solution 25% to pH = 3.8 - 4.2
• ## Acid-containing, crosslinked acrylic acid copolymer (INCI name: Acrylates Copolymer, approx. 28% active substance) (Rohm & Haas)

A preparation C had the following composition (in% by weight):

When so-called "booster" (preparation D) served potassium peroxydisulfate.

Fortsetzung Tabelle 1:

The following mixtures were prepared as staining mixtures: TABLE 1 Blends of staining mixtures

Continuation Table 1:

there were per mixing ratio twelve mixtures using per mixture of a preparation of C1 to C12 manufactured and tested.

Fortsetzung Tabelle 2

Fortsetzung Tabelle 2:

Fortsetzung Tabelle 2:

The following mixtures were prepared as brightening formulations: TABLE 2 Blends of brightening mixtures

Continuation Table 2

Continuation of Table 2:

Continuation of Table 2:

there were per mixing ratio twelve mixtures using per mixture of a preparation of C1 to C12 manufactured and tested.

The ready-to-use colorants were each on a blonde strand of hair (Euronaturhaar, Fa. Kerling) applied (liquor ratio: 1 g of hair on 4 g of application mixture), at a temperature of 32 ° C for 30 minutes leave on the hair and rinsed off the hair. The hair was dried.

The ready-to-use brighteners were each a dark blond strand of hair (Euronaturhaar, Kerling) (liquor ratio: 1 g hair on 4 g of application mixture), at a temperature of 32 ° C for 30 minutes leave on the hair and rinsed off the hair. The hair was dried.

in the Compared to mixtures, the higher Amounts of ammonia but no preparation C contained, became clear reduced odors observed during use. Regarding product performance (brightening performance in the Blondiermischungen or color result and gray coverage at the dye mixtures) were the products of the invention equal to the more ammonia-rich formulations, i. it was diminished despite Ammonia use no loss of performance observed.

Claims (15)

Agent for dyeing and / or lightening keratinic fibers, containing - in each case based on its weight - a) at most 2 wt .-% ammonia (calculated as 100% NH ₃ ); b) 0.01 to 25 wt .-% of at least one substance from the group of b1) silazanes and / or b2) metal amides and / or imides and / or nitrides of the formula M ^{n +} (NH _{3 -x} ) _{n / x} in the M for a metal of the I. and / or II. and / or III. and / or IV. Main group and / or the I. and / or II. and / or III. and / or IV. and / or V. and / or VI. and / or VII and / or VIII. Subgroup of the Periodic Table and n and x are the integers 1, 2, 3. Agent for dyeing and / or whitening keratinic fibers according to Claim 1, characterized in that it contains 0.01 to 25% by weight, preferably 0.05 to 20% by weight, particularly preferably 0.1 to 15% by weight. and in particular from 0.25 to 10% by weight of at least one silazane of the formula X- [SiR ¹ R ² -NH-SiR ³ R ⁴ ] _n -Y in which X or Y are a chemical bond or the radicals R ⁵ and R ⁶ , R ¹ to R ^{6 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , - (CH ₂ ) ₂ CH ₃ , -CH ₂ (CH ₃ ) ₂ , -OH, -NH ₂ and n are the integers 1, 2, 3, 4, 5, 6, 7, 8, 9, 10. Dyeing agent and / or lightening keratinic fibers according to one of claims 1 or 2, characterized in that it 1,1,1,3,3,3-hexamethyldisilazane and / or 1,1,1,3,3,3-hexaethyldisilazane and / or 1,1,1,3,3,3-hexapropyldisilazane and / or 1,1,1,3,3,3-hexaisopropyldisilazane and / or 1,1,1,3,3,5,5,5-octamethyltrisilazane and / or 1,1,1,3,3,5,5,7,7,7-decamethyltetrasilazane and / or 1,1,1,3,3,5,5,7,7,9,9,9-tridecamethylpentasilazane and / or cyclo-1,1,3,3,5,5-hexamethyltrisilazane and / or cyclo-1,1,3,3,5,5,7,7-octamethyltetrasilazane contains. Agent for dyeing and / or lightening keratinic fibers according to one of Claims 1 to 3, characterized in that it contains 0.01 to 25% by weight, preferably 0.05 to 20% by weight, more preferably 0.1 to 15 Wt .-% and in particular 0.25 to 10 wt .-% of at least one metal amide and / or imide and / or nitride of the formula M _{n +} (NH _{3 -x} ) _{n / x} in which M is Na, K, Mg, Ca, Si, Al, Zn, Mg, Cu and n and x are the integers 1, 2, 3, with the following compounds being particularly preferred: Mg (NH ₂ ) ₂ , Ca (NH ₂ ) ₂ , LiAl (NH ₂ ) ₄ , LiAl (NH) ₂ , Zn (NH ₂ ) ₂ , Mg (NH), Ca (NH), Zn (NH), Mg ₃ N ₂ , Ca ₃ N ₂ , Zn ₃ N ₂ . Agent for dyeing and / or lightening keratinic fibers, in particular human hair, which immediately prior to application to the hair of a flowable preparation A, an oxidizing agent B, containing at least one oxidizing agent selected from hydrogen peroxide and its addition compounds to solid carriers and a preparation of C. , which are mixed together to form a dyeing and / or Aufhellansatz is obtained, characterized in that the composition C - based on their weight - 1 to 100 wt .-% of at least one substance from the group of b1) silazanes and / or b2) metal amides and / or imides and / or nitrides of the formula M ^{n +} (NH _{3 -x} ) _{n / x} in the M for a metal of the I. and / or II. and / or III. and / or IV. Main group and / or the I. and / or II. and / or III. and / or IV. and / or V. and / or VI. and / or VII and / or VIII. Subgroup of the Periodic Table and n or x are the integers 1, 2, 3 contains. Agent for dyeing and / or whitening keratinic fibers according to Claim 5, characterized in that the oxidizing agent preparation B - based on its weight - 0.5 to 10 wt .-%, preferably 0.75 to 9.0 wt .-%, especially preferably 1 to 8.0 wt .-%, more preferably 1.25 to 7.0 wt .-% and in particular 1.5 to 6.0 wt .-% hydrogen peroxide (calculated as 100% H ₂ O ₂ ) contains , Dyeing agent and / or lightening keratinic fibers according to one of claims 5 or 6, characterized in that the flowable oxidizing agent preparation B - related on her weight - 40 to 99% by weight, preferably 50 to 95% by weight, more preferably 55 to 90 wt .-%, water. Dyeing agent and / or lightening keratinic fibers according to any one of claims 5 to 7, characterized in that it additionally contains at least one peroxo compound, which is preferably selected of ammonium and alkali metal persulfates and peroxydisulfates, preferred agents comprising at least 2 different peroxydisulfates contain. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 6, characterized in that the flowable preparation A at least one developer-type oxidation dye precursor and / or coupler type. Agent for dyeing and / or lightening keratinic fibers according to one of Claims 1 to 9, characterized in that the composition C additionally contains from 1 to 99% by weight, preferably from 5 to 95% by weight, particularly preferably from 10 to 15% by weight 90 wt .-% and in particular 25 to 85 wt .-% of at least one non-aqueous hydrophobic oil containing oils from the groups - the nut and / or almond oils, preferably almond oil and / or macadamia oil and / or - the silicone oils and / or The hardened castor oils and their condensates with PEG, preferably PEG-40 castor oil and / or PEG-60 castor oil and / or the ether with C _6-22 alkyl radicals, preferably di-n-octyl ether and / or di n-decyl ether are preferred. Agent for dyeing and / or lightening keratinic fibers according to one of Claims 1 to 10, characterized in that it contains at least one developer component as the oxidation dye precursor, preferred developer components being selected from p-phenylenediamine, p-toluenediamine, N, N-bis- ( 2-hydroxyethyl) amino-p-phenylenediamine, 1,3-bis - [(2-hydroxyethyl-4'-aminophenyl) amino] -propan-2-ol, 1,10-bis- (2 ', 5'-diaminophenyl ) -1,4,7,10-tetraoxadecane, 4-aminophenol, 4-amino-3-methylphenol, Bis (5-amino-2-hydroxyphenyl) methane, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4,5-diamino-1- (2-hydroxyethyl) pyrazole , Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 11, characterized in that it as oxidation dye precursor at least one coupler component contains, where preferred coupler components are selected from resorcinol, 2-methylresorcinol, 5-methyl-resorcinol, 2,5-dimethylresorcinol, 4-chlororesorcinol, resorcinol monomethyl ether, 5-aminophenol, 5-amino-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 3 Amino-4-chloro-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 3-amino-2,4-dichlorophenol, 2,4-diaminophenoxyethanol, 2-amino-4- (2'-hydroxyethyl) amino-anisole sulfate, 1,3-bis (2,4-diaminophenoxy) propane, 2-amino-3-hydroxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-phenyl-3-methylpyrazol-5-one, 2,6-bis - [(2'-hydroxyethyl) amino] -toluene, 4-hydroxyindole, 6-hydroxyindole, 6-hydroxybenzomorpholine. Dyeing agent and / or lightening keratinic fibers according to any one of claims 1 to 12, characterized in that it contains at least one substantive dye that is selected from nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols, preferably from the group of international Names or trade names of known dyes HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 Compounds as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 1- (2'-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2-Ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic and their salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. Use of silazanes and / or metal amides and / or imides and / or nitrides of the formula M ^{n +} (NH _{2 -x} ) _{n / x} in the M for a metal of the I. and / or II. and / or III. and / or IV. Main group and / or the I. and / or II. and / or III. and / or IV. and / or V. and / or VI. and / or VII and / or VIII. Subgroup of the Periodic Table and n and x are the integers 1, 2, 3, in means for dyeing and / or lightening keratinic fibers, in particular in ammonia-reduced and / or ammonia-free dyeing and / or lightening keratinic fibers. Use according to claim 14 for the improvement at least one of the properties - Gray cover and or - Brightening performance and or - Color result.