DE102011086727A1 - Agent useful for producing intensive hair colorants for dyeing and optionally simultaneous brightening of keratin fibers, preferably human hair, comprises at least one azanium compound in a cosmetic carrier - Google Patents

Abstract

Agent comprises at least one azanium compound (I) in a cosmetic carrier. Agent comprises at least one azanium compound of formula (I) in a cosmetic carrier. R1, R2 : H, 1-6C alkyl, 2-6C alkenyl, 2-6C hydroxyalkyl, OH, 1-6C-alkoxy, amino, 1-6C alkylamino, 1-6C alkylamino or halo; R3 : H, 1-6 alkyl, 2-6C alkenyl, 2-6C hydroxyalkyl, 2-6C polyhydroxyalkyl, 1-6C alkoxy-2-6C-alkyl, cyano-1-6C-alkyl or aryl-1-6C-alkyl; n : 2-6; Y1 : cationic nitro group of formula (II) or (III); R4 : 1-6C alkyl, 2-6C alkenyl, 2-6C hydroxyalkyl, 2-6C polyhydroxyalkyl, 1-6C alkoxy-2-6C-alkyl, cyano-1-6C-alkyl or aryl-1-6C-alkyl; m : 2-6; and X ->anion, preferably halide, hydrogensulfate, half sulfate, benzene sulfonate, p-toluene sulfonate, acetate, citrate, lactate, half tartrate or trifluoromethanesulfonate. An independent claim is also included for azanium compound (I). [Image] [Image].

Description

The present invention relates to means for dyeing and optionally simultaneous whitening of keratin-containing fibers, in particular human hair, containing certain trimeric nitro dyes. Furthermore, the invention relates to the use of these agents for producing colorfast hair dyeings and the dyes themselves.

For the dyeing of keratinic fibers, either direct dyes or oxidation dyes are generally used. Although intensive dyeings with good fastness properties can be obtained with oxidation dyes, the development of the color is generally carried out under the influence of oxidizing agents such. H ₂ O ₂ , which in some cases may result in damage to the fiber. Furthermore, some oxidation dye precursors or certain mixtures of oxidation dye precursors may have a sensitizing effect on persons with sensitive skin. Direct dyes are applied under gentler conditions. Their disadvantage, however, is that the dyeings often have only insufficient fastness properties, especially in hair washing, but also against external influences, such as sunlight or reactive environmental chemicals, such as swimming pool water.

A particular challenge for hair dyeing with direct dyes is the uniform coloring of frequently pretreated hair, such as bleached or permed hair, in which the fiber has a very different degree of previous damage in the different lengths or differently treated areas. During the dyeing itself, the dye can show uneven dyeing behavior on differently damaged hair, but also by repeated hair washing, the dyes in the different hair areas can be washed out to different extents, whereby a nonuniform and thus undesirable color result is achieved.

The object of the present application is therefore to provide colorants for keratinic fibers, in particular human hair, which have good performance properties in terms of color depth and fastness properties, in particular light fastness, rubfastness and wash fastness, as well as perspiration and cold wave fastness. Finally, it is particularly desirable to provide colorants with good leveling power. In the case of simultaneous use with oxidation dyes and / or oxidants, the substantive dyes should have sufficient stability to H ₂ O ₂ and not lose their positive fastness and dyeing properties. In addition, as bright and intense colors as possible should be achieved.

For the production of color-stable and natural-looking nuances, the use of a dye alone is not sufficient, therefore, in the development of nuances usually different dyes are used in a dyeing product.

Depending on the desired degree of shade, different types of dye can be combined with each other. Low stain colorants typically combine various substantive dyes. If more durable dyeings are desired, the skilled artisan usually uses oxidation dye precursors. These are often combined with substantive dyes for shade.

In most cases, however, a dye can not be combined equally well with all other dyes. Thus, in combination with a first dye, the dye can result in intense and colorfast nuances while providing much less satisfactory staining results in combination with a second dye.

In modern production processes, complexity reduction is an important factor in optimizing the manufacturing process. In this case, it is important to minimize the number of raw materials used in the production of different formulations and thus to make the entire production process more effective. With regard to the production of agents for coloring keratinic fibers, this means that it is advantageous if it is possible to cover the widest possible range of shades with the lowest possible portfolio of different dyes. The nuances created in this way must fully meet all requirements that the user places on the product with regard to the authenticity properties.

Therefore, it is a further object of the present invention to provide novel dyes that can be very well combined with a large number of other dyes or dye precursors and provide in all combinations attractive shades with excellent fastness properties.

It has surprisingly been found that certain trimeric nitro dyes fulfill the task described above in an outstanding manner. In colorations intensive, color-stable nuances were obtained. The trimeric nitro dyes can be used very well in combination with a wide range of other dyes and thereby provide dyeings with very good fastness properties.

Out DE 1941376 are known manufacturing methods for certain dimeric nitro dyes for dyeing industrial fibers and textiles. FR 1540423 A1 describes basic, dimeric dyes, which may also have 2 nitroaryl cores. The FR 2864964 describes cationic trimeric azo dyes and their use in hair dyes. Cationic trimeric nitro dyes have hitherto not been described either in agents for dyeing keratinic fibers or as compounds themselves.

in der
R1, R2 unabhängig voneinander für Wasserstoff, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine Aminogruppe, eine C₁-C₆-Alkylaminogruppe, eine Di-C₁-C₆-alkylaminogruppe oder Halogen stehen,
R3 für Wasserstoff, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine Cyano-C₁-C₆-alkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe steht,
n für eine ganze Zahl von 2 bis 6 steht,
Y für eine kationische Gruppierung der Formeln (II) oder (III) steht,

worin
R4 für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine Cyano-C₁-C₆-alkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe steht,
m für eine ganze Zahl von 2 bis 6 steht und
X- für ein physiologisch verträgliches Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, Benzolsulfonat, p-Toluolsulfonat, Acetat, Citrat, Lactat, ½ Tartrat oder Trifluormethansulfonat steht. A first subject of the present invention is an agent for dyeing and optionally simultaneously lightening keratinic fibers, in particular human hair, comprising in a cosmetic carrier at least one compound of the formula (I),

in the
R _1, R ₂ independently of one another represent hydrogen, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, an amino group, a C ₁ -C ₆ -alkylamino group, a di-C ₁ -C ₆ -alkylamino group or halogen,
R 3 is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ hydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy-C C ₂ -C ₆ -alkyl group, a cyano-C ₁ -C ₆ -alkyl group or an aryl-C ₁ -C ₆ -alkyl group,
n is an integer from 2 to 6,
Y is a cationic grouping of the formula (II) or (III),

wherein
R 4 is a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₂ - C ₆ alkyl group, a cyano C ₁ -C ₆ alkyl group or an aryl C ₁ -C ₆ alkyl group,
m stands for an integer from 2 to 6 and
X- is a physiologically acceptable anion, preferably halide, hydrogen sulfate, ½ sulfate, benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, ½ tartrate or trifluoromethanesulfonate.

Keratinic fibers, keratin-containing fibers or keratin fibers are understood to mean furs, wool, feathers and, in particular, human hair. Although the compositions according to the invention are primarily suitable for whitening keratin fibers, in principle there is nothing to prevent their use in other fields as well.

The term "dyeing of keratin fibers" used in the invention includes any form of color change of the fibers. In particular, color changes encompassed by the terms tinting, bleaching, oxidative dyeing, semi-permanent dyeing, permanent dyeing and temporary dyeing are included. Explicitly encompassed according to the invention are color changes which have a lighter color result in comparison to the starting color, for example coloring bleaching operations.

The agents according to the invention contain the compounds of the formula (I) in a cosmetic carrier. This cosmetic carrier is preferably aqueous, alcoholic or aqueous-alcoholic. For the purpose of hair treatment, such carriers are for example creams, emulsions, gels or surfactant-containing foaming solutions, such as shampoos, foam aerosols or other preparations which are suitable for use on the hair. But it is also possible to provide for storage a powdery or tablet-like formulation. This is then mixed before use in an aqueous solvent or with organic solvents or with mixtures of water and organic solvents to obtain the application mixture. For the purposes of the invention, an aqueous carrier contains at least 40% by weight, in particular at least 50% by weight, of water. For the purposes of the present invention, aqueous-alcoholic carriers are to be understood as meaning water-containing compositions 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 other organic solvents, such as, for example, 4-methoxybutanol, ethyldiglycol, 1,2-propylene glycol, n-propanol, n-butanol, n-butylene glycol, glycerol, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether. Preference is given to all water-soluble organic solvents. Preferred agents according to the invention are characterized in that they additionally comprise a non-aqueous solvent, preferred agents according to the invention containing the solvent in a concentration of 0.1 to 30% by weight, preferably in a concentration of 1 to 20% by weight, very particularly preferably in a concentration of 2 to 10 wt .-%, each based on the agent.

The substituents R _{1 to} R 4 of the compound of the formula (I) are illustrated below by way of example: examples of a C ₁ -C ₆ -alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of a C ₂ -C ₆ -alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C ₂ -C ₆ -alkenyl radicals are vinyl and allyl. Preferred examples of a C ₁ -C ₆ hydroxyalkyl group include hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyhexyl; a 2-hydroxyethyl group is particularly preferred. Examples of a C ₂ -C ₆ polyhydroxyalkyl group are the 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group and the 2,4-dihydroxybutyl group. C ₁ -C ₆ -alkoxy groups preferred according to the invention are the methoxy or the ethoxy group. As examples of a C ₁ -C ₆ -alkylamino group, mention may be made of methylamino, ethylamino, n-propylamino, n-butylamino and isopropylamino. Examples of the di-C ₁ -C ₆ -alkylamino group are dimethylamino, diethylamino, dipropylamino and dibutylamino, with dimethylamino and diethylamino being preferred. Examples of halogen atoms are F, Cl, Br or I atoms, with Br or Cl atoms being very particularly preferred. Preferred examples of C ₁ -C ₆ -alkoxy-C ₂ -C ₆ -alkyl groups according to the invention are the methoxyethyl, ethoxyethyl, methoxypropyl, methoxybutyl, ethoxypropyl, ethoxybutyl and methoxyhexyl groups. Preferred examples of a cyano-C ₁ -C ₆ -alkyl group are a cyanomethyl and a 2-cyanoethyl group. Preferred examples of aryl-C ₁ -C ₆ -alkyl groups are benzyl, 1-phenethyl and 2-phenylethyl.

Dyes of the formula (I) in which R _{1 and} R 2, independently of one another, are hydrogen, a C ₁ -C ₆ -alkyl group, an amino group, a C ₁ -C ₆ -alkylamino group or a di-C ₁ -C ₆ -alkylamino group, provide particularly intensive staining results and are therefore preferred.

A preferred embodiment is an agent for dyeing and optionally simultaneous lightening of keratin fibers, which is characterized in that it contains at least one compound of formula (I), regardless of in which R1 and R2 represent hydrogen, a C ₁ -C ₆ Alkyl group, an amino group, a C ₁ -C ₆ -alkylamino group or a di-C ₁ -C ₆ -alkylamino group.

Particularly preferably, one of the two radicals is selected from R _{1 and} R 2 is hydrogen and the other of the two radicals selected from R _{1 and} R 2 is hydrogen, a C ₁ -C ₆ -alkyl group, an amino group, a C ₁ -C ₆ -alkylamino group or a Di-C ₁ -C ₆ -alkylamino group.

Particularly preferably, R 1 is hydrogen and R 2 is hydrogen, a methyl group, an amino group, a methylamino group or a dimethylamino group.

Furthermore, good dyeing results are achieved especially with the means containing at least one compound of formula (I) in which R3 is hydrogen or a C ₁ -C ₆ alkyl group, preferably hydrogen or a methyl group, more preferably hydrogen.

Compounds of formula (I) in which n is the number 2 or 3 are also preferred.

A further preferred embodiment is therefore an agent for dyeing and optionally simultaneous lightening of keratinic fibers, which is characterized in that it contains at least one compound of formula (I), in which R3 is hydrogen and n is the number 2 or 3.

Compounds of formula (I) in which Y represents the cationic moiety (II) are synthetically the most accessible. In addition, dyeings with particularly high brilliance can be produced with these compounds.

A further preferred embodiment is therefore an agent for dyeing and optionally simultaneously lightening keratinic fibers, which is characterized in that it contains at least one compound of formula (I) in which Y is the cationic moiety (II).

Compounds of the formula (I) in which R 4 is a C ₁ -C ₆ -alkyl group or a C ₂ -C ₆ -alkenyl group have likewise proven to be particularly suitable for achieving the object of the invention and are therefore preferred. R4 is particularly preferably a C ₁ -C ₆ -alkyl group, in particular a methyl group, an ethyl group or a propyl group.

A further preferred embodiment is therefore an agent for dyeing and optionally simultaneous lightening of keratinic fibers, which is characterized in that it contains at least one compound of formula (I) in which R4 is a C ₁ -C ₆ alkyl group or a C C ₂ -C ₆ alkenyl group, preferably a C ₁ -C ₆ -alkyl group, more preferably a methyl group, ethyl group or propyl group.

m is preferably the numbers 2 or 3.

The dyestuffs of the formula (I) according to the invention are trimeric aromatic nitro compounds, it being possible for the nitro groups on the phenyl rings in each case to stand in the ortho, meta or para position relative to the amino group carrying the radical R3.

According to the invention, it is preferred if the nitro groups are in each case in the ortho or in the para position relative to the amino groups carrying the radical R3.

More preferably, the compounds of the formula (I) according to the invention are symmetrical compounds in which the nitro groups on all three rings are either in the ortho position or in the para position to the amino groups carrying the radical R3. In this context, it is also preferred if the radicals R1 and R2 occupy the same positions for all three rings.

Selected combinations of the substituents R 1 to R 4 lead to exceptionally intense dyeing results for compounds of the formula (I) and thus represent a particularly preferred embodiment. Very particularly advantageous are agents which contain at least one compound of the formula (I) in which R 1 and R 3 R 2 is hydrogen, R 2 is hydrogen, a methyl group, a methylamino group or a dimethylamino group, Y is a cationic grouping of the formula (II) and R 4 is a methyl group, an ethyl group or a propyl group.

• – Salzen des Methyltris({3-[(2-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Ethyltris({3-[(2-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Propyltris({3-[(2-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Allyltris({3-[(2-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Methyltris({2-[(2-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Ethyltris({2-[(2-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Propyltris({2-[(2-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Allyltris({2-[(2-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Methyltris({3-[(4-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Ethyltris({3-[(4-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Propyltris({3-[(4-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Allyltris({3-[(4-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Methyltris({2-[(4-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Ethyltris({2-[(4-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Propyltris({2-[(4-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Allyltris({2-[(4-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Methyltris({3-[(3-methyl-4-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Ethyltris({3-[(3-methyl-4-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Propyltris({3-[(3-methyl-4-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Allyltris({3-[(3-methyl-4-nitrophenyl)amino]propyl})azaniums,
  
• – Salzen des Methyltris({2-[(3-methyl-4-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Ethyltris({2-[(3-methyl-4-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Propyltris({2-[(3-methyl-4-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Allyltris({2-[(3-methyl-4-nitrophenyl)amino]ethyl})azaniums,
  
• – Salzen des Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(methyl)azaniums,
  
• – Salzen des Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(ethyl)azaniums,
  
• – Salzen des Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(propyl)azaniums,
  
• – Salzen des Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(allyl)azaniums,
  
• – Salzen des Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(methyl)azaniums,
  
• – Salzen des Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(ethyl)azaniums,
  
• – Salzen des Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(propyl)azaniums,
  
• – Salzen des Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(allyl)azaniums,
  
• – Salzen des Methyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azaniums,
  
• – Salzen des Ethyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azaniums,
  
• – Salzen des Propyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azaniums,
  
• – Salzen des Allyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azaniums,
  
• – Salzen des Methyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azaniums,
  
• – Salzen des Ethyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azaniums,
  
• – Salzen des Propyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azaniums,
  
• – Salzen des Allyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azaniums,
  
• – Salzen des Tris(3-{[4-(dimethylamino)-2-nitrophenyl]amino}propyl)(methyl)azaniums,
  
• – Salzen des Tris(3-{[4-(dimethylamino)-2-nitrophenyl]amino}propyl)(ethyl)azaniums,
  
• – Salzen des Tris(3-{[4-(dimethylamino)-2-nitrophenyl]amino}propyl)(propyl)azaniums,
  
• – Salzen des Tris(3-{[4-(dimethylamino)-2-nitrophenyl]amino}propyl)(allyl)azaniums,
  
• – Salzen des Tris(2-{[4-(dimethylamino)-2-nitrophenyl]amino}ethyl)(methyl)azaniums,
  
• – Salzen des Tris(2-{[4-(dimethylamino)-2-nitrophenyl]amino}ethyl)(ethyl)azaniums,
  
• – Salzen des Tris(2-{[4-(dimethylamino)-2-nitrophenyl]amino}ethyl)(propyl)azanium und
  
• – Salzen des Tris(2-{[4-(dimethylamino)-2-nitrophenyl]amino}ethyl)(allyl)azaniums,
  

According to preferred means for dyeing and optionally simultaneous lightening keratinischer fibers are characterized in that they contain at least one compound of general formula (I), which is selected from

• Salts of methyltris ({3 - [(2-nitrophenyl) amino] propyl}) azanium,
  
• Salts of ethyl tris ({3 - [(2-nitrophenyl) amino] propyl}) azanium,
  
• Salts of propyl tris ({3 - [(2-nitrophenyl) amino] propyl}) azanium,
  
• Salts of allyl tris ({3 - [(2-nitrophenyl) amino] propyl}) azanium,
  
• Salts of methyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of ethyl tris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of propyl tris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of allyl tris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of methyltris ({3 - [(4-nitrophenyl) amino] propyl}) azanium,
  
• Salts of ethyltris ({3 - [(4-nitrophenyl) amino] propyl}) azanium,
  
• Salts of propyl tris ({3 - [(4-nitrophenyl) amino] propyl}) azanium,
  
• Salts of allyl tris ({3 - [(4-nitrophenyl) amino] propyl}) azanium,
  
• Salts of methyltris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of ethyl tris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of propyl tris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of allyl tris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of methyltris ({3 - [(3-methyl-4-nitrophenyl) amino] propyl}) azanium,
  
• Salts of ethyl tris ({3 - [(3-methyl-4-nitrophenyl) amino] propyl}) azanium,
  
• Salts of propyl tris ({3 - [(3-methyl-4-nitrophenyl) amino] propyl}) azanium,
  
• Salts of allyl tris ({3 - [(3-methyl-4-nitrophenyl) amino] propyl}) azanium,
  
• Salts of methyltris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of ethyltris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of propyl tris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of allyl tris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium,
  
• Salts of tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (methyl) azaniums,
  
• Salts of tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (ethyl) azanium,
  
• Salts of tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (propyl) azanium,
  
• Salts of tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (allyl) azanium,
  
• Salts of tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (methyl) azanium,
  
• Salts of tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (ethyl) azanium,
  
• Salts of tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (propyl) azanium,
  
• Salts of tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (allyl) azanium,
  
• Salts of methyltris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium,
  
• Salts of ethyl tris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium,
  
• Salts of propyl tris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium,
  
• Salts of allyl tris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium,
  
• Salts of methyltris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium,
  
• Salts of ethyl tris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium,
  
• Salts of propyl tris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium,
  
• Salts of allyl tris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium,
  
• Salts of tris (3 - {[4- (dimethylamino) -2-nitrophenyl] amino} propyl) (methyl) azaniums,
  
• Salts of tris (3 - {[4- (dimethylamino) -2-nitrophenyl] amino} propyl) (ethyl) azanium,
  
• Salts of tris (3 - {[4- (dimethylamino) -2-nitrophenyl] amino} propyl) (propyl) azanium,
  
• Salts of tris (3 - {[4- (dimethylamino) -2-nitrophenyl] amino} propyl) (allyl) azanium,
  
• Salts of tris (2 - {[4- (dimethylamino) -2-nitrophenyl] amino} ethyl) (methyl) azanium,
  
• Salts of tris (2 - {[4- (dimethylamino) -2-nitrophenyl] amino} ethyl) (ethyl) azanium,
  
• Salts of tris (2 - {[4- (dimethylamino) -2-nitrophenyl] amino} ethyl) (propyl) azanium and
  
• Salts of tris (2 - {[4- (dimethylamino) -2-nitrophenyl] amino} ethyl) (allyl) azanium,
  

• – Methyltris({3-[(2-nitrophenyl)amino]propyl})azanium-p-tolulsulfonat,
• – Ethyltris({3-[(2-nitrophenyl)amino]propyl})azanium-p-tolulsulfonat,
• – Methyltris({2-[(2-nitrophenyl)amino]ethyl})azanium-p-tolulsulfonat,
• – Ethyltris({2-[(2-nitrophenyl)amino]ethyl})azanium-p-tolulsulfonat,
• – Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(methyl)azanium-p-tolulsulfonat,
• – Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(ethyl)azanium-p-tolulsulfonat,
• – Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(methyl)azanium-p-tolulsulfonat,
• – Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(ethyl)azanium-p-tolulsulfonat,
• – Methyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azanium-p-tolulsulfonat,
• – Ethyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azanium-p-tolulsulfonat,
• – Methyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azanium-p-tolulsulfonat,
• – Ethyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azanium-p-tolulsulfonat,
• – Methyltris({3-[(2-nitrophenyl)amino]propyl})azaniumchlorid,
• – Ethyltris({3-[(2-nitrophenyl)amino]propyl})azaniumchlorid,
• – Methyltris({2-[(2-nitrophenyl)amino]ethyl})azaniumchlorid,
• – Ethyltris({2-[(2-nitrophenyl)amino]ethyl})azaniumchlorid,
• – Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(methyl)azaniumchlorid,
• – Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(ethyl)azaniumchlorid,
• – Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(methyl)azaniumchlorid,
• – Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(ethyl)azaniumchlorid,
• – Methyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azaniumchlorid,
• – Ethyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azaniumchlorid,
• – Methyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azaniumchlorid,
• – Ethyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azaniumchlorid,
• – Methyltris({3-[(2-nitrophenyl)amino]propyl})azaniumbromid,
• – Ethyltris({3-[(2-nitrophenyl)amino]propyl})azaniumbromid,
• – Methyltris({2-[(2-nitrophenyl)amino]ethyl})azaniumbromid,
• – Ethyltris({2-[(2-nitrophenyl)amino]ethyl})azaniumbromid,
• – Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(methyl)azaniumbromid,
• – Tris({3-[(4-amino-2-nitrophenyl)amino]propyl})(ethyl)azaniumbromid,
• – Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(methyl)azaniumbromid,
• – Tris({2-[(4-amino-2-nitrophenyl)amino]ethyl})(ethyl)azaniumbromid,
• – Methyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azaniumbromid,
• – Ethyltris(3-{[4-(methylamino)-2-nitrophenyl]amino}propyl)azaniumbromid,
• – Methyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azaniumbromid,
• – Ethyltris(2-{[4-(methylamino)-2-nitrophenyl]amino}ethyl)azaniumbromid,

As a particularly preferred embodiment, means are to be emphasized which contain at least one compound of the formula (I) which is selected from

• Methyltris ({3 - [(2-nitrophenyl) amino] propyl}) azanium p-tolulsulphonate,
• Ethyltris ({3 - [(2-nitrophenyl) amino] propyl}) azanium p-tolulsulphonate,
• Methyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium p-tolulsulphonate,
• Ethyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium p-tolulsulphonate,
• Tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (methyl) azanium p-tolulsulfonate,
• Tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (ethyl) azanium p-tolulsulfonate,
• Tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (methyl) azanium p-tolulsulfonate,
• Tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (ethyl) azanium p-tolulsulfonate,
• Methyltris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium p-tolulsulfonate,
• Ethyltris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium p-tolulsulphonate,
• Methyltris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium p-tolulsulphonate,
• Ethyltris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium p-tolulsulphonate,
• Methyltris ({3 - [(2-nitrophenyl) amino] propyl}) azanium chloride,
• Ethyltris ({3 - [(2-nitrophenyl) amino] propyl}) azanium chloride,
• Methyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium chloride,
• Ethyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium chloride,
• Tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (methyl) azanium chloride,
• Tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (ethyl) azanium chloride,
• Tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (methyl) azanium chloride,
• Tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (ethyl) azanium chloride,
• Methyltris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium chloride,
• Ethyltris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium chloride,
• Methyltris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium chloride,
• Ethyltris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium chloride,
• Methyltris ({3 - [(2-nitrophenyl) amino] propyl}) azanium bromide,
• Ethyltris ({3 - [(2-nitrophenyl) amino] propyl}) azanium bromide,
• Methyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium bromide,
• Ethyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium bromide,
• Tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (methyl) azanium bromide,
• Tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (ethyl) azanium bromide,
• Tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (methyl) azanium bromide,
• Tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (ethyl) azanium bromide,
• Methyltris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium bromide,
• Ethyl tris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium bromide,
• Methyltris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium bromide,
• Ethyltris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium bromide,

Particularly preferred compounds of the formula (I), in particular the compounds mentioned explicitly above, contain as counterion X ^- p-toluenesulfonate or chloride.

The compositions according to the invention for dyeing and, if appropriate, simultaneous lightening of keratin fibers preferably contain the compound (s) of the formula (I) in amounts above 1 ppm and below 10% by weight, in each case based on the total agent. A preferred embodiment is an agent which contains the compound (s) of the formula (I) in an amount of from 0.001 to 5% by weight, preferably from 0.0025 to 2.5% by weight, particularly preferably from 0.005 to 1.5 wt .-% and in particular from 0.01 to 1 wt .-%, each based on the total weight of the composition contains.

In a further preferred embodiment, the agents according to the invention additionally comprise at least one further substantive dye in addition to the compound of the formula (I). Direct dyes can be subdivided into anionic, cationic and nonionic substantive dyes. The substantive dyes are preferably selected from the nitrophenylenediamines, the nitroaminophenols, the azo dyes, the anthraquinones, the triarylmethane dyes or the indophenols and their physiologically acceptable salts. The additional substantive dyes are each preferably used in a proportion of 0.001 to 2 wt .-%, based on the total application preparation.

Preferred anionic substantive dyes are those under the international designations or trade names 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, Acid Black 52, bromophenol blue and tetrabromophenol blue known compounds.

Preferred cationic substantive dyes are cationic triphenylmethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, aromatic systems substituted with a quaternary nitrogen group such as Basic Yellow 57, Basic Red 76, Basic Blue 99 , Basic Brown 16 and Basic Brown 17, cationic anthraquinone dyes such as HC Blue 16 (Bluequat B) and substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31 and Basic Red 51 cationic substantive dyes sold under the trademark Arianor are also preferred cationic substantive dyes in accordance with the invention.

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 10, HC Red 10, HC Red 11, HC Red 10, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds, as well as 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, 4 - [(3 -Hydroxypropyl) amino] -3-nitrophenol, 4-nitro-o-phenylenediamine, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-A Mino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

The compounds of the formula (I) can be used in combination with all of the direct dyes mentioned above in agents for dyeing and, if appropriate, simultaneous lightening of keratinic fibers, dyeing results with good fastness properties being obtained. However, certain dye combinations result in dyeings with particularly good durability, so that these combinations are preferred.

It is particularly preferred if the compound (s) of the formula (I) in combination with Basic Yellow 57, Basic Red 76, Basic Brown 16 and Basic Brown 17 such as HC Blue 16 (Bluequat B), Basic Yellow 87, Basic Orange 31 , HC Red 1, HC Red 1, HC Red 10, HC Red 11, HC Red 11, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, 2-Amino-4 nitrophenol, 1,4-bis (2-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) aminophenol, 4 - [(2-hydroxyethyl) amino] -3-nitrobenzene 1-methylbenzene, 1-amino-4- (2-hydroxyethyl) amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 4 - [(3-hydroxypropyl) amino] -3-nitrophenol and / or 4-nitro-o-phenylenediamine can be used.

The agents according to the invention can furthermore also be used as oxidation colorants. Such oxidation colorants additionally contain at least one oxidation dye precursor, preferably at least one developer-type oxidation dye precursor and at least one coupler-type oxidation dye precursor. Particularly suitable developer-type oxidation dye precursors 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) propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,10-bis- (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (1,2-dihydroxyethyl) phenol, 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, 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and their physiologically acceptable salts.

Particularly suitable coupler-type oxidation dye precursors are selected from the group 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-morpholine-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-methylamine no-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, or mixtures of these compounds or their physiological compatible salts.

The substantive dyes, developer components and coupler components are preferably used in each case in an amount of 0.0001 to 5.0 wt .-%, preferably 0.001 to 2.5 wt .-%, each based on the ready-to-use agent. In this case, developer components and coupler components are generally used in approximately molar amounts to each other. Although the molar use has proven to be expedient, a certain excess of individual oxidation dye precursors is not disadvantageous, so that developer components and coupler components in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2 , can stand.

A further preferred embodiment is an agent for dyeing and optionally simultaneous brightening of keratinic fibers, which is characterized in that it additionally contains - based on its weight - each 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes.

In the case of oxidation colorants, the agents preferably contain an oxidizing agent, preferably hydrogen peroxide. The amounts of hydrogen peroxide correspond to the amounts in the lightening agents according to the invention.

The colorants can also be used as lightening colorants. To achieve the whitening effect, the means for containing hydrogen peroxide and / or one of its solid addition products of organic or inorganic compounds.

A further embodiment of the first subject of the invention is therefore characterized in that the agent additionally contains hydrogen peroxide and / or one of its solid addition products of organic or inorganic compounds.

In a preferred embodiment, hydrogen peroxide itself is used as the aqueous solution. The concentration of a hydrogen peroxide solution in the composition according to the invention is determined on the one hand by the legal requirements and on the other hand by the desired effect; preferably 6 to 12 wt .-% solutions are used in water. According to preferred application-ready means of the first subject of the invention are characterized in that, based on the total weight of the ready-to-use agent, 0.5 to 20 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10 Wt .-% and in particular 3 to 6 wt .-% hydrogen peroxide, each based on the total weight of the composition.

To achieve enhanced whitening and bleaching action, the composition may further contain at least one peroxo salt. Suitable peroxo salts are inorganic peroxo compounds, preferably selected from the group formed from ammonium peroxodisulfate, alkali metal peroxodisulfates, ammonium peroxomonosulfate, alkali metal peroxomonosulfates, alkali metal peroxodiphosphates and alkaline earth metal peroxides. Particularly preferred are peroxodisulfates, in particular ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate.

The persulfates are each in an amount of 0.5 to 20 wt .-%, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10 wt .-% and in particular 3 to 6 wt .-%, based on the total weight of the ready-to-use agent, contained in the agent according to the invention.

A further preferred embodiment is an agent for dyeing and simultaneously lightening keratinic fibers which additionally contains hydrogen peroxide, one of its solid addition products of organic or inorganic compounds, ammonium peroxodisulfate, potassium peroxodisulfate and / or sodium peroxodisulfate in each case in an amount of 0.5 to 20% by weight. %, preferably 1 to 12.5 wt .-%, particularly preferably 2.5 to 10 wt .-% and in particular 3 to 6 wt .-%, based on the total weight of the ready-to-use agent contains.

The agent may contain further bleach boosters to enhance the bleaching effect, such as tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), tetraacetylglycoluril (TAGU), N-nonanoylsuccinimide ( NOSI), n-nonanoyl or isononanoyloxybenzenesulfonate (n- or i-NOBS), phthalic anhydride, triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and carbonate salts or bicarbonate salts, in particular ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, disodium carbonate , Potassium hydrogencarbonate, dipotassium carbonate and calcium carbonate, and nitrogen-containing heterocyclic bleach boosters such as 4-acetyl-1-methylpyridinium p-toluenesulfonate, 2-acetyl-1-methylpyridinium p-toluenesulfonate, and N-methyl-3,4-dihydroisoquinolinium-p -toluolsulfonat.

To further increase the lightening, at least one SiO ₂ compound, such as silica or silicates, in particular water glasses, may additionally be added to the composition according to the invention. 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 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.

The ready-to-use colorants may further contain additional active ingredients, auxiliaries and additives in order to improve the dyeing performance and to adjust other desired properties of the agents.

Preferably, the ready-to-use colorants are provided as a liquid preparation and the surfactants are therefore additionally added to a surfactant, wherein such surfactants are referred to as surfactants or as emulsifiers, depending on the field of application. They are preferably anionic, cationic, zwitterionic, amphoteric and nonionic surfactants and emulsifiers selected.

Agents preferred 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. The anionic 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 the ready-to-use agent.

Agents preferred 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 preferred 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 Addition products 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 proved. 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.

Compositions suitable according to the invention may also contain cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines. Preferred quaternary ammonium compounds are ammonium halides and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. Further according to the invention useful cationic surfactants are the quaternized protein hydrolyzates. A according to the invention particularly suitable compound of the amidoamine is sold under the name Tegoamid ^® S 18 commercially available stearamidopropyl dimethylamine. Preferred esterquats are quaternized Estersalze of fatty acids with triethanolamine, quaternized Estersalze of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. The cationic surfactants are contained in the agents used according to the invention preferably in proportions of 0.05 to 10 wt .-%, based on the total agent.

The ready-to-use colorants may contain other auxiliaries and additives. Thus, it has proved to be advantageous if the agent 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.

• – anionische, synthetische Polymere;
• – kationische, synthetische Polymere;
• – natürlich vorkommende Verdickungsmittel, wie nichtionische Guargums, Skleroglucangums oder Xanthangums, Gummi arabicum, Ghatti-Gummi, Karaya-Gummi, Tragant-Gummi, Carrageen-Gummi, Agar-Agar, Johannisbrotkernmehl, Pektine, Alginate, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, sowie Cellulosederivate, wie beispielsweise Methylcellulose, Carboxyalkylcellulosen und Hydroxyalkylcellulosen;
• – nichtionische, vollsynthetische Polymere, wie Polyvinylalkohol oder Polyvinylpyrrolidinon; sowie
• – anorganische Verdickungsmittel, insbesondere Schichtsilikate wie beispielsweise Bentonit, besonders Smektite, wie Montmorillonit oder Hectorit.

Suitable thickeners are

• Anionic synthetic polymers;
• Cationic synthetic polymers;
• Naturally occurring thickeners, such as nonionic guar gums, scleroglucan gums or xanthan gums, gum arabic, ghatti gum, karaya gum, gum tragacanth, 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; such as
• Inorganic thickening agents, in particular phyllosilicates, for example bentonite, especially smectites, such as montmorillonite or hectorite.

Dyeing processes on keratin fibers 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 if the pH of the ready-to-use agent is between 7 and 11, in particular between 8 and 10.5. For the purposes of the present invention, the pH values are pH values which were measured at a temperature of 22 ° C.

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 ( Earth) alkali metal hydrogen phosphates. Preferred inorganic alkalizing agents are magnesium carbonate, 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.

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. Especially 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 used 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 on the total weight of the application mixture.

For the application of the agents according to the invention is particularly suitable a method for dyeing keratinic fibers, in particular human hair, which is characterized in that an agent of the first subject of the invention applied to the keratin fibers, leave on the fiber for 5 to 60 minutes and then with water again rinsed or washed out with a shampoo. The exposure time of the ready-to-use colorants is preferably from 5 to 45 minutes, in particular from 10 to 40 minutes, particularly preferably from 15 to 35 minutes. During the exposure time of the agent on the fiber, it may be advantageous to assist the lightening process by supplying heat. The heat input may be provided by an external heat source, e.g. warm air of a hot air blower, as well as, especially in a hair whitening on living subjects, done by the body temperature of the subject. In the latter option, usually the brightening lot is covered with a hood. An exposure phase at room temperature is also according to the invention. In particular, the temperature during the exposure time between 20 ° C and 40 ° C, in particular between 25 ° C and 38 ° C. After the end of the exposure time, the remaining dyeing preparation is rinsed with water or a cleaning agent from the hair. As a cleaning agent can be used in particular commercial shampoo, in particular then can be dispensed with the detergent and the rinsing can be done with water when the brightening agent has a strong surfactant-containing carrier.

The compositions according to the invention can be formulated as single-component agents (dyeing and whitening agents) or as multicomponent agents, such as two-component agents or three-component agents, and used accordingly. Separation into multicomponent systems is particularly suitable where incompatibilities of the ingredients are to be expected or feared; the agent to be used in such systems is manufactured by the consumer just prior to use by mixing the component.

A dyeing and whitening process in which the dyeing cream and the oxidizing agent are initially present separately is preferred. A further subject of the present invention is therefore a process for dyeing and lightening human hair, in which an aqueous-based composition containing hydrogen peroxide is mixed with an agent according to the invention containing at least one compound of formula (I) to give a homogeneous composition is applied to the hair.

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

The compounds of general formula (I) are very suitable as substantive dyes for the dyeing of hair, where they - either alone or in combination with other dyes - to colorfast shades with high gloss, good wash fastness, good light fastness, good rubfastness and / or good sweat fastness.

• – erhöhtem Glanz
• – verbesserter Waschechtheit
• – verbesserter Lichtechtheit
• – verbesserter Reibechtheit und/oder
• – verbesserter Shweißechtheit.

Another object of the present invention is therefore the cosmetic use of an agent containing at least one compound of formula (I) for the production of intense hair dyes with

• - increased gloss
• - improved wash fastness
• - improved light fastness
• - improved rubbing fastness and / or
• - improved Shweichtechtheit.

in der
R1, R2 unabhängig voneinander für Wasserstoff, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe, eine Hydroxygruppe, eine C₁-C₆-Alkoxygruppe, eine Aminogruppe, eine C₁-C₆-Alkylaminogruppe, eine Di-C₁-C₆-alkylaminogruppe oder Halogen stehen,
R3 für Wasserstoff, eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe,eine Cyano-C₁-C₆-alkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe steht,
n für eine ganze Zahl von 2 bis 6 steht,
Y für eine kationische Gruppierung der Formeln (II) oder (III) steht,

worin
R4 für eine C₁-C₆-Alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine C₂-C₆-Hydroxyalkylgruppe, eine C₂-C₆-Polyhydroxyalkylgruppe, eine C₁-C₆-Alkoxy-C₂-C₆-alkylgruppe, eine Cyano-C₁-C₆-alkylgruppe oder eine Aryl-C₁-C₆-alkylgruppe steht,
m für eine ganze Zahl von 2 bis 6 steht und
X- für ein physiologisch verträgliches Anion, vorzugsweise für Halogenid, Hydrogensulfat, ½ Sulfat, Benzolsulfonat, p-Toluolsulfonat, Acetat, Citrat, Lactat, ½ Tartrat oder Triflourmethansulfonat steht. The trimeric nitro dyes present in the compositions according to the invention have not hitherto been described in the literature. A further subject of the present invention are therefore compounds of the formula (I)

in the
R _1, R ₂ independently of one another represent hydrogen, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, an amino group, a C ₁ -C ₆ -alkylamino group, a di-C ₁ -C ₆ -alkylamino group or halogen,
R 3 is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ hydroxyalkyl, C ₂ -C ₆ polyhydroxyalkyl, C ₁ -C ₆ alkoxy-C C ₂ -C ₆ -alkyl group, a cyano-C ₁ -C ₆ -alkyl group or an aryl-C ₁ -C ₆ -alkyl group,
n is an integer from 2 to 6,
Y is a cationic grouping of the formula (II) or (III),

wherein
R 4 is a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₂ - C ₆ alkyl group, a cyano C ₁ -C ₆ alkyl group or an aryl C ₁ -C ₆ alkyl group,
m stands for an integer from 2 to 6 and
X- represents a physiologically acceptable anion, preferably halide, hydrogensulfate, ½ sulfate, benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, ½ tartrate or trifluoromethanesulfonate.

With respect to further preferred embodiments of these compounds mutatis mutandis applies to the means of the invention.

The following examples are intended to illustrate the subject matter of the present application without, however, limiting it in any way.

Examples

1. Synthesis examples

Synthesis Example 1: Synthesis of methyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate (DZ 1)

1.1.1 Synthesis of N- {2- [bis ({2 - [(2-nitrophenyl) amino] ethyl}) amino] ethyl} -2-nitroaniline

66.2 g (0.42 mol) of 2-chloronitrobenzene were melted at 60 ° C. and admixed with 15.0 g (0.14 mol) of sodium carbonate. Then, 20.5 g (0.14 mol) of tris (2-aminoethyl) amine were added dropwise. After completion of the addition, the reaction mixture was heated at 120 ° C for 6 hours. After cooling, the batch was mixed with 100 ml of toluene. To separate the inorganic salts was filtered and the filtrate was concentrated on a rotary evaporator in vacuo. As a residue, the product remained in the form of a dark brown, viscous liquid.
Yield: 64.8 g (90.9%) 1.1.2 Synthesis of methyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate (DZ 1)

To a solution of 60.0 g (0.12 mol) of N- {2- [bis ({2 - [(2-nitrophenyl) amino] ethyl}) amino] ethyl} -2-nitroaniline from step 1.1.1 in 500 ml of toluene Add 24.9 g (0.13 mol) of p-toluenesulfonic acid methyl ester and heated for 6 h under reflux. In the course of the reaction, a solid began to precipitate, which was filtered off after cooling the reaction mixture, washed with toluene, boiled in 300 ml of ethanol, filtered again (hot) and dried.
Yield: 8.3 g (10.1%)

Synthesis Example 2: Synthesis of methyltris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate (DZ 2)

1.2.1 Synthesis of N- {2- [bis ({2 - [(4-nitrophenyl) amino] ethyl}) amino] ethyl} -4-nitroaniline

60.0 g (0.42 mol) of 1-fluoro-4-nitrobenzene were introduced into 100 ml of dimethyl sulfoxide, heated to 60 ° C and treated with 15.0 g (0.14 mol) of sodium carbonate. Then, 20.5 g (0.14 mol) of tris (2-aminoethyl) amine were added dropwise. After completion of the addition, the reaction mixture was heated at 120 ° C for 6 hours. After cooling, quenched into 1.0 L of water, precipitating a solid. The solid was filtered off with suction and dried.
Yield: 58.8 g (81.4%) 1.2.2 Synthesis of methyltris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate (DZ 2)

To a solution of 50.0 g (98.0 mmol) of N- {2- [bis ({2 - [(4-nitrophenyl) amino] ethyl}) amino] ethyl} -4-nitroaniline from step 1.2.1. in 500 ml of toluene, 20.2 g (107.2 mmol) of p-toluenesulfonate were added and heated under reflux for 6 h. In the course of the reaction, a solid began to precipitate, which was filtered off after cooling the reaction mixture, washed with toluene, boiled in 300 ml of ethanol, filtered again (hot) and dried.
Yield: 45.0 g (65.9%)

Synthesis Example 3: Synthesis of methyltris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate (DZ 3)

1.3.1 Synthesis N- {2- [bis ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) amino] ethyl} -3-methyl-4-nitroaniline

65.1 g (0.42 mol) of 5-fluoro-2-nitrotoluene presented in 100 ml of dimethyl sulfoxide, heated to 60 ° C and treated with 15.0 g (0.14 mol) of sodium carbonate. Then, 20.5 g (0.14 mol) of tris (2-aminoethyl) amine were added dropwise. After completion of the addition, the reaction mixture was heated to 120 ° C for six hours. After cooling, quenched with 0.5 l of water and the aqueous phase extracted with ethyl acetate. The organic phase was dried over sodium sulfate and concentrated to dryness.
Yield: 52.6 g (68.1%) 1.3.2 Synthesis of methyltris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate (DZ 3)

To a solution of 47.4 g (85.9 mmol) of N- {2- [bis ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) amino] ethyl} -4-nitroaniline from step 1.3.1 in 500 ml of toluene were added 18.9 g (0.10 mol) of p-toluenesulfonate and heated under reflux for 6 h. In the course of the reaction, a solid began to precipitate, which was filtered off after cooling the reaction mixture, washed with toluene, boiled in 300 ml of ethanol, filtered again (hot) and dried.
Yield: 36.0 g (56.8%)

2. Dyeing Examples

2.1. Production of coloring creams

The following coloring creams were prepared: 2.1.1 Coloring Cream 1 (nonionic coloring cream) Cetearyl Alcohol 6.0 g Coconut Alcohol 6.0 g PEG-40 Hydrogenated Castor Oil 1.0 g Ceteareth-12 3.0 g Ceteareth-20 3.0 g PHB Methylester 0.3 g PHB propyl 0.2 g phenoxyethanol 1.0 g PEG-8 5.0 g DZ according to the invention 1.0 g ammonium sulfate 1.0 g (in 30.0 g of water) hydroxyethyl 1.0 g (in 15.0 g of water) NaOH 0.1% ad pH water ad 100 g

The first nine components were melted together at 80 ° C. This mixture was emulsified with an aqueous solution of the direct draw and the ammonium sulfate in 30 g of water. Subsequently, a swelling of 1.0 g of Natrosol 250 HR in 15.0 g of water was added. The indicated pH was adjusted with 0.1% sodium hydroxide solution, then made up to 100 g with water. 2.1.2 Coloring Cream 2 (cationic coloring cream) Cetearyl Alcohol 4.0 g Ceteareth-12 1.0 g Dehyquart® ^® A-CA 2.0 g ammonium sulfate 1.0 g (in 30.0 g of water) DZ according to the invention 1.0 g water at 100 g

The first three components were melted together, then the melt was emulsified with hot water. Then, the water-dissolved or pre-dispersed dye and the aqueous ammonium sulfate solution were added. The pH was adjusted to the stated value with ammonia, then made up to 100 g with water. 2.1.3 Coloring Cream 3 (anionic coloring cream) Cetearyl Alcohol 1.0 g Coconut Alcohol 1.0 g Akypo Soft ^® RLM 45N 1.1 g PHB propyl 0.1 g PHB Methylester 0.1 g ammonium sulfate 1.0 g (in 30.0 g of water) DZ according to the invention 1.0 g water ad 100 g

The first five components were melted together. This melt was emulsified with hot water, then the water-dissolved or predispersed dye was added and the ammonium sulfate solution was added. The indicated pH was adjusted with ammonia, then made up to 100 g with water. 2.2 List of raw materials used Akypo Soft RLM 45 NV ^® Lauryl alcohol 4.5 EO acetic acid sodium salt (at least 22% active ingredient content, INCI name: sodium laureth-5 carboxylate) Dehyquart® ^® A-CA Trimethylhexadecylammonium chloride (about 24-26% active ingredient, INCI name: Aqua (Water), Cetrimonium Chloride)

2.3 colorations

DZ 1:

Methyltris({2-[(2-nitrophenyl)amino]ethyl})azanium p-toluolsulfonat

DZ 2:

Methyltris({2-[(4-nitrophenyl)amino]ethyl})azanium p-toluolsulfonat

DZ 3:

Methyltris({2-[(3-methyl-4-nitrophenyl)amino]ethyl})azanium p-toluolsulfonat

Farbstoff Färbecreme pH-Wert Farbnuance (Intensität) DZ 1 1 9,5 gelb (++) DZ 1 2 9,5 ginstergelb (+++) DZ 1 3 9,5 knallgelb (+++) DZ 2 1 9,5 pastellgelb (+) DZ 2 2 9,5 sonnengelb (++) DZ 2 3 9,5 sonnengelb (++) DZ 3 1 9,5 gelbweiß (+) DZ 3 2 9,5 gelbweiß (+) DZ 3 3 9,5 gelbweiß (+) Intensität: + = niedrig ++ = mittel +++ = hoch Each 1.8 g of the dyeing cream were applied to an approximately 6 cm long strand of human hair (Kerling Euronaturhaar, blond) and left there for 30 minutes at 30 ° C. After the exposure time, the hair was rinsed, washed with a commercial shampoo and then dried. The hair tresses were dyed in the following shades.

DZ 1:

Methyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate

DZ 2:

Methyltris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate

DZ 3:

Methyl tris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium p-toluenesulfonate

dye coloring cream PH value Color nuance (intensity) DZ 1 1 9.5 yellow (++) DZ 1 2 9.5 yellowish-yellow (+++) DZ 1 3 9.5 bright yellow (+++) Double room 2 1 9.5 pastel yellow (+) Double room 2 2 9.5 sunny yellow (++) Double room 2 3 9.5 sunny yellow (++) DZ 3 1 9.5 yellow-white (+) DZ 3 2 9.5 yellow-white (+) DZ 3 3 9.5 yellow-white (+) Intensity: + = low ++ = medium +++ = high

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

• DE 1941376 [0011]
• FR 1540423 A1 [0011]
• FR 2864964 [0011]

Claims (10)

Agent for dyeing and, if appropriate, simultaneous lightening of keratinic fibers, in particular human hair, comprising in a cosmetic carrier at least one compound of the formula (I),

in the R _1, R ₂ independently of one another represent hydrogen, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, one Amino group, a C ₁ -C ₆ -alkylamino group, a di-C ₁ -C ₆ -alkylamino group or halogen, R 3 is hydrogen, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group, a cyano C ₁ -C ₆ alkyl group or an aryl C ₁ -C _{6 is an} alkyl radical, n is an integer from 2 to 6, Y is a cationic moiety of the formula (II) or (III),

wherein R4 is a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₂ -C ₆ alkyl group, a cyano-C ₁ -C ₆ alkyl group or an aryl-C ₁ -C ₆ alkyl group, m is an integer from 2 to 6 and X- is a physiologically acceptable anion, preferably for Halide, hydrogen sulfate, ½ sulfate, benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, ½ tartrate or trifluoromethanesulfonate. Composition according to Claim 1, characterized in that it contains at least one compound of the formula (I) in which R _{1 and} R 2 independently of one another represent hydrogen, a C ₁ -C ₆ -alkyl group, an amino group, a C ₁ -C ₆ -alkylamino group or a di-C ₁ -C ₆ -alkylamino group. Composition according to one of claims 1 or 2, characterized in that it contains at least one compound of formula (I), in which R3 is hydrogen and n is the number 2 or 3. Composition according to one of claims 1 to 3, characterized in that it contains at least one compound of formula (I) in which Y is the cationic group (II). Composition according to one of claims 1 to 4, characterized in that it contains at least one compound of formula (I), in which R4 is a C ₁ -C ₆ alkyl group or a C ₂ -C ₆ alkenyl group, preferably a C C ₁ -C ₆ alkyl group, more preferably a methyl group, ethyl group or propyl group. Agent according to one of claims 1 to 5, characterized in that it contains at least one compound of formula (I) which is selected from Salts of methyltris ({3 - [(2-nitrophenyl) amino] propyl}) azanium, Salts of ethyl tris ({3 - [(2-nitrophenyl) amino] propyl}) azanium, Salts of propyl tris ({3 - [(2-nitrophenyl) amino] propyl}) azanium, Salts of allyl tris ({3 - [(2-nitrophenyl) amino] propyl}) azanium, Salts of methyltris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium, Salts of ethyl tris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium, Salts of propyl tris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium, Salts of allyl tris ({2 - [(2-nitrophenyl) amino] ethyl}) azanium, Salts of methyltris ({3 - [(4-nitrophenyl) amino] propyl}) azanium, Salts of ethyltris ({3 - [(4-nitrophenyl) amino] propyl}) azanium, Salts of propyl tris ({3 - [(4-nitrophenyl) amino] propyl}) azanium, Salts of allyl tris ({3 - [(4-nitrophenyl) amino] propyl}) azanium, Salts of methyltris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium, Salts of ethyl tris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium, Salts of propyl tris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium, Salts of allyl tris ({2 - [(4-nitrophenyl) amino] ethyl}) azanium, Salts of methyltris ({3 - [(3-methyl-4-nitrophenyl) amino] propyl}) azanium, Salts of ethyl tris ({3 - [(3-methyl-4-nitrophenyl) amino] propyl}) azanium, Salts of propyl tris ({3 - [(3-methyl-4-nitrophenyl) amino] propyl}) azanium, Salts of allyl tris ({3 - [(3-methyl-4-nitrophenyl) amino] propyl}) azanium, Salts of methyltris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium, Salts of ethyltris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium, Salts of propyl tris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium, Salts of allyl tris ({2 - [(3-methyl-4-nitrophenyl) amino] ethyl}) azanium, Salts of tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (methyl) azaniums, Salts of tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (ethyl) azanium, Salts of tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (propyl) azanium, Salts of tris ({3 - [(4-amino-2-nitrophenyl) amino] propyl}) (allyl) azanium, Salts of tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (methyl) azanium, Salts of tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (ethyl) azanium, Salts of tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (propyl) azanium, Salts of tris ({2 - [(4-amino-2-nitrophenyl) amino] ethyl}) (allyl) azanium, Salts of methyltris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium, Salts of ethyl tris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium, Salts of propyl tris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium, Salts of allyl tris (3 - {[4- (methylamino) -2-nitrophenyl] amino} propyl) azanium, Salts of methyltris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium, Salts of ethyl tris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium, Salts of propyl tris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium, Salts of allyl tris (2 - {[4- (methylamino) -2-nitrophenyl] amino} ethyl) azanium, Salts of tris (3 - {[4- (dimethylamino) -2-nitrophenyl] amino} propyl) (methyl) azaniums, Salts of tris (3 - {[4- (dimethylamino) -2-nitrophenyl] amino} propyl) (ethyl) azanium, Salts of tris (3 - {[4- (dimethylamino) -2-nitrophenyl] amino} propyl) (propyl) azanium, Salts of tris (3 - {[4- (dimethylamino) -2-nitrophenyl] amino} propyl) (allyl) azanium, Salts of tris (2 - {[4- (dimethylamino) -2-nitrophenyl] amino} ethyl) (methyl) azanium, Salts of tris (2 - {[4- (dimethylamino) -2-nitrophenyl] amino} ethyl) (ethyl) azanium, Salts of tris (2 - {[4- (dimethylamino) -2-nitrophenyl] amino} ethyl) (propyl) azanium, and - Salts of tris (2 - {[4- (dimethylamino) -2-nitrophenyl] amino} ethyl) (allyl) azaniums. Agent according to one of claims 1 to 6, characterized in that it contains the compound (s) of the formula (I) in an amount of 0.001 to 5 wt .-%, preferably from 0.0025 to 2.5 wt .-%, especially preferably from 0.005 to 1.5 wt .-% and particularly preferably from 0.01 to 1 wt .-%, each based on the total weight of the composition contains. Agent according to one of claims 1 to 7, characterized in that it additionally - based on its weight - each containing 0.001 to 5 wt .-% of one or more oxidation dye precursors and / or direct dyes. Cosmetic use of an agent according to any one of claims 1 to 8 for the production of intense hair dyes with - increased gloss - improved wash fastness - improved light fastness - improved rubbing fastness and / or - improved Shweichtechtheit. Compounds of the formula (I)

in the R _1, R ₂ independently of one another represent hydrogen, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a hydroxy group, a C ₁ -C ₆ -alkoxy group, one Amino group, a C ₁ -C ₆ -alkylamino group, a di-C ₁ -C ₆ -alkylamino group or halogen, R 3 is hydrogen, a C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, a C ₂ -C ₆ -hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy-C ₂ -C ₆ alkyl group, a cyano C ₁ -C ₆ alkyl group or an aryl C ₁ -C _{6 is an} alkyl radical, n is an integer from 2 to 6, Y is a cationic moiety of the formula (II) or (III),

wherein R 4 is a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ hydroxyalkyl group, a C ₂ -C ₆ polyhydroxyalkyl group, a C ₁ -C ₆ alkoxy C ₂ - C ₆ alkyl group, a cyano C ₁ -C ₆ alkyl group or an aryl C ₁ -C ₆ alkyl group, m is an integer from 2 to 6 and X- is a physiologically acceptable anion, preferably halide , Hydrogen sulfate, ½ sulfate, benzenesulfonate, p-toluenesulfonate, acetate, citrate, lactate, ½ tartrate or trifluoromethanesulfonate.