DE102014215484A1 - "New oxidation dye precursors of the oxy, thio and aza-bisbenzene type" - Google Patents

Abstract

The invention relates to compositions for the oxidative color change of keratinic fibers, in particular human hair, comprising in a cosmetic carrier (A) at least one oxidation dye precursor of the formula (I) and / or its physiologically acceptable salt, wherein Y1, Y2 independently of one another represent a group R6R7N-, a hydroxy group, a C1-C6 alkyl group or a cyano group, X represents an oxygen atom (-O-), a sulfur atom (-S-) or a group -NR8-, R1, R2, R5 independently of one another Hydrogen, C1-C6 alkyl, C2-C6 alkenyl, hydroxy C2-C6 alkyl, polyhydroxy-C2-C6 alkyl, hydroxy, C1-C6 alkoxy, cyano, C1 C6 alkoxycarbonyl group, a nitro group, an aryl group or a halogen atom (fluorine, chlorine, bromine or iodine), R3, R4 independently represent a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a hydroxy-C2 C6-alk yl group, a polyhydroxy-C 2 -C 6 -alkyl group, a hydroxy group, a C 1 -C 6 -alkoxy group, an amino group, a group R 9 R 10 N-, a cyano group, a C 1 -C 6 -alkoxycarbonyl group, a nitro group, an aryl group or a halogen atom ( Fluorine, chlorine, bromine or iodine), R6, R7, R8, R9, R10 independently represent a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a hydroxy-C2-C6 alkyl group, a polyhydroxy -C 2 -C 6 alkyl group or an aryl group, provided that at least one of the radicals from the group Y1 and Y2 is a group R6R7N-.

Description

The invention relates to agents for the oxidative color change of keratin fibers, in particular human hair, which contain new oxidation dye precursors of the type of oxy, thio and / or aza-bisbenzene. Furthermore, the invention relates to the use of these oxidation dye precursors in the dyeing of keratinic fibers to obtain dyeings having improved perspiration fastness.

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 hair or even 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 the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with coupling with one or more coupler components. The oxidation colorants are characterized by intensive, outstanding, long-lasting dyeing results.

Specific representatives are, for example, p-phenylenediamine, p-toluenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2- (2,5-diaminophenyl) -ethanol, 2- (2,5-diaminophenoxy) ethanol, 1-phenyl-3-carboxyamido-4-amino-pyrazolone-5, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy -4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N, N'-bis (2-hydroxyethyl) -N , N'-bis (4-aminophenyl) -diamino-propan-2-ol.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are generally used. Suitable coupler substances are in particular 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3 -methyl-pyrazolone-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) -propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3 -aminophenol, 2-methylresorcinol, 5-methylresorcinol and 2-methyl-4-chloro-5-aminophenol.

Good oxidation dye precursors are primarily intended to meet the following requirements: They must form the desired color shades in sufficient intensity and authenticity in the oxidative coupling. You must also have a good Aufziehvermögen on the fiber, especially in human hair no significant differences between strained and freshly regrowed hair may exist (leveling ability). They should be resistant to light, heat, sweat, friction and the influence of chemical reducing agents, e.g. Perm liquids. After all, they should not stain the scalp too much, and above all, they should be safe from a toxicological and dermatological point of view. Furthermore, the coloring obtained by bleaching should be easily removed from the hair again, if the person treated expresses a short-term change in color (good color removal behavior).

Especially at high temperatures special demands are placed on the perspiration fastness of the oxidative colorants. The object of the present invention was therefore to find new coupler components which meet the requirements imposed on oxidation dye precursors and provide intensive colorations with good fastness properties, in particular with good perspiration fastness.

Surprisingly, it has now been found that specific oxidation dye precursors of the general formula (I) satisfy the abovementioned requirements to a high degree. The coupler components of the invention enable the production of rich and intense nuances and were characterized in particular by a high perspiration fastness.

worin
Y1, Y2 unabhängig voneinander für eine Gruppe R6R7N-, eine Hydroxygruppe, eine C₁-C₆-Alkylgruppe oder für eine Cyanogruppe stehen,
X für ein Sauerstoffatom (-O-), ein Schwefelatom (-S-) oder für eine Gruppe -NR8- steht,
R1, R2, R5 unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Hydroxy-C₂-C₆-alkylgruppe, eine Polyhydroxy-C₂-C₆-alkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine Cyanogruppe, eine C₁-C₆-Alkoxy-carbonylgruppe, eine Nitrogruppe, eine Arylgruppe oder ein Halogenatom (Fluor, Chlor, Brom oder Jod) stehen,
R3, R4 unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Hydroxy-C₂-C₆-alkylgruppe, eine Polyhydroxy-C₂-C₆-alkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine Aminogruppe, eine Gruppe R9R10N-, eine Cyanogruppe, eine C₁-C₆-Alkoxycarbonylgruppe, eine Nitrogruppe, eine Arylgruppe oder ein Halogenatom (Fluor, Chlor, Brom oder Jod) stehen,
R6, R7, R8, R9, R10 unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Hydroxy-C₂-C₆-alkylgruppe, eine Polyhydroxy-C₂-C₆-alkylgruppe oder eine Arylgruppe stehen,
mit der Maßgabe, dass mindestens einer der Reste aus der Gruppe Y1 und Y2 für eine Gruppe R6R7N- steht. A first subject of the invention is an agent for the oxidative color change of keratinic fibers, in particular of human hair, contained in a cosmetic carrier
(A) at least one oxidation dye precursor of the formula (I) and / or its physiologically acceptable salt,

wherein
Y1, Y2 independently of one another represent a group R6R7N-, a hydroxy group, a C ₁ -C ₆ -alkyl group or a cyano group,
X represents an oxygen atom (-O-), a sulfur atom (-S-) or a group -NR8-,
R _1, R 2, R 5 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a hydroxy-C ₂ -C ₆ -alkyl group, a polyhydroxy-C ₂ -C ₆ -alkyl group , a hydroxy group, a C ₁ -C ₆ -alkoxy group, a cyano group, a C ₁ -C ₆ -alkoxycarbonyl group, a nitro group, an aryl group or a halogen atom (fluorine, chlorine, bromine or iodine),
R 3, R 4 independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a hydroxy C ₂ -C ₆ alkyl group, a polyhydroxy C ₂ -C ₆ alkyl group, a Hydroxy, C ₁ -C ₆ alkoxy, amino, R 9 R 10 N, cyano, C ₁ -C ₆ alkoxycarbonyl, nitro, aryl or halogen (fluoro, chloro, bromo or iodo),
R6, R7, R8, R9, R10 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a hydroxy-C ₂ -C ₆ -alkyl group, a polyhydroxy-C ₂ - C ₆ alkyl group or an aryl group,
with the proviso that at least one of the radicals from the group Y1 and Y2 stands for a group R6R7N-.

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 oxidation dye precursors (A) 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 tableted 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.

The term "agent for oxidative color change" used according to the invention is understood to mean oxidative colorants which contain at least one oxidation dye precursor of the formula (I). The formation of the coloration can be effected by the presence of atmospheric oxygen, but preferably by the presence of an oxidant other than atmospheric oxygen. The latter is usually hydrogen peroxide. Depending on the amount of oxidizing agent used, the keratin fiber is at the same time lightened more or less strongly during dyeing, since the oxidizing agent not only initiates the dye-forming process of developers and couplers but also oxidatively destroys the hair-borne pigments (melanins).

Depending on the amounts used of the oxidation dye precursors and the oxidizing agent, the oxidative color change may therefore primarily be a coloration (with a high proportion of dyestuff) or, primarily, a lightening (with a high proportion of oxidant). In the latter case, the oxidation dye precursors are used mainly for the nuance of the Aufhellergebnisses.

The agents according to the invention for the oxidative color change of keratinic fibers contain, as an oxidation dye precursor (A) essential to the invention, one or more compounds of the formula (I). The compounds of formula (I) are coupler type oxidation dye precursors. Examples of the substituents Y1, Y2, X, R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 mentioned in formula (I) are given below by way of example: A hydroxy group denotes a group -OH. Examples of C ₁ -C ₆ -alkyl radicals are -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 (allyl group), 2-methyl-prop-2-enyl, but-3-enyl, but-2-enyl, pent-4-enyl or pent-3 enyl. 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, wherein -CH ₂ CH ₂ OH is 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 the methoxy group (- OCH ₃ ). An amino group means a group -NH2. A cyano group means a group -C≡N. Examples of a C ₁ -C ₆ alkoxycarbonyl group are a methoxycarbonyl group (H ₃ COC (O) -) an ethoxycarbonyl group, an n-propoxycarbonyl group. The phenyl group is a preferred example of an aryl group. Examples of halogen are fluorine, chlorine, bromine or iodine. Preferred halogen atoms are fluorine, chlorine and bromine.

By choosing suitable substituents R1 to R5, both the absorption of the compounds on the hair can be optimized as well as their Nuancenausfall be modified.

The oxidation dye precursors of the formulas (I) in which R _1, R 2 and R 5 independently of one another represent hydrogen, a C ₁ -C ₆ -alkyl group, a C ₁ -C ₆ -alkoxy group or a halogen atom (fluorine, chlorine, bromine or iodine) , are preferred because with these oxidation dyes particularly intense dyeings could be obtained.

Particularly preferably, the radicals R _1, R 2 and R 5 independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group. From the group of the C1-C6-alkyl groups in turn, the methyl group is very particularly preferred.

In a preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one oxidation dye precursor of the formula (I) in which R _1, R 2 and R 5 independently of one another represent hydrogen or a C ₁ -C ₆ -alkyl group.

Furthermore, it has proved to be advantageous if oxidation dye precursors of the formula (I) are used in which R 3 and R 4 are each independently a hydrogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, an amino group or a nitro group. Particularly preferably, R 3 and R 4 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, an amino group or a nitro group.

In a further preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one oxidation dye precursor of the formula (I) in which R3 and R4 independently of one another represent hydrogen, a C ₁ -C ₆ -alkyl group, an amino group or a nitro group stand.

The substituent X may represent an oxygen atom (-O-), a sulfur atom (-S-) or a group -NR8-. Via the substituent X, the two aromatic systems of the oxidation dye precursors of the formula (I) are linked together. At the same time, the substituent X is an electron-rich heteroatom (with free electron pairs), which activates the two aromatic systems, so that both ring systems are capable of reacting with further oxidation dye precursors. Together with the radicals R 1 to R 5, the group X also influences the absorption properties of the dye formed during the oxidative dyeing process.

When X is a group -NR8-, then R8 is preferably a hydrogen atom for steric reasons. It has been found to be particularly preferable if X stands for an oxygen atom (-O-) or for a group -NR8-, where R8 stands for a hydrogen atom.

In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one oxidation dye precursor of the formula (I) in which X is an oxygen atom (-O-) or a group -NR8-, where R8 is a Hydrogen atom is.

In the oxidation dye precursors of the formula (I), the radicals Y1 and Y2 can independently of one another be a group R6R7N-, a hydroxy group, a C ₁ -C ₆ -alkyl group or a cyano group. The proviso is that at least one of the radicals from the group Y1 and Y2 is a group R6R7N-, since the presence of at least one group R6R7N- in the coupler structures of the formula (I) has proven to be a prerequisite for a sufficiently intense color result.

The radicals R _{6 and} R 7 may in turn be selected independently of one another from a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a hydroxy-C ₂ -C ₆ -alkyl group, a polyhydroxy-C ₂ - C ₆ alkyl group or an aryl group. Particularly preferably, the radicals R6 and R7 are both a hydrogen atom, in which case the group R6R7N- is an amino group.

Particularly good dyeing properties can also be achieved if oxidation dye precursors of the formula (I) are used in which radicals Y1 and / or Y2 stand for an amino group.

A further particularly preferred embodiment is accordingly characterized in that the agent according to the invention comprises at least one oxidation dye precursor of the formula (I) in which Y1 is an amino group and / or Y2 is an amino group.

In a further particularly preferred embodiment, an agent according to the invention is characterized in that it comprises at least one oxidation dye precursor of the formula (I) in which Y1 is an amino group and Y2 is an amino group.

In a further particularly preferred embodiment, an agent according to the invention is characterized in that it comprises at least one oxidation dye precursor of the formula (I) in which Y1 is an amino group or Y2 is an amino group.

Furthermore, it has been found that the dyeing and fastness properties of the oxidation dye precursors of the formula (I) according to the invention are particularly good if one of the two radicals from the group Y1 and Y2 is an amino group and the other of the two radicals is a hydroxy group. When using corresponding compounds of the formula (I) in which Y1 is a hydroxyl group and Y2 is an amino group, or in which Y1 is an amino group and Y2 is a hydroxy group, color results could be obtained on keratin fibers, which are distinguished by their very good perspiration.

• – Y1 für eine Hydroxygruppe steht und Y2 für eine Aminogruppe steht oder
• – Y1 für eine Aminogruppe steht und Y2 für eine Hydroxygruppe steht.

A further particularly preferred embodiment is accordingly characterized in that the agent according to the invention contains at least one oxidation dye precursor of the formula (I) in which

• - Y1 is a hydroxy group and Y2 is an amino group or
• - Y1 is an amino group and Y2 is a hydroxy group.

In summary, in consideration of the abovementioned preferred and particularly preferred embodiments, the oxidation dye precursors of the formula (I) are therefore very particularly preferred in which R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or a methyl group, R 3 is a hydrogen atom, R 4 represents a hydrogen atom, a methyl group, an amino group or a nitro group and R 5 represents a hydrogen atom or a methyl group.

• – R1 für ein Wasserstoffatom oder eine Methylgruppe steht,
• – R2 für ein Wasserstoffatom oder für eine Methylgruppe steht,
• – R3 für ein Wasserstoffatom steht
• – R4 für ein Wasserstoffatom, eine Methylgruppe, eine Aminogruppe oder eine Nitrogruppe steht und
• – R5 für ein Wasserstoffatom oder eine Methylgruppe steht.

A further particularly preferred embodiment is accordingly characterized in that the agents according to the invention comprise at least one oxidation dye precursor of the formula (I) in which

• R1 represents a hydrogen atom or a methyl group,
• R2 is a hydrogen atom or a methyl group,
• - R3 is a hydrogen atom
• R4 represents a hydrogen atom, a methyl group, an amino group or a nitro group, and
• - R5 represents a hydrogen atom or a methyl group.

Very intensive color results with good perspiration fastnesses could also be obtained if oxidation dye precursors of the formula (I) were used in which Y1 is an amino group, Y2 is an amino group and the radical R4 is also an amino group. In addition, it has been found that compounds having this substitution pattern are particularly well suited to the development of matting shades since they have nuances in blue with a wide variety of p-phenylenediamine type (ie, differently substituted 1,4-diaminobenzene derivatives) developers. Gray and turquoise area supply.

• – Y1 für eine Aminogruppe steht
• – Y2 für eine Aminogruppe steht und
• – R4 für eine Aminogruppe steht.

A further particularly preferred embodiment is accordingly characterized in that the agent according to the invention contains at least one oxidation dye precursor of the formula (I) in which

• - Y1 stands for an amino group
• - Y2 is an amino group and
• - R4 stands for an amino group.

– 3-[(3-Aminophenyl)amino]phenol

– 3-(3-Aminophenoxy)anilin

– 3-(3-Aminophenoxy)phenol

– 1-N-(3-Aminophenyl)-4-methylbenzen-1,3-diamin

– 5-[(3-Aminophenyl)amino]-2-methylphenol

– 3-[(3-Amino-4-methylphenyl)amino]phenol

– 5-(3-Aminophenoxy)-2-methylanilin

– 3-(3-Amino-4-methylphenoxy)phenol

– 5-(3-Aminophenoxy)-2-methylphenol

– 1-N-(3-Amino-4-methylphenyl)-4-methylbenzen-1,3-diamin

– 5-[(3-Amino-4-methylphenyl)amino]-2-methylphenol

– 5-(3-Amino-4-methylphenoxy)-2-methylanilin

– 5-(3-Amino-4-methylphenoxy)-2-methylphenol

– 1-N-(3-Aminophenyl)-4-nitrobenzen-1,3-diamin

– 4-N-(3-Aminophenyl)benzen-1,2,4-triamin

– 5-(3-Aminophenoxy)-2-nitroanilin

– 4-(3-Aminophenoxy)benzen-1,2-diamin

– 3-[(3-Amino-4-nitrophenyl)amino]phenol

– 3-[(3,4-Diaminophenyl)amino]phenol

– 5-[(3-Aminophenyl)amino]-2-nitrophenol

– 2-Amino-5-[(3-aminophenyl)amino]phenol

– 1-N-(3-Amino-4-nitrophenyl)-5-methylbenzen-1,3-diamin

– 4-N-(3-Amino-5-methylphenyl)benzen-1,2,4-triamin

– 3-(3-Amino-4-nitrophenoxy)-5-methylanilin

– 4-(3-Amino-5-methylphenoxy)benzen-1,2-diamin

– 3-[(3-Amino-4-nitrophenyl)amino]-5-methylphenol

– 3-[(3,4-Diaminophenyl)amino]-5-methylphenol

– 5-[(3-Amino-5-methylphenyl)amino]-2-nitrophenol

– 2-Amino-5-[(3-amino-5-methylphenyl)amino]phenol

– 4-N-(3-Aminophenyl)-5-methylbenzen-1,2,4-triamin

und/oder deren physiologisch verträglichen Salzen. In a further particularly preferred embodiment, an agent according to the invention is characterized in that it comprises at least one oxidation dye precursor of the formula (I) which is selected from - 1-N- (3-aminophenyl) benzene-1,3-diamine

- 3 - [(3-aminophenyl) amino] phenol

- 3- (3-aminophenoxy) aniline

3- (3-aminophenoxy) phenol

- 1-N- (3-aminophenyl) -4-methylbenzene-1,3-diamine

- 5 - [(3-aminophenyl) amino] -2-methylphenol

- 3 - [(3-amino-4-methylphenyl) amino] phenol

- 5- (3-aminophenoxy) -2-methylaniline

- 3- (3-amino-4-methylphenoxy) phenol

- 5- (3-aminophenoxy) -2-methylphenol

- 1-N- (3-amino-4-methylphenyl) -4-methylbenzene-1,3-diamine

- 5 - [(3-Amino-4-methylphenyl) amino] -2-methylphenol

- 5- (3-amino-4-methylphenoxy) -2-methylaniline

- 5- (3-amino-4-methylphenoxy) -2-methylphenol

1-N- (3-aminophenyl) -4-nitrobenzene-1,3-diamine

4-N- (3-aminophenyl) benzene-1,2,4-triamine

- 5- (3-aminophenoxy) -2-nitroaniline

- 4- (3-aminophenoxy) benzene-1,2-diamine

- 3 - [(3-amino-4-nitrophenyl) amino] phenol

- 3 - [(3,4-diaminophenyl) amino] phenol

- 5 - [(3-aminophenyl) amino] -2-nitrophenol

2-Amino-5 - [(3-aminophenyl) amino] phenol

- 1-N- (3-amino-4-nitrophenyl) -5-methylbenzene-1,3-diamine

4-N- (3-amino-5-methylphenyl) benzene-1,2,4-triamine

- 3- (3-amino-4-nitrophenoxy) -5-methylaniline

- 4- (3-amino-5-methylphenoxy) benzene-1,2-diamine

- 3 - [(3-amino-4-nitrophenyl) amino] -5-methylphenol

- 3 - [(3,4-diaminophenyl) amino] -5-methylphenol

- 5 - [(3-Amino-5-methylphenyl) amino] -2-nitrophenol

2-Amino-5 - [(3-amino-5-methylphenyl) amino] phenol

4-N- (3-aminophenyl) -5-methylbenzene-1,2,4-triamine

and / or their physiologically acceptable salts.

• – 1-N-(3-Aminophenyl)benzen-1,3-diamin
• – 3-[(3-Aminophenyl)amino]phenol
• – 3-(3-Aminophenoxy)anilin
• – 3-(3-Aminophenoxy)phenol
• – 1-N-(3-Aminophenyl)-4-methylbenzen-1,3-diamin
• – 5-[(3-Aminophenyl)amino]-2-methylphenol
• – 3-[(3-Amino-4-methylphenyl)amino]phenol
• – 5-(3-Aminophenoxy)-2-methylanilin
• – 3-(3-Amino-4-methylphenoxy)phenol
• – 5-(3-Aminophenoxy)-2-methylphenol
• – 1-N-(3-Amino-4-methylphenyl)-4-methylbenzen-1,3-diamin
• – 5-[(3-Amino-4-methylphenyl)amino]-2-methylphenol
• – 5-(3-Amino-4-methylphenoxy)-2-methylanilin
• – 5-(3-Amino-4-methylphenoxy)-2-methylphenol
• – 4-N-(3-Aminophenyl)benzen-1,2,4-triamin
• – 4-(3-Aminophenoxy)benzen-1,2-diamin
• – 3-[(3,4-Diaminophenyl)amino]phenol
• – 2-Amino-5-[(3-aminophenyl)amino]phenol
• – 4-N-(3-Amino-5-methylphenyl)benzen-1,2,4-triamin
• – 4-(3-Amino-5-methylphenoxy)benzen-1,2-diamin
• – 3-[(3,4-Diaminophenyl)amino]-5-methylphenol
• – 2-Amino-5-[(3-amino-5-methylphenyl)amino]phenol
• – 4-N-(3-Aminophenyl)-5-methylbenzen-1,2,4-triamin

und/oder deren physiologisch verträglichen Salzen. Within the aforementioned group, the following compounds show a particularly good dyeing performance. The use of one or more oxidation dyes of the formula (I) from the following group is therefore explicitly very explicitly preferred:

• 1-N- (3-aminophenyl) benzene-1,3-diamine
• - 3 - [(3-aminophenyl) amino] phenol
• - 3- (3-aminophenoxy) aniline
• 3- (3-aminophenoxy) phenol
• - 1-N- (3-aminophenyl) -4-methylbenzene-1,3-diamine
• - 5 - [(3-aminophenyl) amino] -2-methylphenol
• - 3 - [(3-amino-4-methylphenyl) amino] phenol
• - 5- (3-aminophenoxy) -2-methylaniline
• - 3- (3-amino-4-methylphenoxy) phenol
• - 5- (3-aminophenoxy) -2-methylphenol
• - 1-N- (3-amino-4-methylphenyl) -4-methylbenzene-1,3-diamine
• - 5 - [(3-Amino-4-methylphenyl) amino] -2-methylphenol
• - 5- (3-amino-4-methylphenoxy) -2-methylaniline
• - 5- (3-amino-4-methylphenoxy) -2-methylphenol
• 4-N- (3-aminophenyl) benzene-1,2,4-triamine
• - 4- (3-aminophenoxy) benzene-1,2-diamine
• - 3 - [(3,4-diaminophenyl) amino] phenol
• 2-Amino-5 - [(3-aminophenyl) amino] phenol
• 4-N- (3-amino-5-methylphenyl) benzene-1,2,4-triamine
• - 4- (3-amino-5-methylphenoxy) benzene-1,2-diamine
• - 3 - [(3,4-diaminophenyl) amino] -5-methylphenol
• 2-Amino-5 - [(3-amino-5-methylphenyl) amino] phenol
• 4-N- (3-aminophenyl) -5-methylbenzene-1,2,4-triamine

and / or their physiologically acceptable salts.

The oxidation dye precursors (A) of the formula (I) according to the invention are amino compounds. These can also 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-toluenesulfonyl sulfonates, C ₁ -C ₄ -alkanesulfonates 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.

The physiologically acceptable salts of the oxidation dye precursors (A) of the formula (I) are in particular the hydrochlorides, the hydrobromides and the sulfates of these compounds.

The oxidation dye precursor or products (A) of the formula (I) can be used in the compositions according to the invention in a total amount of from 0.001 to 5.0% by weight, preferably from 0.1 to 4.5% by weight, more preferably from 0 From 2 to 4.0% by weight, and more preferably from 0.3 to 3.5% by weight, based on the total weight of the composition.

In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that it comprises (A) one or more oxidation dye precursors of the formula (I) in a total amount of from 0.001 to 5.0% by weight, preferably from 0.1 to 4, 5 wt .-%, more preferably from 0.2 to 4.0 wt .-% and particularly preferably from 0.3 to 3.5 wt .-% - based on the total weight of the composition - contains.

As already mentioned, the oxidation dye precursors of formula (I) are coupler type compounds. To form the coloration, the compositions according to the invention therefore preferably comprise at least one further oxidation dye precursor of the developer type (numbered as oxidation dye precursors from group (B).

Preferred further developer components are selected 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) -propan-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, as well as 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 physiologically acceptable salts of the oxidation dye precursors of the developer type from group (B) are in particular the hydrochlorides, hydrobromides and sulfates of these compounds.

The oxidation dyes of the formula (I) react with the developers (B) from the group consisting of p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -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, bis (2-methoxymethyl-p-phenylenediamine) hydroxy-5-aminophenyl) methane, 4-aminophenol, 4-amino-3-methylphenol, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2 , 5,6-triaminopyrimidine and / or 2-hydroxy-4,5,6-triaminopyrimidine. For this reason, the use of these developers (B) and / or their physiologically acceptable salts is particularly preferred.

In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that it additionally contains (B) one or more oxidation dye precursors from the group which is formed from p-phenylenediamine, p-toluenediamine, 2- (2-hydroxyethyl) -p phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole-1 -yl) propyl] amine, bis (2-hydroxy-5-aminophenyl) methane, 4-aminophenol, 4-amino-3-methylphenol, 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 / or their physiologically acceptable salts.

The agents according to the invention may contain the developer component (s) from group (B) in a total amount of from 0.001 to 5.0% by weight, preferably from 0.1 to 4.5% by weight, more preferably from 0.2 to 4.0 wt .-% and particularly preferably from 0.3 to 3.5 wt .-% - based on the total weight of the composition - included.

In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains one or more oxidation dye precursors from group (B) in a total amount of from 0.001 to 5.0% by weight, preferably from 0.1 to 4.5% by weight .-%, more preferably from 0.2 to 4.0 wt .-% and particularly preferably from 0.3 to 3.5 wt .-% - based on the total weight of the composition - contains.

To form a very specific color loss and to further improve the leveling ability, the compositions of the invention may additionally contain other coupler-type oxidation dyes other than the compounds of formula (I).

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 permit at least one substitution of a chemical residue of the coupler by the oxidized form of the developer component. Covalent bonds form between 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. As a further suitable coupler component according to the invention, preference is given to selecting 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,
• - Chinoxalinderivate, 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.

The following couplers from the group (C) together with the oxidation dye precursors (A) of the formula (I) and the developers from the group (B) form very intense colorations, therefore, the couplers (C) selected from 3 are preferred -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-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2- {3 - [(2-Hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol , 2 - ({3 - [(2-hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-yl-phenyl) -amino] -ethanol, 3-amino-4- (2- methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis (2-hydroxyet hyl) aminobenzene, 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 and / or 7-hydroxyindoline and their physiologically acceptable salts.

In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that it additionally contains (C) one or more oxidation dye precursors from the group which is formed 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-diaminophenyl) propane, 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene, 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy 5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-hydroxyethyl) amino] - 4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4-ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine, 1-amino-3-bis ( 2-hydroxyethyl) a minobenzene, 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 / or their physiologically acceptable salts.

The agents according to the invention may in principle contain one or more coupler components from group (C) in a total amount of from 0.001 to 10.0% by weight, based on the total weight of the composition. However, the coupler (s) from the group (C) is preferably in the total amount of from 0.001 to 5.0% by weight, preferably from 0.025 to 4.5% by weight, more preferably from 0.05 to 4 , 0 wt .-% and particularly preferably from 0.1 to 3.5 wt .-% - based on the total weight of the composition - included.

In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that it contains one or more oxidation dye precursors from group (C) in a total amount of from 0.001 to 5.0% by weight, preferably from 0.025 to 4.5% by weight. %, more preferably from 0.05 to 4.0 wt .-% and particularly preferably from 0.1 to 3.5 wt .-% - based on the total weight of the composition - contains.

All of the abovementioned quantities for the total amount of the oxidation dye precursors (A) of the formula (I) in the composition according to the invention are based on the total weight of the compounds of the formula (I) in the color cream, ie in the storage-stable form Formulation before preparation of the application mixture and before mixing with a second, oxidizing agent-containing component.

All of the abovementioned quantities for the total amount of the oxidation dye precursors (B) in the composition according to the invention relate to their total weight in the color cream, i. in the storage stable formulation prior to preparation of the application mixture and prior to mixing with a second, oxidant-containing component.

All of the abovementioned quantities for the total amount of the oxidation dye precursors (C) in the composition according to the invention relate to their total weight in the color cream, i. in the storage stable formulation prior to preparation of the application mixture and prior to mixing with a second, oxidizing agent-containing component.

The agents according to the invention may additionally 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, triarylmethane dyes 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 according to 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), HC Blue No. 16, Basic Brown 16, Basic Brown 16, Basic Brown 17, 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.

The agents according to the invention may also contain naturally-analogous dyes in addition to the compound or compounds of the formula (I). 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.

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.

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.

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 brightening 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 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 separately prepared containers and wherein a container is a colorant (K1) which contains in a cosmetic carrier at least one oxidation dye precursor (A) according to formula (I), and a further container containing an oxidizing agent preparation (K2) containing at least one oxidizing agent.

Preferably, products containing the agents according to the invention are accordingly packaged as multicomponent packaging units (kit-of-parts) containing
K1: a first component which is a previously described inventive agent (containing at least one oxidation dye precursor (A) according to formula (I)), and
K2: a second component which is an oxidizer preparation.

Shortly before use, K1 and K2 are mixed together to form the ready-to-use colorant.

The agents (K1) and (K2) can be mixed together, for example, in a mixing ratio of 1: 4 to 4: 1. In particular, mixing ratios of 1: 2 to 2: 1 are usual, the mixing ratios in each case referring to the ratio of the amounts by weight of (K1) and (K2) (eg 200 g of the agent (K1) can be mixed with 100 g of the agent (K2). are mixed, resulting in a mixing ratio of 2: 1).

The oxidizing agent preparation (K2) 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.

Preferably, the amount of oxidizing agent in the ready-to-use agent is 0.5 to 12% by weight, preferably 2 to 10% by weight, more preferably 3 to 6% by weight (calculated as 100% H ₂ O ₂ ), respectively 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 for. For example, certain enzymes, iodides, quinones or metal ions.

For sufficient swelling of the keratin fibers, the ready-to-use oxidative colorant is preferably adjusted to an alkaline pH. The dyeing processes on keratin fibers also usually take place in an alkaline medium. However, in order to preserve the keratin fibers as well as the skin as much as possible, the setting of too high a pH value is not desirable. Therefore, it is preferred that the pH of the ready-to-use agent is from 8.0 to 10.5, more preferably from 8.7 to 10.3, even more preferably from 9.0 to 10.2, and most preferably from 9.2 to 10.1. The pH values given are values measured at a temperature of 22 ° C with a glass electrode.

The alkalizing agents which can be used according to the invention for adjusting the preferred pH can be selected from the group consisting of ammonia, alkanolamines, basic amino acids, and inorganic alkalizing agents such as (earth) alkali metal hydroxides, (earth) alkali metal metasilicates, (alkaline) alkaline metal phosphates and (alkaline) alkali metal hydrogen phosphates. Preferred inorganic alkalizing agents are sodium hydroxide, potassium hydroxide, sodium silicate and sodium metasilicate. Organic alkalizing agents which can be used according to the invention are preferably selected from monoethanolamine, 2-amino-2-methylpropanol and triethanolamine. The basic amino acids which can be used as alkalizing agents according to the invention are preferably selected from the group formed from arginine, lysine, ornithine and histidine, more preferably arginine. However, it has been found in the context of the investigations on the present invention that further preferred agents according to the invention are characterized in that they additionally contain an organic alkalizing agent. An embodiment of the first subject of the invention is characterized in that the agent additionally contains at least one alkalizing agent which is selected from the group consisting of ammonia, alkanolamines and basic amino acids, in particular ammonia, monoethanolamine and arginine or its compatible salts. Preferably, the or the alkalizing agents are compounded together with the oxidation dye precursors in the dyeing preparation (K1).

To further increase the whitening the coloring preparation (K1) and / or the oxidizing agent preparation (K2), in addition at least one SiO ₂ compound, such as silica or silicates, in particular water glass, be added. The SiO 2 compound may in this case be present in the dyeing preparation (K1) and / or in the oxidizing agent preparation (K2). It may be preferred according to the invention, the SiO ₂ compounds in amounts of 0.05 wt .-% to 15 wt .-%, more preferably in amounts of 0.15 wt .-% to 10 wt .-% and most preferably in amounts of from 0.2% by weight to 5% by weight, based in each case on the total weight of the dyeing preparation (K1) or on the total weight of the oxidizing agent preparation (K2). The amounts given in each case the content of the SiO ₂ compounds (without their water content) in the funds again.

The oxidative color-changing agents (i.e., the coloring preparation (K1) and / or the oxidizing agent preparation (K2)) may further contain additional active ingredients, auxiliaries and additives in order to improve the coloring performance and to adjust other desired properties of the agents.

Preferably, the ready-to-use colorants are provided as a liquid preparation and the agents therefore optionally additionally added a further surfactant, said surfactants depending on the field of application as surfactants or as emulsifiers: They are preferably anionic, zwitterionic, amphoteric and nonionic surfactants and emulsifiers selected.

Agents suitable according to the invention are characterized in that the agent additionally contains at least one anionic surfactant. Preferred anionic surfactants are fatty acids, alkyl sulfates, alkyl ether sulfates and ether carboxylic acids having 10 to 20 carbon atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

Agents suitable according to the invention are characterized in that the agent additionally contains at least one zwitterionic surfactant. Preferred zwitterionic surfactants are betaines, N-alkyl-N, N-dimethylammonium glycinates, N-acylaminopropyl-N, N-dimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines. A preferred zwitterionic surfactant is known by the INCI name Cocamidopropyl Betaine.

Agents suitable according to the invention are characterized in that the agent additionally contains at least one amphoteric surfactant. Preferred 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. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acylsarcosine.

Furthermore, it has proven to be advantageous if the agents contain other, nonionic surfactants. Preferred nonionic surfactants are alkyl polyglycosides and alkylene oxide adducts of fatty alcohols and fatty acids with 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.

The nonionic, zwitterionic or amphoteric surfactants are used in proportions of from 0.1 to 45% by weight, preferably from 1 to 30% by weight and very particularly preferably from 1 to 15% by weight, based on the total amount of ready-to-use agents.

The ready-to-use color-change agents may also contain at least one thickener. With regard to these thickeners, there are no fundamental restrictions. Both organic and purely inorganic thickening agents can be used.

Suitable thickeners are anionic, synthetic polymers, cationic synthetic polymers, naturally occurring thickeners such as nonionic guar gums, scleroglucan gums or xanthan gum, gum arabic, ghatti gum, karaya gum, tragacanth gum, carrageenan gum, agar-agar, locust bean gum, Pectins, alginates, starch fractions and derivatives such as amylose, amylopectin and dextrins, as well as cellulose derivatives such as methylcellulose, carboxyalkylcelluloses and hydroxyalkylcelluloses, nonionic fully synthetic polymers such as polyvinyl alcohol or polyvinylpyrrolidinone; and inorganic thickening agents, in particular phyllosilicates such as bentonite, especially smectites, such as montmorillonite or hectorite.

Furthermore, it has proved to be advantageous if the colorants, in particular if they additionally contain hydrogen peroxide, contain at least one stabilizer or complexing agent. Particularly preferred stabilizers are phenacetin, alkali benzoates (sodium benzoate) and salicylic acid. Furthermore, all complexing agents of the prior art can be used. Preferred complexing agents according to the invention are nitrogen-containing polycarboxylic acids, in particular EDTA and EDDS, and phosphonates, in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) and / or ethylenediamine tetramethylenephosphonate (EDTMP) and / or diethylenetriaminepentamethylenephosphonate (DTPMP) or their sodium salts.

Furthermore, the agents according to the invention may contain other active ingredients, auxiliaries and additives, for example nonionic polymers such as, for example, vinylpyrrolidinone / vinyl acrylate copolymers, polyvinylpyrrolidinone, vinylpyrrolidinone / vinyl acetate copolymers, polyethylene glycols and polysiloxanes; additional silicones, such as volatile or nonvolatile, straight-chain, branched or cyclic, crosslinked or uncrosslinked polyalkylsiloxanes (such as dimethicones or cyclomethicones), polyarylsiloxanes and / or polyalkylarylsiloxanes, in particular 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; 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; anionic polymers such as polyacrylic acids or crosslinked polyacrylic acids; Structurants such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example, lecithin and cephalins; Perfume oils, dimethylisosorbide and cyclodextrins; fiber structure improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose; Dyes for staining the agent; Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole; Amino acids and oligopeptides; Protein hydrolysates on animal and / or vegetable basis, as well as in the form of their fatty acid condensation products or optionally anionically or cationically modified derivatives; vegetable oils; Sunscreens and UV blockers; Active ingredients 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 or pseudoceramides; Vitamins, provitamins and vitamin precursors; Plant extracts; Fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; Swelling and penetration 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 and propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air.

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. The additional active ingredients and auxiliaries are preferably present in the agents according to the invention in amounts of from 0.0001 to 25% by weight, in particular from 0.0005 to 15% by weight, based in each case on the total weight of the dyeing preparation (K1) and / or the oxidizing agent preparation (K2) used.

The oxidation dye precursors (A) of the formula (I) can be dyed in particular with one or more oxidation dye precursors of the developer type (from the aforementioned group (B)) on keratinic fibers. The dyeings obtained in this way are characterized by a very good perspiration fastness.

worin
Y1, Y2 unabhängig voneinander für eine Gruppe R6R7N-, eine Hydroxygruppe, eine C₁-C₆-Alkylgruppe oder für eine Cyanogruppe stehen,
X für ein Sauerstoffatom (-O-), ein Schwefelatom (-S-) oder für eine Gruppe -NR8- steht,
R1, R2, R5 unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Hydroxy-C₂-C₆-alkylgruppe, eine Polyhydroxy-C₂-C₆-alkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine Cyanogruppe, eine C₁-C₆-Alkoxycarbonylgruppe, eine Nitrogruppe, eine Arylgruppe oder ein Halogenatom (Fluor, Chlor, Brom oder Jod) stehen,
R3, R4 unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Hydroxy-C₂-C₆-alkylgruppe, eine Polyhydroxy-C₂-C₆-alkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine Aminogruppe, eine Gruppe R9R10N-, eine Cyanogruppe, eine C₁-C₆-Alkoxy-carbonylgruppe, eine Nitrogruppe, eine Arylgruppe oder ein Halogenatom (Fluor, Chlor, Brom oder Jod) stehen,
R6, R7, R8, R9, R10 unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Hydroxy-C₂-C₆-alkylgruppe, eine Polyhydroxy-C₂-C₆-alkylgruppe oder eine Arylgruppe stehen,
mit der Maßgabe, dass mindestens einer der Reste aus der Gruppe Y1 und Y2 für eine Gruppe R6R7N- steht. A further subject of the present invention is therefore the use of an oxidation dye precursor of the formula (I) in the dyeing of keratinic fibers for producing dyeings having improved perspiration fastness,

wherein
Y1, Y2 independently of one another represent a group R6R7N-, a hydroxy group, a C ₁ -C ₆ -alkyl group or a cyano group,
X represents an oxygen atom (-O-), a sulfur atom (-S-) or a group -NR8-,
R _1, R 2, R 5 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a hydroxy-C ₂ -C ₆ -alkyl group, a polyhydroxy-C ₂ -C ₆ -alkyl group , a hydroxy group, a C ₁ -C ₆ -alkoxy group, a cyano group, a C ₁ -C ₆ -alkoxycarbonyl group, a nitro group, an aryl group or a halogen atom (fluorine, chlorine, bromine or iodine),
R 3, R 4 independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a hydroxy C ₂ -C ₆ alkyl group, a polyhydroxy C ₂ -C ₆ alkyl group, a Hydroxy group, a C ₁ -C ₆ -alkoxy group, an amino group, a group R 9 R 10 N-, a cyano group, a C ₁ -C ₆ -alkoxycarbonyl group, a nitro group, an aryl group or a halogen atom (fluorine, chlorine, bromine or iodine) stand,
R6, R7, R8, R9, R10 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a hydroxy-C ₂ -C ₆ -alkyl group, a polyhydroxy-C ₂ - C ₆ alkyl group or an aryl group,
with the proviso that at least one of the radicals from the group Y1 and Y2 stands for a group R6R7N-.

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

Examples

1. Syntheses

Synthesis Example 1: Synthesis of 4-N- (3-aminophenyl) benzene-1,2,4-triamine trihydrochloride (K1)

1.1. Synthesis of 3-fluoroacetanilide

3-Fluoroaniline (50.0 g, 0.45 mol) was initially charged at room temperature and acetic anhydride (115.0 ml, 1.04 mol, 2.3 eq.) Was slowly added dropwise with stirring, so that the temperature did not exceed 50 ° C. After completion of the addition, the mixture was stirred for 3 h at 50 ° C and the mixture was then poured onto ice-water. The precipitate was filtered off and washed with water. After drying, 3-fluoroacetanilide (53.1 g, 0.35 mol, 77%) was obtained as a white solid.
¹ H-NMR (300 MHz, d ₆ -DMSO): δ = 2.08 (s, 3H, Me), 6.83 (t, 1H, 4-H), 7.29 (m, 2H, 5-H, 6-H) , 7.61 (d, 1H, 2-H), 10.15 (s, 1H, NH).
¹³ C-NMR (125 MHz, d ₆ -DMSO): δ = 23.8 (Me), 105.5 (d, 2-C), 109.4 (d, 4-C), 114.7 (6-C), 130.2 (5- C), 141.0 (d, 1-C), 161.0 / 163.4 (d, 3-C), 168.7 (C = O). 1.2. Synthesis of 5-fluoro-2-nitroaniline

3-Fluoroacetanilide (53.0 g, 0.35 mol) was dissolved in conc. Sulfuric acid (175.0 ml) at 0-5 ° C dissolved. With stirring, a solution of nitrating acid (175.0 ml of concentrated sulfuric acid and 28.0 ml of concentrated nitric acid) was slowly added dropwise so that the temperature did not exceed 5 ° C. After the addition was stirred for 2 h at 5 ° C and the mixture was then poured onto ice water. The mixture was extracted with ethyl acetate and the organic phase was concentrated. The residue was half-concentrated in 500 ml. Hydrochloric acid heated for one hour at reflux, neutralized after cooling with potassium carbonate and the mixture extracted again with ethyl acetate. The combined organic phases were concentrated and the residue was purified by steam distillation. From the steam distillate, it was possible to extract 5-fluoro-2-nitroaniline as a yellow solid (5.0 g, 0.03 mol, 8%) by extraction with ethyl acetate and renewed concentration.
¹ H-NMR (300 MHz, d ₆ -DMSO): δ = 6.46 (t, 1H, 4-H), 6.74 (d, 1H, 2-H), 7.49 (br s, 2H, NH ₂ ), 8.04 (dd, 1H, 5-H) 1.3. Synthesis of 1-N- (3-aminophenyl) -4-nitrobenzene-1,4-diamine

5-Fluoro-2-nitroaniline (5.0 g, 0.03 mol) was melted together with 1,3-diaminobenzene (3.5 g, 0.03 mol) and potassium carbonate (4.4 g, 0.03 mol) with stirring and stirred at 160 ° C for 3 h. After cooling, the mixture was mortared and boiled with water. The residue was triturated with ethanol, filtered and the residue was dried in vacuo. 1-N- (3-Aminophenyl) -4-nitrobenzyl-1,4-diamine (6.0 g, 0.02 mol, 76%) was obtained as a black solid. 1.4. Synthesis of 4-N- (3-aminophenyl) benzene-1,2,4-triamine trihydrochloride (K1)

1-N- (3-Aminophenyl) -4-nitrobenzyl-1,4-diamine (6.0 g, 0.02 mol) was slurried together with the catalyst Pd / C (0.2 g) in ethanol (400 ml) and treated with 1 bar hydrogenated hydrogen. After completion of the reaction, the suspension in 6 M aq. HCl, the residue was filtered off and the filtrate was concentrated in vacuo. The residue was dried in vacuo.
4-N- (3-Aminophenyl) benzene-1,2,4-triamine (3.4 g, 0.01 mol, 39%) was obtained as a black solid.
¹ H-NMR (300 MHz, d ₆ -DMSO): δ = 6.33 (d, 1H, Ar-H), 6.45-6.55 (m, 2H, Ar-H), 6.78 (dd, 1H, Ar-H) , 7.11 (d, 1H, Ar-H), 7.33 (m, 2H, Ar-H).
¹³ C-NMR (125 MHz, d ₆ -DMSO): δ = 98.3 (ArCH), 103.5 (ArCH), 104.6 (ArCH), 107.5 (ArCH), 115.5 (ArCH), 117.0 (ArCH), 130.6 (ArC) , 131.2 (ArC), 141.9 (ArC), 148.7 (ArC), 149.7 (ArC).

Synthesis Example 2: Synthesis of 4-N- (3-aminophenyl) -5-methylbenzene-1,2,4-triamine trihydrochloride (K2)

2.1. Synthesis of N- (3-fluoro-4-methylphenyl) acetamide

3-Fluoro-4-methylaniline (25.0 g, 0.20 mol) was initially charged at room temperature and acetic anhydride (27.5 ml, 0.25 mol, 1.2 eq.) Was slowly added dropwise with stirring, so that the temperature did not exceed 15 ° C. After the addition was stirred for 3 h at room temperature, the resulting precipitate was filtered off and washed with toluene. After drying, N- (3-fluoro-4-methyl-phenyl) -acetamide (22.3 g, 0.13 mol, 65%) was obtained as a white solid.
¹ H-NMR (300 MHz, d ₆ -DMSO): δ = 2.08 (s, 3H, Me), 2.17 (s, 3H, Me), 7.18 (s, 1H, 2-H), 7.52 (d, 1H , 6-H), 7.58 (d, 1H, 5-H).
¹³ C-NMR (125 MHz, d ₆ -DMSO): δ = 13.6 (Me), 23.8 (Me), 105.5 (d, 2-C), 114.4 (6-C), 118.2 (d, 4-C) , 131.2 (5-C), 138.8 (d, 1-C), 159.2 / 161.4 (d, 3-C), 168.4 (C = O). 2.2. Synthesis of 5-fluoro-4-methyl-2-nitroaniline

N- (3-Fluoro-4-methylphenyl) acetamide (22.0 g, 0.13 mol) was dissolved in conc. Sulfuric acid (125.0 ml) at 0-5 ° C dissolved. While stirring, 11.0 ml of conc. Sulfuric acid slowly added dropwise so that the temperature did not exceed 5 ° C. After completion of the addition, stirring was continued overnight at room temperature and the mixture was subsequently poured into ice-water. The precipitate was filtered off and washed with water. The residue was semi-concentrated in 150 ml. Hydrochloric acid heated for 5 h at reflux, neutralized after cooling with sodium hydroxide solution and the mixture extracted with ethyl acetate. The combined organic phases were concentrated to give 5-fluoro-4-methyl-2-nitroaniline as a white solid (4.7 g, 0.03 mol, 21%).
¹ H-NMR (300 MHz, d ₆ -DMSO): δ = 2.13 (s, 3H, Me), 6.75 (d, 1H, 6-H,) 7.97 (d, 1H, 3-H).
¹³ C NMR (125 MHz, d ₆ -DMSO): δ = 13.2 (Me), 103.1 (d, 6-C), 113.0 (4-C), 127.1 (d, 1-C), 128.2 (3) C), 146.7 (2-C), 163.8 / 166.3 (d, 5-C). 2.3. Synthesis of N3- (3-aminophenyl) -4-methyl-6-nitrobenzene-1,3-diamine

5-Fluoro-4-methyl-2-nitroaniline (4.5 g, 26.5 mmol) was melted together with 1,3-diaminobenzene (2.9 g, 26.5 mmol) and potassium carbonate (3.7 g, 26.5 mmol) with stirring and 160 h for 3 h ° C stirred. After cooling, the mixture was mortared and boiled with water. The residue was triturated with ethanol, filtered and the residue was dried in vacuo. N3- (3-Aminophenyl) -4-methyl-6-nitrobenzene-1,3-diamine (4.0 g, 15.5 mmol, 58%) was obtained as a black solid. 2.4. Synthesis of 4-N- (3-aminophenyl) -5-methylbenzene-1,2,4-triamine trihydrochloride (K2)

1-N- (3-Aminophenyl) -4-nitrobenzyl-1,4-diamine (4.0 g, 15.5 mmol) was slurried together with the catalyst Pd / C (0.2 g) in ethanol (400 ml) and treated with 1 bar hydrogenated hydrogen. After completion of the reaction, the suspension in 6 M aq. HCl, the residue was filtered off and the filtrate was concentrated in vacuo. The residue was dried in vacuo.
This gave 4-N- (3-aminophenyl) benzene-1,2,4-triamine (2.1 g, 6.22 mmol 40%) as a black solid.
¹ H-NMR (300 MHz, d ₆ -DMSO): δ = 2.13 (s, 3H, Me), 6.70 (d, 2H, Ar-H), 7.12 (d, 2H, Ar-H), 7.38 (i.e. , 1H, Ar-H), 7.58 (m, 1H, Ar-H).
¹³ C-NMR (125 MHz, d ₆ -DMSO): δ = 13.7 (Me), 104.3 (ArCH), 104.6 (ArCH), 113.9 (ArC), 116.7 (ArC) 117.6 (ArCH), 122.1 (ArCH), 126.1 (ArCH), 131.3 (ArCH), 134.4 (2C, ArC), 158.9 (ArC), 161.1 (ArC).

2. colorations

The following color creams were produced: Hydrenol D ^{® 1} 8.5% by weight Lorol® ^® tech. ² 2.0% by weight Texapon.RTM ^® NSO ³ 20.0% by weight Dehyton ^® K ⁴ 12.5% by weight Eumulgin ^® B2 ⁵ 0.75% by weight sodium 1.0% by weight ammonium sulfate 1.0% by weight developer component 3 mmol Kupplerkomponente 3 mmol water ad 100 ¹ C _16-18 fatty alcohol (INCI name: Cetearyl alcohol) (Cognis)
² C _12-18 fatty alcohol (INCI name: Coconut alcohol) (Cognis)
³ lauryl ether sulfate, sodium salt (about 27.5% active ingredient, INCI name: Sodium Laureth Sulfate) (Cognis)
⁴ N, N-dimethyl-N- (C _8-18 -cocoamidopropyl) -ammonium acetobetaine (about 30% active ingredient, INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis)
⁵ cetylstearyl alcohol with approx. 20 EO units (INCI name: Ceteareth-20) (Cognis)

Hydrenol D and Lorol techn. were melted together with Texapon NSO, 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 was dissolved in a further portion of the indicated amount of water with heating and added with stirring. The coupler of the invention 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 dyeing cream thus obtained was mixed in a ratio of 1: 1 with the following developer dispersion having a hydrogen peroxide content of 6%. dipicolinic 0.1% by weight sodium pyrophosphate 0.03% by weight Turpinal SL ^{® 6} 1.50% by weight Texapon ^® N28 ⁷ 2.00% by weight Acrysol ^® 22 ⁸ 0.60% by weight Hydrogen peroxide, 50% 6.00% by weight Sodium hydroxide, 45% 0.80% by weight water ad 100% by weight ⁶ 1-Hydroxyethane-1,1-diphosphonic acid (about 58-61% active ingredient content, INCI name: Etidronic Acid, Aqua (Water)) (Solutia)
⁷ lauryl ether sulfate sodium salt (at least 26.5% active ingredient content, INCI name: Sodium Laureth Sulfate) (Cognis)
⁸ acrylic polymer (about 29.5-30.5% solids in water, INCI name: Acrylates / Steareth-20 Methacrylate Copolymer)

For the dyeing process, 4 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. K1: colorations with 4-N- (3-aminophenyl) benzene-1,2,4-triamine trihydrochloride (K1) developer pimp Nuance / color intensity 2,5-diaminotoluene, sulphate K1 blue-gray +++ 2,4,5,6-tetraaminopyrimidine, sulfate K1 bronze green ++ 2- (2,5-diminophenyl) ethanol, sulfate K1 dark turquoise +++ 4,6-diamino-1- (2-hydroxyethyl) pyrazole, sulfate K1 port wine red +++ N, N-bis (2-hydroxyethyl) -p-phenylenediamine K1 dark turquoise +++ +++ high intensity
++ medium intensity
+ low intensity K2: colorations with 4-N- (3-aminophenyl) -5-methylbenzene-1,2,4-triamine trihydrochloride developer pimp Nuance / color intensity 2,4,5,6-tetraaminopyrimidine, sulfate K2 olive ++ 2- (2,5-diminophenyl) ethanol, sulfate K2 olive-gray ++ p-phenylenediamine K2 black and blue +++ +++ high intensity ++ medium intensity + low intensity

Claims (10)

Agent for the oxidative color change of keratinic fibers, in particular human hair, containing in a cosmetic carrier (A) at least one oxidation dye precursor of the formula (I) and / or its physiologically acceptable salt,

wherein Y1, Y2 independently of one another are a group R6R7N-, a hydroxy group, a C ₁ -C ₆ -alkyl group or a cyano group, X is an oxygen atom (-O-), a sulfur atom (-S-) or a group -NR 8 -, R _1, R 2, R 5 independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a hydroxy-C ₂ -C ₆ -alkyl group, a polyhydroxy-C ₂ -C ₆ alkyl group, a hydroxy group, a C ₁ -C ₆ alkoxy group, a cyano group, a C ₁ -C ₆ alkoxy-carbonyl group, a nitro group, an aryl group or a halogen atom (fluorine, chlorine, bromine or iodine) , R3, R4 represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a hydroxy-C ₂ -C ₆ alkyl group independently of one another, a polyhydroxy-C ₂ -C ₆ alkyl group, a hydroxy group, a C ₁ -C ₆ alkoxy group, an amino group, a group R 9 R 10 N-, a cyano group, a C ₁ -C ₆ alkoxycarbonyl group, a nitro group, an aryl group or R6, R7, R8, R9, R10 independently represent a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a hydroxyC C ₂ -C ₆ alkyl group, a polyhydroxy C ₂ -C ₆ alkyl group or an aryl group, with the proviso that at least one of the radicals from the group Y1 and Y2 is a group R6R7N-. Composition according to Claim 1, characterized in that it contains at least one oxidation dye precursor of the formula (I) in which R _1, R 2 and R 5 independently of one another represent hydrogen or a C ₁ -C ₆ -alkyl group. Composition according to one of claims 1 to 2, characterized in that it contains at least one oxidation dye precursor of the formula (I), in which R3 and R4 independently of one another represent hydrogen, a C ₁ -C ₆ -alkyl group, an amino group or a nitro group , Composition according to one of claims 1 to 3, characterized in that it contains at least one oxidation dye precursor of formula (I), in which X represents an oxygen atom (-O-) or a group -NR8-, wherein R8 represents a hydrogen atom , Agent according to one of claims 1 to 4, characterized in that it contains at least one oxidation dye precursor of formula (I), in which Y1 is an amino group and / or Y2 is an amino group. Composition according to one of claims 1 to 5, characterized in that it contains at least one oxidation dye precursor of the formula (I), in which - Y1 stands for a hydroxy group and Y2 stands for an amino group or - Y1 stands for an amino group and Y2 stands for a hydroxy group stands. Composition according to one of claims 1 to 6, characterized in that it contains at least one oxidation dye precursor of the formula (I), in which - R1 is a hydrogen atom or a methyl group, - R2 is a hydrogen atom or a methyl group, - R3 is represents a hydrogen atom - R 4 represents a hydrogen atom, a methyl group, an amino group or a nitro group, and - R 5 represents a hydrogen atom or a methyl group. Agent according to one of claims 1 to 7, characterized in that it contains at least one oxidation dye precursor of the formula (I) in which - Y1 is an amino group - Y2 is an amino group and - R4 stands for an amino group Composition according to one of claims 1 to 8, characterized in that it contains at least one oxidation dye precursor of formula (I), which is selected from - 1-N- (3-aminophenyl) benzene-1,3-diamine - 3 - [( 3-aminophenyl) amino] phenol - 3- (3-aminophenoxy) aniline - 3- (3-aminophenoxy) phenol - 1-N- (3-aminophenyl) -4-methylbenzene-1,3-diamine - 5 - [( 3-aminophenyl) amino] -2-methylphenol - 3 - [(3-amino-4-methylphenyl) amino] phenol - 5- (3-aminophenoxy) -2-methylaniline - 3- (3-amino-4-methylphenoxy) phenol - 5- (3-aminophenoxy) -2-methylphenol - 1-N- (3-amino-4-methylphenyl) -4-methylbenzene-1,3-diamine - 5 - [(3-amino-4-methylphenyl) amino] -2-methylphenol - 5- (3-amino-4-methylphenoxy) -2-methylaniline - 5- (3-amino-4-methylphenoxy) -2-methylphenol-1-N- (3-aminophenyl) -4 nitrobenzene-1,3-diamine - 4-N- (3-aminophenyl) benzene-1,2,4-triamine - 5- (3-aminophenoxy) -2-nitroaniline - 4- (3-aminophenoxy) benzene-1 , 2-diamine - 3 - [(3-amino-4-nitrophenyl) amino] phenol-3 - [(3,4-diaminophenyl) am ino] phenol - 5 - [(3-aminophenyl) amino] -2-nitrophenol - 2-amino-5 - [(3-aminophenyl) amino] phenol-1-N- (3-amino-4-nitrophenyl) -5 -methylbenzene-1,3-diamine - 4-N- (3-amino-5-methylphenyl) benzene-1,2,4-triamine - 3- (3-amino-4-nitrophenoxy) -5-methylaniline-4- (3-Amino-5-methylphenoxy) benzene-1,2-diamine - 3 - [(3-amino-4-nitrophenyl) amino] -5-methylphenol-3 - [(3,4-diaminophenyl) amino] -5 -methylphenol - 5 - [(3-amino-5-methylphenyl) amino] -2-nitrophenol - 2-amino-5 - [(3-amino-5-methylphenyl) amino] phenol-4-N- (3-aminophenyl ) -5-methylbenzene-1,2,4-triamine and / or their physiologically acceptable salts. Agent according to one of claims 1 to 9, characterized in that it comprises (A) one or more oxidation dye precursors of formula (I) in a total amount of 0.001 to 5.0 wt .-%, preferably from 0.1 to 4.5 wt .-%, more preferably from 0.2 to 4.0 wt .-% and particularly preferably from 0.3 to 3.5 wt .-% - based on the total weight of the composition - contains.