DE102011079773A1 - Agent useful e.g. for oxidative color change of keratin fibers, comprises substituted 1-(((4-amino-phenyl)-methyl-amino)-methyl)-4-aza-1-azonia-bicyclo(2.2.2)octane derivative as a developer type oxidation dye precursor, in a carrier - Google Patents

Abstract

Agent comprises at least one substituted 1-{[(4-amino-phenyl)-methyl-amino]-methyl}-4-aza-1-azonia-bicyclo[2.2.2]octane derivative (I), as a developer type oxidation dye precursor, in a carrier. Agent comprises at least one substituted 1-{[(4-amino-phenyl)-methyl-amino]-methyl}-4-aza-1-azonia-bicyclo[2.2.2]octane derivative of formula (I) and/or its salt, as a developer type oxidation dye precursor, in a carrier. R1 : H, 2-6C alkenyl, 1-6C (hydroxy)alkyl, 2-6C polyhydroxyalkyl, 1-6C alkoxy or halo; R2 : (hetero)aryl (optionally substituted), H, 1-6C alkyl, 2-6C alkenyl, OH, acetoxy, 1-6C alkoxy, NH 2, 1-6C alkylamino, di-(1-6C alkyl)amino, CN, -COOH, -SO 3H, carbamoyl or 1-6C alkoxycarbonyl; n : 1-6; m : 2-6; and X : anion. An independent claim is also included for (I). [Image].

Description

The invention relates to an agent for the oxidative color change of keratin-containing fibers, in particular human hair, which contains certain bicyclic p-phenylenediamine derivatives with cationic charge, the use of these agents as color-change agents of keratin-containing fibers to improve the dyeing results and a process for dyeing keratin-containing fibers, in particular human hair.

The change in the shape and color of the hair is an important area of modern cosmetics dar. For fashionable color design of hairstyles or lamination of gray or white hair with fashionable or natural colors, the consumer accesses to color-changing agents.

To provide color-changing cosmetic agents, in particular for the skin or keratin-containing fibers such as human hair, the skilled person knows various systems depending on the requirements of the coloring or color change.

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components, the actual dyes. The oxidation colorants are characterized by intensive, outstanding, long-lasting dyeing results. For natural-looking dyeings, a mixture of a larger number of oxidation dye precursors can be used, and in many cases direct substantive dyes are additionally used for shading.

In particular, oxidative hair dyes are disadvantageous to the user despite their advantageous dyeing properties. In particular, it is assumed for some of the common oxidation dye precursors, including p-phenylenediamine, to act irritating or irritating for some consumers and thereby trigger sensitization or even allergic reactions. Therefore, there is still room for improvement in their physiological compatibility profile for these substances. In the search for substitutes, many compounds have been explored, but often suffer from application problems, in particular lack of gray coverage. In addition, despite already advanced dyeing systems, there is still a need for dyeing systems that achieve excellent brightness and intensity of dyeing, yet have very good shelf life and excellent homogeneity.

Object of the present invention is therefore to lower the above-mentioned disadvantages of oxidative hair dyes. The colorants should produce intense colorations with high color and good resistance to external influences, in particular with good lightfastness and wash fastness, which suffer no color attenuation or color shift even after repeated shampooing of the hair. In addition, the dyes should be as selective as possible, d. H. achieve as uniform, uniform staining results on differently pretreated hair as possible. In addition, the colorants should have a toxicologically advantageous profile.

It has been found that certain bicyclic p-phenylenediamine derivatives with cationic charge as oxidation dye precursors are outstandingly suitable for dyeing keratin-containing fibers. They result in colorations with high color intensity and excellent brilliance as well as excellent gray coverage.

Out CH 552032 For example, cationic azo dyes having a cationic bicycle are known for use as direct dyes. Dimer oxidation dye precursors based on aminophenylpyrrolidines with cationic bicycles are made EP 1396486 and EP 1348695 known.

R1 für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₁-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxygruppe oder ein Halogenatom stehen,
R2 für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Hydroxygruppe, eine Acetoxygruppe, eine C₁-C₆-Alkoxygruppe, eine Aminogruppe, eine C₁-C₆-Alkylaminogruppe, eine Di-(C₁-C₆-Alkyl)aminogruppe, eine Cyanogruppe, eine Carbonsäuregruppe, eine Sulfonsäuregruppe, eine Carbamoylgruppe oder eine C₁-C₆-Alkyloxycarbonylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Heteroarylgruppe, steht,
n für eine ganze Zahl von 1 bis 6 steht,
m für eine ganze Zahl von 2 bis 6 steht und
X^– für ein physiologisch verträgliches Anion steht,
und/oder eines dessen physiologisch verträglichen Salzes enthält.A first subject of the invention is therefore an agent for the oxidative color change of keratinic fibers, which is characterized in that it comprises, in a cosmetic carrier as a developer-type oxidation dye precursor, at least one compound of the formula (I)

R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy group or are a halogen atom,
R _{2 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a hydroxy group, an acetoxy group, a C ₁ -C ₆ -alkoxy group, an amino group, a C ₁ -C ₆ -alkylamino group, a di (C ₁ -C ₆ alkyl) amino group, a cyano group, a carboxylic acid group, a sulfonic acid group, a carbamoyl group or a C ₁ -C ₆ alkyloxycarbonyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group,
n is an integer from 1 to 6,
m stands for an integer from 2 to 6 and
X ^{- represents} a physiologically acceptable anion,
and / or one of its physiologically acceptable salt.

Keratin fibers are wool, furs, feathers and especially human hair. The colorants of the invention can in principle but also for dyeing other natural fibers such. As cotton, jute, sisal, linen or silk, modified natural fibers, such as regenerated cellulose, nitro, alkyl or hydroxyalkyl or acetyl cellulose can be used.

The agents according to the invention contain the compounds of the formula (I) in a cosmetic carrier, preferably in a suitable aqueous, alcoholic or aqueous-alcoholic carrier. For the purpose of hair coloring such carriers are, for example, creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations which are suitable for use on the hair. However, it is also conceivable to integrate the dye precursors according to formula (I) into a pulverulent or tablet-formulated formulation.

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

Examples of the substituents R1 and R2 mentioned in formula (I) are given below by way of example:
Examples of C ₁ -C ₆ -alkyl radicals are the groups -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , - (CH ₂ ) ₄ CH ₃ , - (CH ₂ ) ₅ CH ₃ . Particularly preferred alkyl radicals are methyl and ethyl. Examples of C ₂ -C ₆ alkenyl groups are prop-2-enyl group (allyl group), 2-methyl-prop-2-enyl group, but-3-enyl group, but-2-enyl group, pent-4-enyl group or pent-3 -enylgruppe. Preferred examples of C ₁ -C ₆ -hydroxyalkyl groups are -CH ₂ OH, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH (OH) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ OH, with -CH ₂ CH ₂ OH being preferred. Examples of C ₂ -C ₆ polyhydroxyalkyl groups are 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, 2,4-dihydroxybutyl group and 1,2-dihydroxyethyl group. Examples of C ₁ -C ₆ -alkoxy groups are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ or -OC (CH ₃ ) ₃ , preferably methoxy group (-OCH ₃ ). Examples of C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl groups are -CH ₂ OCH ₃ , -CH ₂ OCH ₂ CH ₃ , -CH ₂ OCH (CH ₃ ) ₂ , -CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₃ , -CH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₃ , -CH ₂ CH ₂ OCH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ OCH (CH ₃ ) ₂ . Examples of halogen are fluorine, chlorine, bromine or iodine, in particular fluorine and chlorine. Examples of cyano-C ₁ -C ₆ -alkyl groups are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN, -CH ₂ CH (CN) CH ₃ and -CH ₂ CH ₂ CH ₂ CH ₂ CN. Examples of a C ₁ -C ₆ -alkylamino group are methylamino, ethylamino and propylamino group. Examples of di- (C ₁ -C ₆ -alkyl) -amino group are dimethylamino group, diethylamino group and dipropylamino group. Examples of C ₁ -C ₆ -alkyloxycarbonyl are methoxycarbonyl or ethoxycarbonyl. The phenyl group and the naphthyl group are examples of aryl groups which may optionally be substituted by a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ - Polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy group or a halogen atom (fluorine, chlorine, bromine or iodine). Exemplary of a heteroaryl group are 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-imidazolyl group, 2-imidazolyl group, 4-imidazolyl group, 2-pyrrolidyl group, 3-pyrrolidyl group, 1-triazolyl group, 2-triazolyl group, 2-furyl group, 3-furyl group, 2-thienyl group or 3-thienyl group.

In one embodiment of the first subject of the invention, an agent according to the invention is characterized in that it contains a compound of the formula (I) in which R _{1 is} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -alkoxy group or a Halogen atom, particularly preferably represents a hydrogen atom.

In a further embodiment of the first subject of the invention, an agent is characterized in that it contains a compound of the formula (I) in which R _{2 is} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group or a C ₁ -C ₆ alkoxy group.

In a further preferred embodiment, the agent contains a compound of the formula (I) in which R 2 is a hydrogen atom.

Preference is given to compositions containing compounds of the formula (I) in which R _{1 is} hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy or halogen, and R 2 is hydrogen.

Particular preference is furthermore given to compounds of the formula (I) in which n is the number 1 or 2. Particular preference is furthermore given to compounds of the formula (I) in which m is the number 2 or 3.

A further embodiment of the first subject of the invention is an agent which is characterized in that it contains a compound of the formula (I) in which n is the number 1 or 2 and / or m is the number 2 or 3.

X ^- is a physiologically acceptable anion. X ^- is therefore preferably selected from chloride, ½ sulfate, hydrogen sulfate, bromide, benzenesulfonate, p-toluenesulfone sulfonate, C ₁ -C ₄ -alkanesulfonate, C ₁ -C ₄ alkyl sulfate or trifluoromethanesulfonate and acetate, lactate, citrate, tartrate and / or the anionic salt content of other physiologically acceptable, organic acids.

• – des 1-{2-[(4-Aminophenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Amino-3-methylphenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-CH₃, R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Amino-2-methylphenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-CH₃, R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Amino-3-methoxyphenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-OCH₃, R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Amino-2-methoxyphenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-OCH₃, R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Amino-3-bromphenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-Br, R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Amino-2-bromphenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-Br, R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Amino-3-chlorphenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-Cl, R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Amino-2-chlorphenyl)(methyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-Cl, R2 = H; n = 1, m = 2),
  
• – des 1-{2-[(4-Aminophenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = R2 = H; n = 2, m = 2),
  
• – des 1-{2-[(4-Amino-3-methylphenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-CH₃, R2 = H; n = 2, m = 2),
  
• – des 1-{2-[(4-Amino-2-methylphenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-CH₃, R2 = H; n = 2, m = 2),
  
• – des 1-{2-[(4-Amino-3-methoxyphenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-OCH₃, R2 = H; n = 2, m = 2),
  
• – des 1-{2-[(4-Amino-2-methoxyphenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-OCH₃, R2 = H; n = 2, m = 2),
  
• – des 1-{2-[(4-Amino-3-bromphenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-Br, R2 = H; n = 2, m = 2),
  
• – des 1-{2-[(4-Amino-2-bromphenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-Br, R2 = H; n = 2, m = 2),
  
• – des 1-{2-[(4-Amino-3-chlorphenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-Cl, R2 = H; n = 2, m = 2),
  
• – des 1-{2-[(4-Amino-2-chlorphenyl)(ethyl)amino]ethyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-Cl, R2 = H; n = 2, m = 2),
  
• – des 1-{3-[(4-Aminophenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Amino-3-methylphenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-CH₃, R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Amino-2-methylphenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-CH₃, R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Amino-3-methoxyphenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-OCH₃, R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Amino-2-methoxyphenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-OCH₃, R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Amino-3-bromphenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-Br, R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Amino-2-bromphenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-Br, R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Amino-3-chlorphenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-Cl, R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Amino-2-chlorphenyl)(methyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-Cl, R2 = H; n = 1, m = 3),
  
• – des 1-{3-[(4-Aminophenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = R2 = H; n = 2, m = 3),
  
• – des 1-{3-[(4-Amino-3-methylphenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-CH₃, R2 = H; n = 2, m = 3),
  
• – des 1-{3-[(4-Amino-2-methylphenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-CH₃, R2 = H; n = 2, m = 3),
  
• – des 1-{3-[(4-Amino-3-methoxyphenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-OCH₃, R2 = H; n = 2, m = 3),
  
• – des 1-{3-[(4-Amino-2-methoxyphenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-OCH₃, R2 = H; n = 2, m = 3),
  
• – des 1-{3-[(4-Amino-3-bromphenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-Br, R2 = H; n = 2, m = 3),
  
• – des 1-{3-[(4-Amino-2-bromphenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-Br, R2 = H; n = 2, m = 3),
  
• – des 1-{3-[(4-Amino-3-chlorphenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 3-Cl, R2 = H; n = 2, m = 3),
  
• – des 1-{3-[(4-Amino-2-chlorphenyl)(ethyl)amino]propyl}-4-aza-1-azonia-bicyclo[2.2.2]octans (R1 = 2-Cl, R2 = H; n = 2, m = 3),
  

A further embodiment of the first subject of the invention is characterized in that the agent comprises at least one compound according to formula (I) which is selected from salts

• - of the 1- {2 - [(4-aminophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = R2 = H; n = 1, m = 2 )
  
• - of 1- {2 - [(4-amino-3-methylphenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-CH _3, R 2 = H; n = 1, m = 2),
  
• - of 1- {2 - [(4-amino-2-methylphenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-CH _3, R 2 = H; n = 1, m = 2),
  
• - of 1- {2 - [(4-amino-3-methoxyphenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-OCH _3, R2 = H; n = 1, m = 2),
  
• - of 1- {2 - [(4-amino-2-methoxyphenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-OCH _3, R2 = H; n = 1, m = 2),
  
• - of the 1- {2 - [(4-amino-3-bromophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-Br, R2 = H n = 1, m = 2),
  
• - of the 1- {2 - [(4-amino-2-bromophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-Br, R2 = H n = 1, m = 2),
  
• - of the 1- {2 - [(4-amino-3-chlorophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-Cl, R2 = H n = 1, m = 2),
  
• - of the 1- {2 - [(4-amino-2-chlorophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-Cl, R2 = H n = 1, m = 2),
  
• - of the 1- {2 - [(4-aminophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = R2 = H; n = 2, m = 2 )
  
• - of 1- {2 - [(4-amino-3-methylphenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-CH _3, R 2 = H; n = 2, m = 2),
  
• - of 1- {2 - [(4-amino-2-methylphenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-CH _3, R 2 = H; n = 2, m = 2),
  
• - of 1- {2 - [(4-amino-3-methoxyphenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-OCH _3, R2 = H; n = 2, m = 2),
  
• - of 1- {2 - [(4-amino-2-methoxyphenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-OCH _3, R2 = H; n = 2, m = 2),
  
• - of the 1- {2 - [(4-amino-3-bromophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-Br, R2 = H n = 2, m = 2),
  
• - of 1- {2 - [(4-amino-2-bromophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-Br, R2 = H n = 2, m = 2),
  
• - of the 1- {2 - [(4-amino-3-chlorophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-Cl, R2 = H n = 2, m = 2),
  
• - of the 1- {2 - [(4-amino-2-chlorophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-Cl, R2 = H n = 2, m = 2),
  
• - of the 1- {3 - [(4-aminophenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = R2 = H; n = 1, m = 3 )
  
• - of 1- {3 - [(4-amino-3-methylphenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-CH _3, R 2 = H; n = 1, m = 3),
  
• - of 1- {3 - [(4-amino-2-methylphenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-CH _3, R 2 = H; n = 1, m = 3),
  
• - of 1- {3 - [(4-amino-3-methoxyphenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-OCH _3, R2 = H; n = 1, m = 3),
  
• - of 1- {3 - [(4-Amino-2-methoxyphenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-OCH _3, R2 = H; n = 1, m = 3),
  
• - of the 1- {3 - [(4-amino-3-bromophenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-Br, R2 = H n = 1, m = 3),
  
• - of the 1- {3 - [(4-amino-2-bromophenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-Br, R2 = H n = 1, m = 3),
  
• - of the 1- {3 - [(4-amino-3-chlorophenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-Cl, R2 = H n = 1, m = 3),
  
• - of the 1- {3 - [(4-amino-2-chlorophenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-Cl, R2 = H n = 1, m = 3),
  
• - of the 1- {3 - [(4-aminophenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = R2 = H; n = 2, m = 3 )
  
• - of 1- {3 - [(4-amino-3-methylphenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-CH _3, R 2 = H; n = 2, m = 3),
  
• - of 1- {3 - [(4-amino-2-methylphenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-CH _3, R 2 = H; n = 2, m = 3),
  
• - of 1- {3 - [(4-amino-3-methoxyphenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-OCH _3, R2 = H; n = 2, m = 3),
  
• - of 1- {3 - [(4-Amino-2-methoxyphenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-OCH _3, R2 = H; n = 2, m = 3),
  
• - of the 1- {3 - [(4-amino-3-bromophenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-Br, R2 = H n = 2, m = 3),
  
• - of the 1- {3 - [(4-amino-2-bromophenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-Br, R2 = H n = 2, m = 3),
  
• - of the 1- {3 - [(4-amino-3-chlorophenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 3-Cl, R2 = H n = 2, m = 3),
  
• - of the 1- {3 - [(4-amino-2-chlorophenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane (R1 = 2-Cl, R2 = H n = 2, m = 3),
  

And / or their physiologically acceptable salts.

A particular embodiment of the first subject of the invention is characterized in that the agent comprises at least one compound according to formula (I) which is selected from the group consisting of salts of 1- {2 - [(4-aminophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-aminophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-aminophenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane and of 1- {3- [ (4-aminophenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane.

The compounds of the formula (I) can be used in the form of their physiologically tolerated salts, in particular the chlorides, the sulfates and bromides. Further preferred salts are derived from sulfonic acids, such as benzenesulfonates, p-toluenesulfonates, C ₁ -C ₄ -alkanesulfonates, C ₁ -C ₄ -alkyl sulfates or trifluoromethanesulfonates. Depending on the number of amino groups present in the compounds according to the invention, mono-, di-, tri-, tetra- and higher adducts may be present as salts.

Agents preferred according to the invention are characterized in that they contain the compounds of the formula (I) and / or their physiologically tolerable salts, in a proportion by weight of from 0.001 to 10.0% by weight, in particular from 0.05 to 5% by weight, based on the total weight of the ready-to-use agent.

The compounds of the formula (I) can be present as sole, color-changing compounds in the composition according to the invention. However, it is preferred according to the invention if the agent additionally contains at least one oxidation dye precursor of the type of a coupler component.

Coupler components do not form a significant color within the framework of the oxidative dyeing alone, but always require the presence of developer components.

Coupler components according to the invention allow at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. This forms covalent bonds between the coupler and developer components.

• – m-Aminophenol und/oder dessen Derivate,
• – m-Diaminobenzol und/oder dessen Derivate,
• – o-Diaminobenzol und/oder dessen Derivate,
• – o-Aminophenolderivate, wie beispielsweise o-Aminophenol,
• – Naphthalinderivate mit mindestens einer Hydroxygruppe,
• – Di- beziehungsweise Trihydroxybenzol und/oder deren Derivate,
• – Pyridinderivate,
• – Pyrimidinderivate,
• – Monohydroxyindol-Derivate und/oder Monoaminoindol-Derivate,
• – Monohydroxyindolin-Derivate und/oder Monoaminoindolin-Derivate,
• – Pyrazolonderivate, wie beispielsweise 1-Phenyl-3-methylpyrazol-5-on,
• – Morpholinderivate, wie beispielsweise 6-Hydroxybenzomorpholin oder 6-Aminobenzomorpholin,
• – Chinoxalinderivate, wie beispielsweise 6-Methyl-1,2,3,4-tetrahydrochinoxalin,

Gemische aus zwei oder mehreren Verbindungen aus einer oder mehreren dieser Klassen sind im Rahmen dieser Ausführungsform ebenso erfindungsgemäß.Coupler components according to the invention are preferably selected as at least one compound from one of the following classes:

• M-aminophenol and / or its derivatives,
• M-diaminobenzene and / or its derivatives,
• O-diaminobenzene and / or its derivatives,
• O-aminophenol derivatives, such as o-aminophenol,
• Naphthalene derivatives having at least one hydroxy group,
• Di- or trihydroxybenzene and / or derivatives thereof,
• - pyridine derivatives,
• - pyrimidine derivatives,
• Monohydroxyindole derivatives and / or monoamine indole derivatives,
• Monohydroxyindoline derivatives and / or monoaminoindoline derivatives,
• Pyrazolone derivatives such as 1-phenyl-3-methylpyrazol-5-one,
• Morpholine derivatives, such as, for example, 6-hydroxybenzomorpholine or 6-aminobenzomorpholine,
• Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline,

Mixtures of two or more compounds from one or more of these classes are also within the scope of this embodiment according to the invention.

Particularly preferred coupler components according to the invention are selected from 3-amino-phenol, 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-amino-phenoxyethanol, 5-amino-4-chloro 2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro-3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1, 3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2-hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenylpropane, 2,6-bis (2'-bis) 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, 1-amino-3-bis (2-hydroxyethyl) aminobenzene, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene , 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydrox Y-3,4-d-imethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1 , 7-Dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline or mixtures of these compounds or the physiologically acceptable salts of the aforementioned compounds. Very particular preference is given to resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol, 3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1 Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 2-amino-3-hydroxypyridine and 1-naphthol and one of their physiologically acceptable salts.

The following combinations of a developer according to the invention with selected couplers are particularly advantageous:
1- {2 - [(4-Aminophenyl) (ethyl) amino] ethyl} -4-aza-1-azoniabicyclo [2.2.2] octane, chloride and one or more compounds selected from 5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2,4-dichloro-3-aminophenol, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, resorcinol, 2 -Methylresorcinol, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene.

The coupler components are preferably used in an amount of 0.0001 to 10 wt .-%, preferably 0.01 to 5.0 wt .-%, each based on the ready-to-use agent.

In order to achieve a balanced and subtle nuance formation, it is advantageous according to the invention if further coloring components are contained in the composition according to the invention.

It may therefore be preferred according to the invention if the composition contains at least one further coloring component which is selected from additional oxidation dye precursors of the developer type and / or substantive dyes.

In addition to the developer-type oxidation dye precursors according to formula (I), the compositions according to the invention may additionally comprise at least one further developer component.

Preferred further developer components are selected from at least one compound from the group formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2- (1,2-dihydroxyethyl) -p-phenylenediamine , N, N-bis- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p- phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, N, N'-bis (2-hydroxyethyl) -N, N'- bis (4-aminophenyl) -1,3-diamino-propan-2-ol, bis (2-hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) -propane-2 -ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1,2-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1 (2-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds. Particularly preferred additional developer components are p-toluenediamine, 2- (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-) imidazol-1-yl) propyl] amine, and / or 4,5-diamino-1- (2-hydroxyethyl) pyrazole and their physiologically acceptable salts.

The additional developer components are preferably used in an amount of 0.0001 to 10 wt .-%, preferably 0.001 to 5 wt .-%, each based on the ready-to-use agent.

Furthermore, the agents according to the invention may contain at least one substantive dye. These are dyes that raise directly on the hair and do not require an oxidative process to form the color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols.

The substantive dyes are each preferably used in an amount of 0.001 to 20 wt .-%, in particular from 0.05 to 5 wt .-%, each based on the total application preparation. The total amount of substantive dyes is preferably at most 3% by weight.

Direct dyes may be subdivided into anionic, cationic and nonionic substantive dyes which are selected and used by those skilled in the art for the requirements of the carrier base.

Preferred anionic substantive dyes are those having the international designations or trade names bromophenol blue, tetrabromophenol blue, Acid Yellow 1, Yellow 10, Acid Yellow 23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red 57: 1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1 and Acid Black 52 known compounds.

Preferred cationic substantive dyes are Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), Basic Blue 99, Basic Brown 16 and Basic Brown 17 and Yellow 87, Basic Orange 31 and Basic Red 51.

Suitable nonionic substantive dyes are in particular nonionic nitro and quinone dyes and neutral azo dyes. Preferred nonionic substantive dyes are those under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC HC Red 11, HC Red 11, HC Red 11, HC Red 11, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 well-known compounds, as well 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 2- (2-hydroxyethyl) amino-4,6-dinitrophenol, 4 - [(2-hydroxyethyl) amino] -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5- Chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 2 - [(4-amino-2-nitrophenyl) amino] benzoic 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-4-nitrophenol.

It is not necessary that the optionally contained substantive dyes each represent uniform compounds. Rather, due to the production process for the individual dyes, in minor amounts, other components may be included, as far as they do not adversely affect the dyeing or for other reasons, eg. As toxicological, must be excluded.

The compositions according to the invention may, in addition to the compound of the formula (I), also contain nature-analogous dyes. Compositions according to the invention which comprise precursors of naturally-analogous dyes are preferably used as air-oxidative colorants. Consequently, in this embodiment said compositions are not added with an additional oxidizing agent.

The dye precursors of naturally-analogous dyes are each preferably used in an amount of from 0.001 to 5% by weight, based on the total application preparation. Derivatives of 5,6-dihydroxyindoline, in particular 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6, are particularly suitable as precursors of naturally-analogous hair dyes -dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and 5,6-dihydroxyindoline-2-carboxylic acid, and also derivatives of 5,6-dihydroxyindole, in particular 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, and physiologically acceptable salts of the aforementioned compounds.

In the case of oxidative dyeings, the development of the color can in principle be done with atmospheric oxygen. Preferably, however, a chemical oxidizing agent is used, especially if, in addition to the coloring, a lightening effect on human hair is desired. This lightening effect may be desired regardless of the staining method. As the oxidizing agent are persulfates, peroxodisulfates, chlorites, hypochlorites and in particular hydrogen peroxide or and / or one of its solid addition products of organic or inorganic compounds in question.

In order to prevent a premature, undesired reaction of the oxidation dye precursors by the oxidizing agent, oxidation dye precursors and oxidizing agents themselves are expediently prepared separately from each other and brought into contact only immediately before use.

In a further embodiment of the present invention, therefore, agents are preferred which are characterized in that they are prepared immediately before use by mixing at least two preparations, wherein the at least two preparations are provided in at least two separate prefabricated containers and wherein a container is a colorant (A) which contains in a cosmetic carrier at least one oxidation dye precursor according to formula (I), and a further container contains an oxidizing agent preparation (B) containing at least one oxidizing agent.

The oxidizing agent preparation (B) preferably contains as the oxidizing agent hydrogen peroxide and / or one of its solid addition products of organic or inorganic compounds, such as urea, melamine and sodium borate.

The amount of oxidizing agent in the ready-to-use agent is preferably from 0.5 to 12% by weight, preferably from 2 to 10% by weight, more preferably from 3 to 6% by weight (calculated as 100% H ₂ O ₂ ), in each case based on the ready-to-use means.

Such oxidizer formulations are preferably aqueous, flowable oxidizer formulations. Preferred preparations are characterized in that the flowable oxidizing agent preparation - based on their weight - 40 to 90 wt .-%, preferably 50 to 85 wt .-%, particularly preferably 55 to 80 wt .-%, more preferably 60 to 77, 5 wt .-% and in particular 65 to 75 wt .-% water.

According to the invention, however, the oxidation dye can also be applied to the hair together with a catalyst which activates the oxidation of the dye precursors. Such catalysts are z. For example, certain enzymes, iodides, quinones or metal ions.

Furthermore, it has proven to be advantageous if the oxidizing agent preparations contain at least one stabilizer or complexing agent. Typical complexing agents and stabilizers which are preferred for the purposes of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediamine disuccinic acid (EDDS), hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N- Di- (2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), ethylenediaminediglutaric acid (EDGA), 2 -Hydroxypropylenediamine disuccinic acid (HPDS), glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG), 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS), diaminoalkyldi (sulfosuccinic acid) ( DDS), ethylenedicysteic acid (EDC), ethylenediamine-N-N'-bis (ortho-hydroxyphenyl) acetic acid (EDDHA), N-2-hydroxyethylamine-N, N-diacetic acid, glyceryliminodiacetic acid, Iminodi acetic acid N-2-hydroxypropylsulfonic acid, aspartic acid-N-carboxymethyl-N-2,5-hydroxypropyl-3-sulfonic acid, β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N- monoacetic acid, dipicolinic acid, and their salts and / or derivatives, geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), whose higher homologues having up to 8 carbon atoms and derivatives containing hydroxy or amino groups thereof and 1-aminoethane 1,1-diphosphonic acid, its higher homologues having up to 8 carbon atoms and hydroxyl- or amino-containing derivatives, aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) (EDTMP), diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) and their higher homologs, or nitrilotri (methylenephosphonic acid) , Phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, cyclodextrins, and alkali stannates (sodium stannate), alkali pyrophosphates (tetrasodium pyrophosphate, disodium pyrophosphate), Alkal iphosphate (sodium phosphate), and phosphoric acid and its salts.

In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Preferred complexing agents according to the invention are nitrogen-containing polycarboxylic acids, in particular EDTA, and phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its Hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta or Octosatriumsalz.

The dyeing preparation and optionally oxidizing agent preparation contain other auxiliaries and additives. Thus, it has proved to be preferred according to the invention if the dyeing preparation and / or the oxidizing agent preparation contains at least one thickener. With regard to these thickeners, there are no fundamental restrictions. Both organic and purely inorganic thickening agents can be used.

In a first preferred embodiment, the thickener is an anionic synthetic polymer. Preferred anionic groups are the carboxylate and sulfonate groups.

Examples of anionic monomers from which the polymeric anionic thickeners may consist are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are maleic anhydride and in particular 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

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 trade drawing Carbopol ^® commercially. Also preferred is 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 first embodiment, it may further be preferred to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid esters, methacrylic acid esters, itaconic acid mono- and diesters, vinylpyrrolidinone, vinyl ethers and vinyl esters.

The anionic acrylic acid and / or methacrylic acid polymers or copolymers are in the inventive compositions preferably in an amount of 0.1 to 10 wt .-%, particularly preferably from 1 to 5 wt .-%, each based on the weight of By means of, included.

Preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas. However, preference is also given to copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are in particular steareth-20 or ceteth-20. Such copolymers are sold by Rohm & Haas under the trade name Aculyn ^® 22 and by National Starch under the trade names Structure ^® Structure 2001 ^® 3,001th

Preferred anionic copolymers are also 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% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the sulfonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer may also be present in crosslinked form, with crosslinking agents preferably being polyolefinically unsaturated compounds such as tetraallyloxythane, allylsucrose, allylpentaerythritol and methylenebisacrylamide. Such a polymer is in the Trade products Sepigel ^® 305 and Simulgel ^® 600 from SEPPIC included. The use of these compounds which, in addition to the polymer component, a hydrocarbon mixture (C ₁₃ -C ₁₄ isoparaffin or Isohexadecan) and a nonionic emulsifier (Laureth-7 or polysorbate-80), has proved to be particularly advantageous in the context of the teaching of the invention.

Polymers of maleic anhydride and methyl vinyl ether, in particular those with crosslinks, are preferred thickeners. A crosslinked with 1,9-decadiene maleic acid-methyl copolymer available under the name Stabileze® ^® QM.

• – Polymerisate z. B. aus wenigstens 10 Gew.-% Acrylsäure-Niedrigalkylester, 25 bis 70 Gew.-% Methacrylsäure und ggf. bis zu 40 Gew.-% eines weiteren Comonomeren,
• – Mischpolymerisate aus 50 bis 75 Gew.-% Ethylacrylat, 25 bis 35 Gew.-% Acrylsäure und 0 bis 25 Gew.-% anderer Comonomeren bekannt. Geeignete Dispersionen dieser Art sind im Handel erhältlich, z. B. unter der Handelsbezeichnung Latekoll^® D (BASF).
• – Copolymerisate aus 50 bis 60 Gew.-% Ethylacrylat, 30 bis 40 Gew.-% Methacrylsäure und 5 bis 15 Gew.-% Acrylsäure, vernetzt mit Ethylenglycoldimethacrylat.

The agent according to the invention may additionally comprise at least one anionic acrylic acid and / or methacrylic acid polymer or copolymer. Preferred polymers of this type are:

• - Polymers z. From at least 10% by weight of acrylic acid lower alkyl ester, from 25 to 70% by weight of methacrylic acid and optionally up to 40% by weight of a further comonomer,
• - Copolymers of 50 to 75 wt .-% ethyl acrylate, 25 to 35 wt .-% acrylic acid and 0 to 25 wt .-% of other comonomers known. Suitable dispersions of this type are commercially available, for. B. under the trade name Latekoll ^® D (BASF).
• Copolymers of 50 to 60% by weight of ethyl acrylate, 30 to 40% by weight of methacrylic acid and 5 to 15% by weight of acrylic acid, crosslinked with ethylene glycol dimethacrylate.

In another embodiment, the thickener is a cationic synthetic polymer. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C ₁ -C ₄ -hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

in der R1 = -H oder -CH₃ ist, R2, R3 und R4 unabhängig voneinander ausgewählt sind aus C₁-C₄-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 (HP-1) aufgeführten Monomereinheiten sowie nichtionogenen Monomereinheiten, sind besonders bevorzugte kationische polymere Gelbildner. Im Rahmen dieser Polymeren 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 (HP-1),

wherein R ₁ is -H or -CH ₃ , R 2, R 3 and R ₄ are independently selected from C ₁ -C ₄ -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is one 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 (HP-1) and nonionic monomer units, are particularly preferred cationic polymeric gelling agents. 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:

• R1 is a methyl group
• - R2, R3 and R4 stand for 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 the, if desired cross-linked, poly (methacryloxyethyltrimethylammonium chloride) with the INCI name Polyquaternium-37. 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 non-aqueous 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 50% polymer content, an additional component: 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 tridecyl-polyoxypropylene-polyoxyethylene-ether (INCI name : PPG-1-trideceth-6) are commercially available.

Copolymers with monomer units of the formula (HP-1) contain as nonionic monomer units preferably acrylamide, methacrylamide, acrylic acid-C ₁ -C ₄ -alkyl esters and methacrylic acid-C ₁ -C ₄ -alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above for the homopolymers. A preferred copolymer according to the invention is the crosslinked acrylamide-methacryloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

In a further preferred embodiment, naturally occurring thickeners are used. Preferred thickening agents of this embodiment are, for example, nonionic guar gum. According to the invention, both modified and unmodified guar gums can be used. Unmodified guar gums are marketed under the trade name Jaguar ^® C from Rhone Poulenc. Modified guar gums preferred according to the invention contain C ₁ -C ₆ -hydroxyalkyl groups. Preferably, the groups are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. Such modified guar gums are known in the art and can be prepared, for example, by reaction of the guar gums with alkylene oxides. The degree of hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed in relation to the number of guar gum free hydroxy groups, is preferably between 0.4 and 1.2. Such modified guar gums are available under the trade names Jaguar ^® HP8, Jaguar ^® HP60, Jaguar ^® HP120, Jaguar DC 293 and Jaguar ^{® ®} HP105 Rhone Poulenc.

Further suitable natural thickening agents are also already known from the prior art.

Also preferred according to this embodiment are biosaccharide gums of microbial origin, such as scleroglucan gums or xanthan gums, vegetable exudate gums such as gum arabic, ghatti gum, karaya gum, tragacanth gum, carrageenan gum, agar, locust bean gum, pectins, Alginates, starch fractions and derivatives such as amylose, amylopectin and dextrins, cellulose derivatives such as methylcellulose, carboxyalkylcelluloses and hydroxyalkylcelluloses.

Preferred hydroxyalkylcelluloses are, in particular, the hydroxyethylcelluloses sold under the names Cellosize ^® Amerchol and Natrosol ^® Hercules. Suitable carboxyalkyl are especially the carboxymethylcelluloses as sold under the names Blanose ^® by Aqualon, Aquasorb ^® and ambergum ^® from Hercules and Cellgon ^® from Montello.

Starch and its derivatives are also preferred. Starch is a storage material of plants, which occurs mainly in tubers and roots, in grain seeds and in fruits and can be obtained from a variety of plants in high yield. The polysaccharide which is insoluble in cold water and forms a colloidal solution in boiling water may be, for example, potatoes, cassava, maranta, maize, cereals, rice, legumes such as peas and beans, bananas or the pulp of certain types of palms (e.g. the sago palm). Natural, plant-derived starches and / or chemically or physically modified starches can be used according to the invention. Modification can be achieved, for example, by introducing different functional groups on one or more of the hydroxyl groups of the starch. Usually, they are esters, ethers or amides of starch with optionally substituted C ₁ -C ₄₀ radicals. Especially advantageous is a etherified with 2-hydroxypropyl corn starch as it is, for example, sold by National Starch under the trade name Amaze ^®.

But also nonionic, fully synthetic polymers, such as polyvinyl alcohol or polyvinylpyrrolidinone, can be used as thickeners according to the invention. Preferred nonionic, fully synthetic polymers are for example marketed by BASF under the trade name Luviskol ^®. Such nonionic polymers, in addition to their excellent thickening properties, also allow a significant improvement in the sensory feeling of the resulting preparations.

As inorganic thickeners, phyllosilicates (polymeric, crystalline sodium disilicates) have proven to be particularly suitable in the context of the present invention. In particular clays, in particular magnesium aluminum silicates, such as bentonite, especially smectites such as montmorillonite or hectorite, which may optionally be modified also suitable, and synthetic layered silicates such as that sold by Sud Chemie under the trademark Optigel ^® magnesium phyllosilicate, are preferred ,

To further increase the performance of the oxidizing agent preparation, at least one optionally hydrated SiO ₂ compound may additionally be added to the composition according to the invention. It may be preferred according to the invention, the optionally hydrated SiO ₂ compounds in amounts of 0.05 wt .-% to 15 wt .-%, particularly preferably in amounts of 0.15 wt .-% to 10 wt .-% and completely particularly preferably used in amounts of from 0.2 wt .-% to 5 wt .-%, each based on the anhydrous composition according to the invention. The amounts given in each case the content of the SiO ₂ compounds (without their water content) in the funds again.

With regard to the optionally hydrated SiO ₂ compounds, the present invention is in principle subject to no restrictions. Preference is given to silicic acids, their oligomers and polymers and their salts. Preferred salts are the alkali salts, especially the potassium and sodium salts. The sodium salts are very particularly preferred.

The optionally hydrated SiO ₂ compounds can be present in various forms. According to the invention, the SiO ₂ compounds are preferably used in the form of silica gels (silica gel) or particularly preferably as water glass. These SiO ₂ compounds may be partially present in aqueous solution.

Very particularly preferred according to the invention are water glasses which are formed from a silicate of the formula (SiO ₂ ) _n (Na ₂ O) _m (K ₂ O) _p , where n is a positive rational number and m and p are each independently one positive rational number or 0, with the provisos that at least one of the parameters m or p is different from 0 and the ratio between n and the sum of m and p is between 1: 4 and 4: 1. Preference is given to metasilicates in which the ratio between n and the sum of m and p is 1: 2 or less.

In addition to the components described by the empirical formula, the water glasses in small amounts may contain other additives, such as phosphates or magnesium salts.

According to the invention particularly preferred water glasses are sold among others by Henkel under the names Ferrosil® ^® 119, soda water glass 40/42, Portil ^® A, Portil ^® AW and Portil ^® W and by Akzo under the name Britesil® ^® C20.

Preferably, the preparation (A) and / or optionally the oxidizing agent preparation (B) are formulated as flowable preparations.

Preferably, an emulsifier or a surfactant is added to the flowable preparations (A) and / or (B), surface-active substances being referred to as surfactants or as emulsifiers, depending on the field of application, and anionic, cationic, zwitterionic, amphoteric and nonionic surfactants and emulsifiers are selected. These substances will be described in detail below.

• – lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel RO(CH₂CH₂O)_xCH₂COOH, 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,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• – lineare α-Olefinsulfonate mit 8 bis 24 C-Atomen,
• – Sulfonate ungesättigter Fettsäuren mit 8 bis 24 C-Atomen und 1 bis 6 Doppelbindungen,
• – α-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• – Alkylsulfate und Alkylethersulfate der Formel RO(CH₂CH₂O)_xSO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2–15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen,
• – Alkyl- und/oder Alkenyletherphosphate der Formel
  
  in der R bevorzugt für einen aliphatischen, gegebenenfalls ungesättigten Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen, R' für Wasserstoff, einen Rest (CH₂CH₂O)_yR und x und y unabhängig voneinander für eine Zahl von 1 bis 10 steht,
• – sulfatierte Fettsäurealkylenglykolester der Formel RC(O)O(alkO)_nSO₃H, in der R für einen linearen oder verzweigten, aliphatischen, gesättigten und/oder ungesättigten Alkylrest mit 6 bis 22 C-Atomen, alk für CH₂CH₂, CHCH₃CH₂ und/oder CH₂CHCH₃ und n für eine Zahl von 0,5 bis 5 steht,
• – Monoglyceridsulfate und Monoglyceridethersulfate.

Suitable anionic surfactants in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group of 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 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,
• Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,
• - linear alkanesulfonates having 8 to 24 carbon atoms,
• Linear α-olefinsulfonates having 8 to 24 C atoms,
• Sulfonates of unsaturated fatty acids having 8 to 24 C atoms and 1 to 6 double bonds,
• Α-sulfofatty acid methyl esters of fatty acids having 8 to 30 carbon atoms,
• Alkyl sulfates and alkyl ether sulfates of the formula RO (CH ₂ CH ₂ O) _x SO ₃ H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12,
• Mixtures of hydroxysulfonates,
• Sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene glycol ethers,
• Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms,
• - Alkyl and / or alkenyl ether of the formula
  
  in which R is an aliphatic, optionally unsaturated hydrocarbon radical having 8 to 30 carbon atoms, R 'is hydrogen, a radical (CH ₂ CH ₂ O) _y R and x and y independently of one another have a number from 1 to 10,
• - sulfated Fettsäurealkylenglykolester of the formula RC (O) O (AlkO) _n SO ₃ H, in which R is a linear or branched, aliphatic, saturated and / or unsaturated alkyl radical having 6 to 22 carbon atoms, Alk is CH ₂ CH ₂ CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ and n is a number from 0.5 to 5,
• Monoglyceride sulfates and monoglyceride ether sulfates.

Preferred anionic surfactants are alkyl sulfates, alkyl ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate, sulfonate or sulfate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyl-di-methylammoniumglycinat, N-acyl-aminopropyl-N, N-dimethylammoniumglycinate, for example Kokosacylaminopropyl-dimethylammoniumglycinat, and 2 Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Amphoteric surfactants are understood to mean those surface-active compounds which, apart from a C ₈ -C ₂₄ -alkyl or -acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which are capable of forming internal salts , Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 24 C Atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

• – Anlagerungsprodukte von 1 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, wie beispielsweise beispielsweise Lauryl-, Myristyl-, Cetyl-, aber auch Stearyl-, Isostearyl- und Oleylalkohol, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – mit einem Methyl- oder C₂-C₆-Alkylrest endgruppenverschlossene Anlagerungsprodukte von 1 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, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol^® LS, Dehydol^® LT (Cognis) erhältlichen Typen,
• – Polyglycerinester und alkoxylierte Polyglycerinester, wie beispielsweise Poly(3)glycerindiisostearat (Handelsprodukt: Lameform^®TGI (Henkel)) und Poly(2)glycerinpolyhydroxy-stearat (Handelsprodukt: Dehymuls^®PGPH (Henkel)).
• – Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen^® HSP (Cognis) oder Sovermol-Typen (Cognis),
• – höher alkoxylierte, bevorzugt propoxylierte und insbesondere ethoxylierte, Mono-, Di- und Triglyceride, wie beispielsweise Glycerinmonolaurat + 20 Ethylenoxid und Glycerinmonostearat + 20 Ethylenoxid,
• – Aminoxide,
• – Hydroxymischether,
• – Sorbitanfettsäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate und Sorbitanmonolaurat + 20 Mol Ethylenoxid (EO),
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Fettsäure-N-alkylglucamide,
• – Alkylphenole und Alkylphenolalkoxylate mit 6 bis 21, insbesondere 6 bis 15 Kohlenstoffatomen in der Alkylkette und 1 bis 30 Ethylenoxid- und/oder Propylenoxid-Einheiten. Bevorzugte Vertreter dieser Klasse sind beispielsweise Nonylphenol + 9 EO und Octylphenol + 8 EO;
• – Alkylpolyglykoside entsprechend der allgemeinen Formel RO-(Z)_x, wobei R für Alkyl, Z für Zucker sowie x für die Anzahl der Zuckereinheiten steht. Die erfindungsgemäß verwendbaren Alkylpolyglykoside können lediglich einen bestimmten Alkylrest R enthalten. Üblicherweise werden diese Verbindungen aber ausgehend von natürlichen Fetten und Ölen oder Mineralölen hergestellt. In diesem Fall liegen als Alkylreste R Mischungen entsprechend den Ausgangsverbindungen bzw. entsprechend der jeweiligen Aufarbeitung dieser Verbindungen vor.

Furthermore, it has proved to be advantageous if the dyeing and whitening agents according to the invention contain further nonionic surfactants. Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

• - Addition products of 1 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, such as, for example, lauryl, myristyl, cetyl, but also stearyl, isostearyl and oleyl alcohol , fatty acids having 8 to 30 carbon atoms and alkylphenols having 8 to 15 carbon atoms in the alkyl group,
• - With a methyl or C ₂ -C ₆ -alkyl radical endgruppenverschlossene addition products of 1 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 C atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as those available under the trade names Dehydol ^® LS, LT Dehydol ^® types (Cognis),
• - polyglycerol esters and alkoxylated polyglycerol esters, such as poly (3) glycerol diisostearate (commercial product: Lameform ^® TGI (Henkel)) and poly (2) glycerinpolyhydroxy stearate (commercial product: Dehymuls ^® PGPH (Henkel)).
• - polyol, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol types (Cognis),
• Higher alkoxylated, preferably propoxylated and in particular ethoxylated, mono-, di- and triglycerides, such as glycerol monolaurate + 20 ethylene oxide and glycerol monostearate + 20 ethylene oxide,
• - amine oxides,
• - hydroxymix ether,
• Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates and sorbitan monolaurate + 20 moles of ethylene oxide (EO),
• Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,
• Adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Fatty acid N-alkylglucamides,
• - Alkylphenols and Alkylphenolalkoxylate having 6 to 21, in particular 6 to 15 carbon atoms in the alkyl chain and 1 to 30 ethylene oxide and / or propylene oxide units. Preferred representatives of this class are, for example, nonylphenol + 9 EO and octylphenol + 8 EO;
• - Alkylpolyglykoside according to the general formula RO- (Z) _x , wherein R is alkyl, Z is sugar and x is the number of sugar units. The alkyl polyglycosides which can be used according to the invention can only contain one particular alkyl radical R. Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

Suitable nonionic surfactants are, in particular, C ₈ -C ₂₂ -alkyl mono- and oligoglycosides and their ethoxylated analogs. In particular, the nonethoxylated compounds have been found to be particularly suitable.

• – 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.

Particularly preferred are those alkyl polyglycosides of the formula RO- (Z) _x , in which R

• Essentially C ₈ and C ₁₀ alkyl groups,
• Essentially of C ₁₂ and C ₁₄ alkyl groups,
• Essentially of C ₈ to C ₁₆ alkyl groups or
• Substantially from C ₁₂ to C ₁₆ alkyl groups or
• - Consists essentially of C ₁₆ to C ₁₈ alkyl groups.

These compounds are characterized in that any mono- or oligosaccharides can be used as the sugar unit Z. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

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

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

Further preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations having excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

Particularly preferred non-ionic surface-active substances are substances that are commercially available as solids or liquids in pure form because of their ease of processing. The definition of purity in this context does not refer to chemically pure compounds. Rather, especially when it comes to products on a natural basis, mixtures of different homologs can be used, for example, with different alkyl chain lengths, as in Products based on natural fats and oils. Even with alkoxylated products, mixtures of different degrees of alkoxylation are usually present. The term purity in this context refers rather to the fact that the selected substances should preferably be free from solvents, adjuvants and other impurities.

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

The anionic, nonionic, zwitterionic or amphoteric surfactants are used in amounts of 0.1 to 45 wt .-%, preferably 1 to 30 wt .-% and most preferably from 1 to 15 wt .-%, based on the total amount of ready for use By means of, used.

Also preferred 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, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines and are characterized in addition to a good conditioning effect especially by their good biodegradability. An inventively particularly suitable compound from this group of substances under the name Tegoamid ^® S 18 commercial stearamidopropyl dimethylamine is.

Likewise very readily biodegradable are quaternary ester compounds, so-called "ester quats". Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® 180 and Dehyquart ^® AU-35 are examples of such esterquats.

The cationic surfactants are contained in the compositions according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

In a preferred embodiment, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof may be preferred.

• – 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 bis 6 Kohlenstoffatomen mit gesättigten Fettsäuren mit 8 bis 22 C-Atomen,
• – Sterine, wobei als Sterine eine Gruppe von Steroiden verstanden wird, 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, vor allem Glucose-Phospolipide, die z. B. als Lecithine bzw. Phosphatidylcholine aus z. B. Eidotter oder Pflanzensamen (z. B. Sojabohnen) gewonnen werden,
• – 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 effect of the active ingredient according to the invention can be increased by emulsifiers. Such emulsifiers 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 to 6 carbon atoms with saturated fatty acids having 8 to 22 C atoms,
• Sterols, sterols being understood as meaning a group of steroids which carry a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterines) 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, especially glucose phospholipids, the z. B. as lecithins or phosphatidylcholines from z. Egg yolks or plant seeds (eg 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 carbon atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The agents according to the invention preferably contain the emulsifiers in amounts of from 0.1 to 25% by weight, in particular from 0.5 to 15% by weight, based on the total amount of the ready-to-use agent.

Nonionic emulsifiers or surfactants having an HLB value of 10-15 may be particularly preferred according to the invention. Among the emulsifier types mentioned, the emulsifiers which do not contain any ethylene oxide and / or propylene oxide in the molecule can be very particularly preferred.

• – nichtionische Polymere wie beispielsweise Vinylpyrrolidinon/Vinylacrylat-Copolymere, Polyvinylpyrrolidinon, Vinylpyrrolidinon/Vinylacetat-Copolymere, Polyethylenglykole und Polysiloxane;
• – Silikone wie flüchtige oder nicht flüchtige, geradkettige, verzweigte oder cyclische, vernetzte oder nicht vernetzte Polyalkylsiloxane (wie Dimethicone oder Cyclomethicone), Polyarylsiloxane und/oder Polyalkylarylsiloxane, insbesondere Polysiloxane mit organofunktionelle Gruppen, wie substituierten oder unsubstituierten Aminen (Amodimethicone), Carboxyl-, Alkoxy- und/oder Hydroxylgruppen (Dimethiconcopolyole), lineare Polysiloxan(A)-Polyoxyalkylen(B)-Blockcopolymere, gepfropften Silikonpolymere mit nicht silikonhaltigem, organischen Grundgerüst oder mit Polysiloxan-Grundgerüst, wie beispielsweise das unter der INCI-Bezeichnung Bis-PEG/PPG-20/20 Dimethicone vertriebene Handelsprodukt Abil B 8832 der Firma Degussa, oder deren Gemischen;
• – kationische Polymere wie quaternisierte Celluloseether, Polysiloxane mit quaternären Gruppen, Dimethyldiallylammoniumchlorid-Polymere, Acrylamid-Dimethyldiallyl-ammoniumchlorid-Copolymere, mit Diethylsulfat quaternierte Dimethylamino-ethylmethacrylat-Vinylpyrrolidinon-Copolymere, Vinylpyrrolidinon-Imidazolinium-methochlorid-Copolymere und quaternierter Polyvinylalkohol;
• – zwitterionische und amphotere Polymere wie beispielsweise Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere und Octylacrylamid/Methyl-methacrylat/tert-Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere, Diallyldimethylammoniumchlorid/Acrylat-Copolymere, t-Butylaminoethylmethacrylat/N-(1,1,3,3-Tetramethylbutyl)acrylamid/Acrylat(/Methacrylat)-Copolymere,
• – anionische Polymere wie beispielsweise Polyacrylsäuren, vernetzte Polyacrylsäuren, Vinylacetat/Crotonsäure-Copolymere, Vinylpyrrolidinon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornylacrylat-Copolymere, Methylvinylether/Malein-säureanhydrid-Copolymere und Acrylsäure/Ethylacrylat/N-t-Butyl-acrylamid-Terpolymere,
• – weitere 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 Glucose, Maleinsäure und Milchsäure,
• – haarkonditionierende Verbindungen wie Phospholipide, beispielsweise Sojalecithin, Ei-Lecitin und Kephaline sowie Silikonöle,
• – 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
• – Entschäumerwie Silikone,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – Aminosäuren und Oligopeptide, insbesondere Arginin und/oder Serin,
• – Proteinhydrolysate auf tierischer und/oder pflanzlicher Basis, wie beispielsweise Elastin-, Kollagen-, Keratin-, Seiden- und Milcheiweiß-Proteinhydrolysate, oder Mandel-, Reis-, Erbsen-, Kartoffel- und Weizenproteinhydrolysate, sowie in Form ihrer Fettsäure-Kondensationsprodukte oder gegebenenfalls anionisch oder kationisch modifizierten Derivate,
• – pflanzliche Öle, beispielsweise Macadamianussöl, Kukuinussöl, Palmöl, Amaranthsamenöl, Pfirsichkernöl, Avocadoöl, Olivenöl, Kokosöl, Rapsöl, Sesamöl, Jojobaöl, Sojaöl, Erdnussöl, Nachtkerzenöl und Teebaumöl
• – Lichtschutzmittel, insbesondere derivatisierte Benzophenone, Zimtsäure-Derivate und Triazine,
• – Substanzen zur Einstellung des pH-Wertes, wie beispielsweise übliche Säuren, insbesondere Genusssäuren und Basen,
• – Wirkstoffe wie Panthenol, Pantothensäure, Pantolacton, Allantoin, Pyrrolidinoncarbonsäuren und deren Salze sowie Bisabolol,
• – Polyphenole, insbesondere Hydroxyzimtsäuren, 6,7-Dihydroxycumarine, Hydroxybenzoesäuren, Catechine, Tannine, Leukoanthocyanidine, Anthocyanidine, Flavanone, Flavone und Flavonole;
• – Ceramide, bevorzugt die Sphingolipide wie Ceramide I, Ceramide II, Ceramide 1, Ceramide 2, Ceramide 3, Ceramide 5 und Ceramide 6, oder Pseudoceramide, wie insbesondere N-(C₈-C₂₂-Acyl)-(C₈-C₂₂-acyl)-hydroxyprolin,
• – Vitamine, Provitamine und Vitaminvorstufen, insbesondere solche der Gruppen A, B₃, B₅, B₆, C, E, F und H,
• – Pflanzenextrakte wie beispielsweise die Extrakte aus Aloe Vera, Angelica, Anis, Aprikose, Benzoe, Bergamotte, Birke, Brennnessel, Calmus, Cassis, Costus, Eibisch, Eichenrinde, Elemi, Estragon, Fichtennadel, Galbanum, Geranium, Ginseng, Grapefruit, Guajakholz, grünem Tee, Hamamelis, Hauhechel, Hopfen, Huflattich, Ingwerwurzel, Iris, Jasmin, Kamille, Kardamon, Klee, Klettenwurzel, Kiefer, Kiwi, Kokosnuss, Koriander, Kümmel, Latschen, Lavendel, Lemongras, Lilie, Limone, Lindenblüten, Litchi, Macis, Malve, Mandel, Mango, Melisse, Melone, Meristem, Myrrhe, Neroli, Olibanum, Opoponax, Orange, Patchouli, Petitgrain, Pinie, Quendel, Rooibos, Rosen, Rosmarin, Rosskastanie, Sandelholz, Salbei, Schachtelhalm, Schafgarbe, Sellerie, Tanne, Thymian, Wacholder, Weinblättern, Weißdorn, Weizen, Wiesenschaumkraut, Ylang-Ylang, Zeder und Zitrone.
• – Cholesterin,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fette und Wachse wie Walrat, Bienenwachs, Montanwachs und Paraffine,
• – Fettsäurealkanolamide,
• – 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.

Furthermore, the agents according to the invention may contain other active ingredients, auxiliaries and additives, such as, for example

• Nonionic polymers such as vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone, vinylpyrrolidinone / vinyl acetate copolymers, polyethylene glycols and polysiloxanes;
• Silicones, such as volatile or nonvolatile, straight-chain, branched or cyclic, crosslinked or uncrosslinked polyalkylsiloxanes (such as dimethicones or cyclomethicones), polyarylsiloxanes and / or polyalkylarylsiloxanes, especially polysiloxanes with organofunctional groups, such as substituted or unsubstituted amines (amodimethicones), carboxyl, Alkoxy and / or hydroxyl groups (dimethicone copolyols), linear polysiloxane (A) -polyoxyalkylene (B) block copolymers, grafted silicone polymers with non-silicone-containing organic backbone or with polysiloxane backbone, such as those under the INCI name Bis-PEG / PPG -20 / 20 dimethicone sold commercial product Abil B 8832 from Degussa, or mixtures thereof;
• Cationic polymers such as quaternized cellulose ethers, quaternary group polysiloxanes, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallyl-ammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidinone copolymers, vinylpyrrolidinone-imidazolinium methochloride copolymers, and quaternized polyvinyl alcohol;
• Zwitterionic and amphoteric polymers such as, for example, acrylamidopropyltrimethylammonium chloride / acrylate copolymers and octylacrylamide / methylmethacrylate / tert-butylaminoethylmethacrylate / 2-hydroxypropylmethacrylate copolymers, diallyldimethylammonium chloride / acrylate copolymers, t-butylaminoethylmethacrylate / N- (1,1,3, 3-tetramethylbutyl) acrylamide / acrylate (/ methacrylate) copolymers,
• Anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidinone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and acrylic acid / ethyl acrylate / Nt-butyl acrylamide terpolymers,
• - Other thickeners such as agar-agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, eg. For example, methylcellulose, hydroxyalkylcellulose and carboxymethylcellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays such. As bentonite or fully synthetic hydrocolloids such. For example, polyvinyl alcohol,
• - structurants such as glucose, maleic acid and lactic acid,
• Hair-conditioning compounds such as phospholipids, for example soybean lecithin, egg lecithin and cephalins and silicone oils,
• 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,
• Amino acids and oligopeptides, in particular arginine and / or serine,
• Animal and / or plant-based protein hydrolysates, for example elastin, collagen, keratin, silk and milk protein protein hydrolysates, or almond, rice, pea, potato and wheat protein hydrolysates, and in the form of their fatty acid condensation products or optionally anionically or cationically modified derivatives,
• Vegetable oils, for example, macadamia nut oil, kukui nut oil, palm oil, amaranth seed oil, peach kernel oil, avocado oil, olive oil, coconut oil, rapeseed oil, sesame oil, jojoba oil, soybean oil, peanut oil, evening primrose oil and tea tree oil
• - light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and triazines,
• Substances for adjusting the pH, for example customary acids, in particular edible acids and bases,
• - active substances such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol,
• Polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols;
• Ceramides, preferably the sphingolipids such as ceramides I, ceramides II, ceramides 1, ceramides 2, ceramides 3, ceramides 5 and ceramides 6, or pseudoceramides, in particular N- (C ₈ -C ₂₂ -acyl) - (C ₈ -C _22- acyl) -hydroxyproline,
• 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 the extracts of aloe vera, angelica, anise, apricot, benzoin, bergamot, birch, nettle, calmus, cassis, costus, marshmallow, oak bark, elemi, tarragon, spruce needle, galbanum, geranium, ginseng, grapefruit, guaiac wood, green tea, witch hazel, toadstool, hops, coltsfoot, ginger root, iris, jasmine, chamomile, cardamom, clover, burdock root, pine, kiwi, coconut, cilantro, caraway, pine, lavender, lemongrass, lily, lime, lime blossom, litchi, mace , Mallow, almond, mango, melissa, melon, meristem, myrrh, neroli, olibanum, opoponax, orange, patchouli, petitgrain, pine, quenelle, rooibos, roses, rosemary, horse chestnut, sandalwood, sage, horsetail, yarrow, celery, fir , Thyme, juniper, grape leaves, hawthorn, wheat, meadowfoam, ylang-ylang, cedar and lemon.
• - 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,
• - 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.

The choice of these other substances will be made by those skilled in the art according to the desired properties of the agents.

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

The additional active ingredients and auxiliaries are preferably used in the agents according to the invention in amounts of from 0.0001 to 10% by weight, in particular from 0.0005 to 5% by weight, based on the total weight of the application mixture.

For the strong lightening of very dark hair, the sole use of hydrogen peroxide or its addition products to organic or inorganic compounds is often not sufficient. The compositions according to the invention may therefore additionally contain further bleaching and / or bleaching agents.

If a strong lightening is desired in addition to the coloring of the keratinic fiber, it is therefore preferred according to the invention if in addition a bleaching preparation (C) containing at least one bleach activator, the mixture of oxidizing agent preparation (B) and the preparation (A) containing at least one oxidation dye precursor according to formula (I) is admixed.

It may be irrelevant whether first a mixture of (A) and (B) is prepared, and then the Blondierzubereitung (C) is added, or whether a different order of mixing of the individual components is used. It is preferred to mix the individual preparations in the earliest possible chronological order and preferably to apply the ready-to-use agent promptly to the keratinic fibers.

A further embodiment of the present application is therefore an agent for bleaching and dyeing keratinic fibers, characterized in that it comprises mixing at least one oxidizing agent preparation (B) containing at least one oxidizing agent selected from hydrogen peroxide, its addition compounds to solid carriers, at least one bleaching preparation ( C) containing at least one bleaching power enhancer, and at least one preparation (A) comprising, in a cosmetic carrier, at least one oxidation dye precursor according to formula (I), prepared before use.

In a further embodiment, it is preferred if the colorant according to the invention additionally contains as bleaching preparation (C) at least one inorganic peroxo compound. Preferably, the inorganic peroxy compound is selected from ammonium persulfate, alkali metal persulfates, ammonium peroxomonosulfate, alkali metal hydrogen peroxomonosulfates, alkali metal peroxodiphosphates and alkaline earth metal peroxides. Particularly preferred inorganic peroxy compounds as bleaching force enhancers are ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxodisulfate, potassium hydrogen peroxomonosulfate, potassium peroxodiphosphate, magnesium peroxide and barium peroxide, in particular ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate.

The inorganic peroxo compounds are preferably contained in an amount of 0.1 to 25 wt .-%, in particular in an amount of 0.5 to 15 wt .-%, based on the total weight of the ready-to-use agent.

The use of persulfate salts or peroxodisulfate salts is generally carried out in the form of an optionally dedusted powder or a molding pressed into the mold.

However, it may be advantageous according to the invention if the agents are free of inorganic peroxo compounds. However, the compositions according to the invention may therefore instead of and / or in addition to the solid peroxo compounds contain a further bleaching power enhancer.

In the context of this invention, additional bleach boosters which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids and / or substituted perbenzoic acid, carbonic acid derivatives, alkyl carbonates and carbamates and also silyl carbonates and carbamates.

As bleach boosters which give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid under perhydrolysis conditions, substances are suitable which contain O- and / or N-acyl groups of the C-groups mentioned above. Atom number and / or optionally substituted benzoyl groups bear. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or i-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

As bleach booster of the carbonic acid derivatives type, carbonate salts or bicarbonate salts may preferably be used according to the invention. These are preferably selected from the group the ammonium, alkali metal (in particular sodium and potassium) and alkaline earth metal (in particular calcium), carbonate salts or bicarbonate salts. Particularly preferred carbonate or bicarbonate salts are ammonium hydrogencarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate and calcium carbonate. These particularly preferred salts can be used alone or in their mixtures of at least two representatives as bleaching amplifiers.

As further additional bleach boosters, in the compositions according to the invention preferably at least one compound selected from acetic acid, lactic acid, tartaric acid, citric acid, salicylic acid and ortho-phthalic acid may be contained.

The bleach boosters used in addition to or instead of peroxo compounds are preferred in amounts of from 0.05 to 10% by weight, in particular in amounts of from 0.2 to 5% by weight, in each case based on the total weight of the ready-to-use cosmetic agents By means of, included.

Although in principle there are no restrictions with regard to the formulation of the blonding preparation (C), it has proved to be preferred according to the invention if the preparation (C) is formulated anhydrous.

Anhydrous in the sense of the present invention means a water content based on the preparation (C) of less than 5 wt .-%, in particular of less than 2 wt .-%. Blondierzubereitungen containing less than 0.1 wt .-% water, according to the invention may be very particularly preferred. The preparation (C) is preferably formulated as a powder or as an anhydrous paste.

In a further preferred embodiment, the agent in the preparation (C) as bleaching force enhancer may contain at least one cationic pyridinium derivative. In particular, agents according to the invention are preferred which contain as cationic pyridinium derivative at least one compound of 2-acetyl-1-methylpyridinium p-toluenesulfonate and / or 4-acetyl-1-methylpyridinium p-toluenesulfonate and / or N-methyl-3, 4-dihydroisoquinolinium p-toluenesulfonate.

An inventively preferred embodiment of the present invention is that the ready-to-use agent has a pH between 7 and 11, in particular between 8 and 10.5, particularly preferably between 8.5 and 10.0.

Usually, the pH is adjusted with pH adjusters. In order to adjust the pH, those skilled in the art are familiar with common acidifying and alkalizing agents. The alkalizing agents which can be used for adjusting the pH are typically selected from inorganic salts, in particular the alkali metals and alkaline earth metals, organic alkalizing agents, in particular amines, basic amino acids and alkanolamines, and ammonia. Acidifying agents which are preferred according to the invention are pleasure acids, such as, for example, citric acid, acetic acid, malic acid or tartaric acid, and also dilute mineral acids.

For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ° C.

Organic alkalizing agents which can be used according to the invention are preferably selected from alkanolamines of primary, secondary or tertiary amines having a C ₂ -C ₆ -alkyl basic body which carries at least one hydroxyl group. Particularly preferred alkanolamines are selected from the group 2-aminoethane-1-ol (monoethanolamine), 2-amino-2-methylpropan-1-ol, 2-amino-2-methyl-propane-1,3-diol and triethanolamine.

However, it has been found in the context of the investigations of the present invention that furthermore preferred agents according to the invention are characterized in that they additionally contain an inorganic alkalizing agent. The inorganic alkalizing agent of the present invention is preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate and potassium carbonate. Very particular preference is given to sodium hydroxide and / or potassium hydroxide.

The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from L-arginine, D-arginine, D / L-arginine, L-lysine, D-lysine, D / L-lysine, more preferably L-arginine, D-arginine, D / L-arginine used as an alkalizing agent according to the invention.

Finally, another preferred alkalizing agent is ammonia.

The alkalizing agents are preferably contained in an amount of from 0.05 to 10% by weight, in particular from 0.5 to 5% by weight, based in each case on the total weight of the ready-to-use agent.

As already mentioned, the compositions according to the invention can also be prepared directly before use from two or more separately packaged preparations. This is particularly useful for the separation of incompatible ingredients to avoid premature reaction. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or to be feared. The ready-to-use agent in such systems is manufactured by the consumer just prior to application by mixing the components. A dyeing and / or whitening agent in which the oxidation dye precursors are initially separate from the oxidizing agent preparation, preferably containing hydrogen peroxide, is preferred.

• – in einem Container A mindestens eine Zubereitung (A) enthält, enthaltend in einem kosmetischen Träger mindestens ein Oxidationsfarbstoffvorprodukt gemäß der Formel (I), und
• – in einem Container B mindestens eine Oxidationsmittelzubereitung (B), enthaltend in einem kosmetischen Träger mindestens ein Oxidationsmittel,

enthält.A preferred dosage form of the agent according to the invention is a packaging unit (kit-of-parts), which is made up of separately packaged containers

• In a container A, at least one preparation (A) comprising, in a cosmetic carrier, at least one oxidation dye precursor according to the formula (I), and
• In a container B, at least one oxidizing agent preparation (B) comprising, in a cosmetic carrier, at least one oxidizing agent,

contains.

• – in einem Container A mindestens eine Zubereitung (A), enthaltend in einem kosmetischen Träger mindestens ein Oxidationsfarbstoffvorprodukt gemäß der Formel (I),
• – in einem Container B mindestens eine Oxidationsmittelzubereitung (B), enthaltend mindestens ein Oxidationsmittel, und
• – in einem Container C mindestens eine Blondierzubereitung (C), enthaltend mindestens einen Bleichkraftverstärker,

enthält.If a particularly strong lightening effect is desired, a preferred further dosage form of the agent according to the invention is a packaging unit (kit-of-parts), which is made up of containers which are made up separately

• In a container A at least one preparation (A) comprising in a cosmetic carrier at least one oxidation dye precursor according to the formula (I),
• In a container B, at least one oxidizing agent preparation (B) containing at least one oxidizing agent, and
• In a container C, at least one bleaching preparation (C) containing at least one bleaching power booster,

contains.

The multi-component packaging unit (kit-of-parts) preferably additionally contains an instruction manual. In addition, it may be preferred if an application aid, such as a comb or a brush, and / or personal protective equipment, such as disposable gloves, are also included in the kit.

With regard to further preferred embodiments of the multi-component packaging unit (kit-of-parts), what has been said about the agents according to the invention applies mutatis mutandis.

The actual hair dye is expediently prepared immediately before use by mixing the preparations (A) with (B) and optionally (C). The application temperatures can range between 15 and 40 ° C. After a contact time of 5 to 45 minutes, the hair dye is removed by rinsing of the hair to be dyed. The washing with a shampoo is eliminated if a strong surfactant-containing carrier, eg. As a dyeing shampoo was used.

Another object of the present invention is therefore a process for dyeing and optionally whitening human hair, in which an inventive composition according to the above instructions is applied to the hair, for a contact time of 5 to 45 minutes, preferably from 8 to 35 minutes, on the Hair is left, and rinsed out of the hair or washed out with a shampoo.

During the contact time of the agent on the fiber, it may be advantageous to assist the dyeing process by supplying heat. The heat can be supplied by an external heat source, such. B. warm air of a hot air blower, as well as, especially in a hair dye on living subjects through the Body temperature of the subject done. In the latter case, usually the part to be dyed is covered with a hood. In particular, the temperature during the exposure time is between 10 ° C and 45 ° C, especially between 20 ° C and 40 ° C. The colorants according to the invention give intensive dyeings even at physiologically compatible temperatures of below 45.degree. They are therefore particularly suitable for dyeing human hair.

Another object of the present invention is the use of an agent according to the invention in oxidative colorants for human hair to improve the gray coverage, the leveling, the color intensity, the durability and / or the color of the dyeing results.

With regard to further preferred embodiments of the methods and uses according to the invention, mutatis mutandis the statements made regarding the agents according to the invention apply.

Finally, a last subject of the present invention relates to compounds according to formula (I) of the first subject of the invention. With respect to further preferred embodiments of these compounds mutatis mutandis applies to the means of the invention.

Examples - Synthesis Examples

Synthesis Example 1: 1- {2 - [(4-Aminophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane chloride, hydrochloride salt (E 1)

1.1. Synthesis of N- (2-chloroethyl) -N-ethylaniline:

76.6 g (0.50 mol) of phosphorus oxychloride were initially charged and heated to 80.degree. To this was added dropwise 82.6 g (0.50 mol) of N- (2-hydroxyethyl) -N-ethylaniline (exothermic reaction). After completion of the dropwise addition, stirring was continued for 1 h at 80.degree. After cooling, the reaction mixture was poured onto 300 ml of ice water. With 530 ml of a 10 wt .-% aqueous sodium hydroxide solution, a pH of 5 was set. In this case, a brown oil separated, which was separated and distilled at a vacuum of 30 mbar (transition temperature 142 ° C). The product was obtained as a colorless oil. Yield: 64.1 g (70.0%).

1.2. Synthesis of 1- [2- (N-ethyl-N-phenylamino) ethyl] -4-aza-1-azoniabicyclo [2.2.2] octane, chloride:

23.1 g (0.20 mol) of 1,4-diazabicyclo [2.2.2] octane were dissolved in 400 ml of toluene and at room temperature with 32.8 g (0.178 mol) of N- (2-chloroethyl) -N-ethylaniline offset from level 1.1. This mixture was stirred for 72 h at an oil bath temperature of 90 ° C. After every 24 h, the reaction mixture was allowed to cool and filtered from the resulting precipitate. The various fractions of the precipitate were combined, washed with methyl tert-butyl ether and dried at 50 ° C in a vacuum. Yield: 17.4 g (32.9%).

1.3. Synthesis of 1- (2- {ethyl [4- (phenyldiazenyl) phenyl] amino} ethyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride:

3.73 g (0.04 mol) of aniline was dissolved in 50 ml of a 2N aqueous hydrochloric acid solution and cooled to 5 ° C. While cooling, a solution of 2.76 g (0.04 mol) of sodium nitrite in 40 ml of water was added dropwise. After completion of the dropwise addition, stirring was continued for 15 minutes, then the excess of sodium nitrite still present was destroyed by addition of 4 drops of a 20% strength by weight sulfamic acid solution. This resulted in a transparent yellow solution of the diazonium salt. 11.83 g (0.04 mol) of 1- [2- (N-ethyl-N-phenylamino) ethyl] -4-aza-1-azoniabicyclo [2.2.2] octane, chloride from step 1.2. were dissolved in a mixture of 75 ml of water and 18 ml of 2 N aqueous hydrochloric acid. After cooling to 5 ° C., the solution of the previously freshly prepared diazonium salt was added dropwise to this solution. During the dropping, a slow red coloration of the reaction mixture was observed. After completion of the dropwise addition, stirring was continued for 2 h at 0 to 5 ° C. Thereafter, a pH of 5 was adjusted by adding a 30% aqueous sodium acetate solution. The resulting solution was diluted by the addition of 1 l of water (dist.). This aqueous phase was washed 5 times with 200 ml of dichloromethane (the organic phase was discarded). Subsequently, the aqueous phase was completely concentrated to dryness. The residue was taken up several times in 300 ml of ethanol (abs.), Separated from the undissolved remaining anorgansichen salts by filtration and concentrated again completely to dryness. Here, the product was obtained as a residue in the form of a dark oil, which crystallized after about 2 weeks. Yield: 10.1 g (63%)

1.4 Synthesis of 1- {2 - [(4-Aminophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, chloride, hydrochloride salt (E 1):

10.0 g (0.03 mol) of 1- (2- {ethyl- [4- (phenyldiazenyl) phenyl] amino} ethyl) -4-aza-1-azoniabicyclo [2.2.2] octane, chloride from stage 1.3. were dissolved in a mixture of 2000 ml of ethanol and 40 ml of water, as a catalyst, 2.2 g of palladium on carbon (5%) were added. The solution of the educt was then reduced in an autoclave at RT and a hydrogen pressure of 10 bar. After completion of the reduction, the catalyst was filtered off and the filtrate was mixed with 50 ml of a 10% aqueous hydrochloric acid solution. The filtrate was then concentrated completely on a rotary evaporator under reduced pressure, leaving the product as a residue in the form of a light, purple solid. Yield: 9.6 g (95%); C ₁₆ H ₂₇ N ₄ Cl x 2.5 HCl (402.02 g / mol) calc. C 47.8 H 7.40 N 13.9 Cl 30.9. C 46.6 H 7.19 N 11.6 Cl 30.3.

Examples - Dyeing Examples

Preparation of the coloring cream

The following coloring creams were made: Hydrenol D 8.5% by weight Lorol tech. 2.0% by weight Texapon NSO UP 20.0% by weight Dehyton K. 12.5% by weight Eumulgin B2 0.75% by weight sodium 1.0% by weight ammonium sulfate 1.0% by weight Developer component E1 3 mmol Kupplerkomponente 3 mmol water ad 100% by weight Used raw materials: Hydrenol D C ₁₂ -C ₁₈ fatty alcohol, (INCI name: Cetearyl alcohol, Cognis) Lorol, techn. C ₁₂ - / C ₁₈ fatty alcohol, (INCI name: Cetearyl alcohol, Cognis) Texapon NSO UP Lauryl alcohol diglycol ether sulfate, Na salt (28% solution) (INCI name: Sodium Laureth Sulfate; Cognis) Dehyton K. Cocoylbetaine (INCI name: Cocamidopropyl betaine; Cognis) Eumulgin B2 C ₁₆ - / C ₁₈ -fatty alcohol, ethoxylated (20 EO) (INCI name: Ceteareth-10; Cognis)

Hydrenol D and Lorol, techn. were melted together with Texapon NSO-UP, Dehyton K and Eumulgin B2 at 80 ° C. Then, the melt was emulsified with the sodium sulfite dissolved in a part of the water and ammonium sulfate. The developer according to the invention was dissolved in propylene glycol and a further portion of the stated amount of water with heating and added with stirring. The coupler was also dissolved in a portion of the indicated amount of water and added with stirring. Then the formulation was made up to 100% with water and stirred cold.

The coloring cream thus obtained was mixed in a ratio of 2: 1 with the following developer dispersion having a hydrogen peroxide content of 3%. dipicolinic 0.1% by weight sodium pyrophosphate 0.03% by weight Turpinal SL 1.50% by weight Texapon N28 2.00% by weight Acrysol 22 0.60% by weight Hydrogen peroxide, 50% by weight 6.00% by weight Sodium hydroxide, 45% by weight 0.80% by weight water ad 100% by weight Used raw materials: Turpinal SL 1-hydroxyethane-1,1-diphosphonic acid (about 58-61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia) Texapon N28 Lauryl ether sulfate sodium salt (at least 26.5% active ingredient content, INCI name: Sodium Laureth Sulfate) (Cognis) Acrysol 22 Acrylic polymer (about 29.5-30.5% solids in water, INCI name: Acrylates / Steareth-20 Methacrylate Copolymer)

Mixing with the developer dispersion and application

For the dyeing process, four times the amount of ready-to-use mixture was applied to one strand of 80% gray hair (Kerling). After a contact time of 30 minutes at 32 ° C, the locks were rinsed and washed out with a conventional shampoo. The streaking of the streaks was visually assessed under the daylight lamp after drying. The staining results are summarized in the following tables. E1: 1- {2 - [(4-Aminophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, chloride, hydrochloride salt example Kupplerkomponente got nuance color intensity E1-1 resorcinol dun ++ E1-2 3-amino-2-methylamino-6-methoxypyridine blue gray +++ E1-3 5-amino-2-methylphenol matt purple + E1-4 3-amino-2-hydroxypyridine dark purple ++ E1-5 1,3-bis (2,4-diaminophenoxy) propane nordischblau +++ E1-6 2,7-dihydroxynaphthalene olivgrau + Color intensity: +++ high ++ medium + low

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• CH 552032 [0008]
• EP 1396486 [0008]
• EP 1348695 [0008]

Cited non-patent literature

• Kh. Schrader, Basics and Formulations of Cosmetics, 2nd Edition, Hüthig Buch Verlag, Heidelberg, 1989 [0112]

Claims (10)

Agent for the oxidative color change of keratinic fibers, characterized in that it comprises, in a cosmetic carrier as a developer-type oxidation dye precursor, at least one compound of the formula (I)

R _{1 represents} a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₁ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ -polyhydroxyalkyl group, a C ₁ -C ₆ -alkoxy group or R _{2 is} a halogen atom, R _{2 is} a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a hydroxy group, an acetoxy group, a C ₁ -C ₆ alkoxy group, an amino group, a C ₁ -C _6- Alkylamino group, a di (C ₁ -C ₆ alkyl) amino group, a cyano group, a carboxylic acid group, a sulfonic acid group, a carbamoyl group or a C ₁ -C ₆ alkyloxycarbonyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group , n is an integer from 1 to 6, m is an integer from 2 to 6 and X ^{- is} a physiologically acceptable anion, and / or one of its physiologically acceptable salt. Composition according to Claim 1, characterized in that it contains a compound of the formula (I) in which R _{1 is} hydrogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy or halogen, more preferably is a hydrogen atom. Composition according to one of claims 1 to 2, characterized in that it contains a compound of formula (I) in which R _{2 is} a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group or a C ₁ -C ₆ alkoxy group. Agent according to one of claims 1 to 3, characterized in that it contains a compound of formula (I), in which n is the number 1 or 2 and / or m is the number 2 or 3. Composition according to one of claims 1 to 4, characterized in that the compound according to formula (I) is selected from the group formed from salts of 1- {2 - [(4-aminophenyl) (methyl) amino] ethyl} - 4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-3-methylphenyl) (methyl) amino] ethyl} -4-aza-1-azoniabicyclo [2.2. 2] octane, of 1- {2 - [(4-amino-2-methylphenyl) (methyl) amino] ethyl} -4-aza-1-azoniabicyclo [2.2.2] octane, of 1- {2 - [( 4-amino-3-methoxyphenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-2-methoxyphenyl) (methyl ) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-3-bromophenyl) (methyl) amino] ethyl} -4-aza 1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-2-bromophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-3-chlorophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [( 4-amino-2-chlorophenyl) (methyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-aminophenyl) (ethyl) amino] ethyl } -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-3-methylphenyl) (ethyl) amino] ethyl} -4-aza-1-azonia bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-2-methylphenyl) (ethyl) amino] ethyl} -4-aza 1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-3-methoxyphenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-2-methoxyphenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [( 4-amino-3-bromophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-2-bromophenyl) (ethyl ) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of the 1- {2 - [(4-amino-3-chlorophenyl) (ethyl) amino] ethyl} -4-aza 1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-amino-2-chlorophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-phenyl) (methyl) amino] -propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4- Amino-3-methylphenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-2-methylphenyl) (methyl) amino ] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-3-methoxyphenyl) (methyl) amino] -propyl} -4-aza-1 azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-2-methoxyphenyl) (methyl) amino] propyl} -4-aza 1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-3-bromophenyl) (methyl) amino] -propyl} -4-aza-1-azonia-bicyclo [2.2.2 ] octane, of 1- {3 - [(4-amino-2-bromophenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of the 1- {3- [ (4-Amino-3-chlorophenyl) (methyl) amino] -propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-2-chlorophenyl) ( methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-aminophenyl) (ethyl) amino] -propyl} -4-aza-1-azonia -bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-3-methylphenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, des 1- {3 - [(4-Amino-2-methylphenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, the 1- {3 - [(4-amino 3-methoxyphenyl) (ethyl) amino] propyl} -4-aza-1-azoniabicyclo [2.2.2] octane, of 1- {3 - [(4-amino-2-methoxyphenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-3-bromophenyl) (ethyl) amino] -propyl} -4-aza-1-azonia -bicyclo [2.2.2] octane, of the 1- {3 - [(4-amino-2-bromophenyl) (ethyl) amino] propyl} -4-aza- 1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-3-chlorophenyl) (ethyl) amino] -propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {3 - [(4-amino-2-chlorophenyl) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane. Composition according to one of claims 1 to 5, characterized in that the compound according to formula (I) is selected from the group formed from salts of 1- {2 - [(4-aminophenyl) (methyl) amino] ethyl} 4-aza-1-azonia-bicyclo [2.2.2] octane, of 1- {2 - [(4-aminophenyl) (ethyl) amino] ethyl} -4-aza-1-azonia-bicyclo [2.2.2 ] octane, of 1- {3 - [(4-aminophenyl) (methyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane and of 1- {3 - [(4-aminophenyl ) (ethyl) amino] propyl} -4-aza-1-azonia-bicyclo [2.2.2] octane. Agent according to one of claims 1 to 6, characterized in that it contains the compounds according to formula (I), in a proportion by weight of 0.001 to 10.0 wt .-%, in particular 0.05 to 5 wt .-%, based on Total weight of the ready-to-use agent. Composition according to one of claims 1 to 7, characterized in that it additionally contains at least one coupler-type oxidation dye precursor which is selected from the group consisting of selected from 3-aminophenol, 5-amino-2-methylphenol, 3 -Amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol, 5- (2-hydroxyethyl) amino-2-methylphenol, 2,4-dichloro 3-aminophenol, 2-aminophenol, 3-phenylenediamine, 2- (2,4-diaminophenoxy) ethanol, 1,3-bis (2,4-diaminophenoxy) propane, 1-methoxy-2-amino-4- (2 -hydroxyethylamino) benzene, 1,3-bis (2,4-diaminophenylpropane, 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, 1-amino-3-bis - (2-hydroxyethyl) amine above zol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene, 2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4- dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine, 1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindoline and their physiologically acceptable salts. Use of a composition according to any one of claims 1 to 8 in human hair oxidative colorants for improving gray coverage, leveling, color intensity, durability and / or color of the dyeing results. Compounds of the formula (I) according to one of Claims 1 to 6.