DE102019211597A1 - Oxidant-free process for coloring keratin material, comprising the use of an organic C1-C6 alkoxysilane and an oxidation dye precursor - Google Patents

Abstract

The present invention relates to a method for coloring keratinic material, in particular human hair, in which the keratinic material is used: a first composition (A) which contains: (A1) one or more organic C1-C6-alkoxy Silanes and / or their condensation products, and a second composition (B) which contains (B1) one or more oxidation dye precursors, with the proviso that in the process no composition is applied to the keratinic material which contains one or more peroxo compounds.

Description

The present application is in the field of cosmetics and relates to a method for the treatment of keratinic material, in particular human hair, which comprises the use of two compositions (A) and (B). The composition (A) is a preparation which contains at least one organic C ₁ -C ₆ -alkoxysilane, and the composition (B) contains at least one compound from the group of oxidation dye precursors. For the method there is the stipulation that no composition is applied to the keratinic material in the method which contains one or more peroxo compounds.

A second subject of the present invention is a multi-component packaging unit (kit-of-parts) for coloring keratinous material, which, separately packaged in two packaging units, comprises the two compositions (A) and (B) described above

The change in the shape and color of keratinic fibers, in particular of hair, represents an important area of modern cosmetics. The person skilled in the art knows various coloring systems for changing the hair color, depending on the coloring requirements. Oxidation dyes are usually used for permanent, intense dyeings with good fastness properties and good gray coverage. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes with one another. Oxidation dyes are characterized by very long-lasting coloring results.

If substantive dyes are used, dyes that have already been developed diffuse from the dye into the hair fiber. Compared to oxidative hair coloring, the coloring obtained with substantive dyes is less durable and can be washed out more quickly. Colorations with substantive dyes usually remain on the hair for a period of between 5 and 20 washes.

The use of color pigments is known for brief color changes on the hair and / or the skin. Color pigments are generally understood to mean insoluble, coloring substances. These are present undissolved in the form of small particles in the coloring formulation and are only deposited on the outside of the hair fibers and / or the skin surface. Therefore, they can usually be removed without residue by a few washes with detergents containing surfactants. Various products of this type are available on the market under the name of hair mascara.

If the user wants particularly long-lasting coloring, the use of oxidative coloring agents has so far been his only option. However, despite multiple attempts at optimization, an unpleasant smell of ammonia or amine cannot be completely avoided with oxidative hair coloring. The hair damage still associated with the use of oxidative coloring agents also has an adverse effect on the user's hair.

EP 2168633 B1 deals with the task of producing long-lasting hair color using pigments. The document teaches that when a combination of pigment, organic silicon compound, hydrophobic polymer and a solvent is used, hair can be colored which is particularly resistant to shampooing.

In the EP 2168633 B1 The organic silicon compounds used are reactive compounds from the class of alkoxy-silanes. These alkoxy-silanes hydrolyze in the presence of water at high speed and - depending on the particular amounts of alkoxy-silane and water used - form hydrolysis products and / or condensation products. The influence of the amount of water used in this reaction on the properties of the hydrolysis or condensation product are for example in WO 2013068979 A2 described.

If these alkoxy-silanes or their hydrolysis or condensation products are used on keratin material, a film or also a coating forms on the keratin material, which completely envelops the keratin material and in this way strongly influences the properties of the keratin material. Possible areas of application are, for example, permanent styling or the permanent change in shape of keratin fibers. Here the keratin fibers are mechanically brought into the desired shape and then fixed in this shape by forming the above-described coating. Another quite A particularly suitable application is the coloring of keratin material. In the context of this application, the coating or the film is produced in the presence of a coloring compound, for example a pigment. The film colored by the pigment remains on the keratin material or the keratin fibers and results in surprisingly wash-resistant colorations.

The great advantage of the alkoxy-silane-based coloring principle is that the high reactivity of this class of compounds enables very fast coating. Good staining results can be achieved after only a few minutes of use. In addition, the coating is created on the surface of the keratin material and does not change the structure inside the keratin, so this coloring technology is a very gentle method of changing the color of the keratin material.

Coloring processes which use the formation of colored films or coatings are, however, also associated with various disadvantages. The staining is done with the technique of EP 2168633 B1 on uniform, not graying hair, the first color result is in principle not objectionable. However, if the user has partially grayed hair, the formulations of the EP 2168633 only a very inadequate gray coverage can be obtained. This dyeing process is therefore not suitable and must be optimized, especially for users who have a graying percentage between 10 and 90%.

It was therefore the object of the present application to find a method for coloring keratin materials, in particular human hair, which has an improved gray coverage without damaging the keratin material or the hair.

It has surprisingly been found that this object can be achieved in full if the keratin material is treated in a method in which two compositions (A) and (B) are applied to the keratin material. The first composition (A) contains at least one organic C ₁ -C ₆ -alkoxy-silane (A1) and / or its condensation product, and the second composition (B) is characterized by its content of at least one oxidation dye precursor (B1). The oxidation dye precursor can be a substance of the developer type and / or the coupler type. In particular, the observation that the use of the compositions (A) and (B) leads to colorations with very good gray coverage even without the use of one of the oxidizing agents otherwise customary in oxidative hair coloring, could not have been foreseen by the person skilled in the art. For this reason, it was possible to dispense with the use of oxidizing agents in the coloring process, and the keratin material was colored very gently and not damaged by the coloring process.

• - eine erste Zusammensetzung (A), die enthält:
  • (A1) ein oder mehrere organische C₁-C₆-Alkoxy-Silane und/oder deren Kondensationsprodukte, und
• - eine zweite Zusammensetzung (B), die enthält
  • (B1) ein oder mehrere Oxidationsfarbstoffvorprodukte,

mit der Maßgabe, dass im Verfahren keine Zusammensetzung auf dem keratinischen Material angewendet wird, die eine oder mehrere Peroxoverbindungen enthält.A first object of the present invention is a method for coloring keratinic material, in particular human hair, in which the keratinic material is used:

• - a first composition (A) containing:
  • (A1) one or more organic C ₁ -C ₆ -alkoxy-silanes and / or their condensation products, and
• - a second composition (B) which contains
  • (B1) one or more oxidation dye precursors,

with the proviso that in the process no composition is applied to the keratinic material which contains one or more peroxo compounds.

If the composition (A) was applied to the keratin material as part of a coloring process, an improvement in the gray coverage could be determined in particular when the composition (B) was applied to the keratin material in the form of an aftertreatment agent after the application of the composition (A). Even if the compositions (A) and (B) were mixed with one another before use and added to the keratin material in their mixture, very good results could be obtained. It was particularly surprising that these results could be achieved without using an oxidizing agent customary for oxidative hair coloring.

Coloring of keratinic material

Keratinic material is understood to mean hair, skin, and nails (such as fingernails and / or toenails, for example). Furthermore, wool, furs and feathers also fall under the definition of keratinic material.

Keratinic material is preferably understood to mean human hair, human skin and human nails, in particular fingernails and toenails. Keratinic material is very particularly preferably understood to mean human hair.

Organic C ₁ -C ₆ -alkoxy-silanes (A1) and / or their condensation products in the composition (A)

The composition (A) is characterized in that it contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) and / or their condensation products.

The organic C ₁ -C ₆ -alkoxy-silane (s) are organic, non-polymeric silicon compounds which are preferably selected from the group of silanes having one, two or three silicon atoms

Organic silicon compounds, which are alternatively referred to as organosilicon compounds, are compounds that either have a direct silicon-carbon bond (Si-C) or in which the carbon is attached to the silicon via an oxygen, nitrogen or sulfur atom. Atom is linked. The organic silicon compounds according to the invention are preferably compounds which contain one to three silicon atoms. The organic silicon compounds particularly preferably contain one or two silicon atoms.

According to the IUPAC rules, the term silane stands for a group of chemical compounds based on a silicon backbone and hydrogen. In the case of organic silanes, the hydrogen atoms have been completely or partially replaced by organic groups such as, for example, (substituted) alkyl groups and / or alkoxy groups.

A characteristic of the C ₁ -C ₆ -alkoxy-silanes according to the invention is that at least one C ₁ -C ₆ -alkoxy group is bonded directly to a silicon atom. The C ₁ -C ₆ -alkoxy-silanes according to the invention thus comprise at least one structural unit R'R''R '''Si-O- (C ₁ -C ₆ -alkyl) where the radicals R', R '' and R ''' stand for the three remaining bond valences of the silicon atom.

The C ₁ -C ₆ alkoxy group or groups bonded to the silicon atom are very reactive and are hydrolyzed at high speed in the presence of water, the reaction rate also depending, inter alia, on the number of hydrolyzable groups per molecule. If the hydrolyzable C ₁ -C ₆ -alkoxy group is an ethoxy group, the organic silicon compound preferably contains a structural unit R'R "R"'Si-O-CH2-CH3. The radicals R ', R''andR'"again represent the three remaining free valences of the silicon atom.

Even the addition of small amounts of water initially leads to hydrolysis and then to a condensation reaction of the organic alkoxysilanes with one another. For this reason, both the organic alkoxysilanes (A1) and their condensation products can be included in the composition.

A condensation product is understood to mean a product that is formed by the reaction of at least two organic C ₁ -C ₆ -alkoxy-silanes with elimination of water and / or with elimination of a C ₁ -C ₆ -alkanol.

The condensation products can be, for example, dimers, but also trimers or oligomers, the condensation products being in equilibrium with the monomers.

Depending on the amount of water used or consumed in the hydrolysis, the equilibrium shifts from monomeric C ₁ -C ₆ -alkoxysilane to condensation product.

In a particularly preferred embodiment, a method according to the invention is characterized in that the composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) which are selected from silanes with one, two or three silicon atoms wherein the organic silicon compound further comprises one or more basic chemical functions.

This basic group can be, for example, an amino group, an alkylamino group or a dialkylamino group, which is preferably connected to a silicon atom via a linker. The basic group is preferably an amino group, a C ₁ -C ₆ -alkylamino group or a di (C ₁ -C ₆ ) alkylamino group.

A very particularly preferred method according to the invention is characterized in that the composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) which are selected from the group of silanes with one, two or three silicon atoms, and wherein the C ₁ -C ₆ -alkoxy-silanes further comprise one or more basic chemical functions.

Very particularly good results could be obtained if C ₁ -C ₆ -alkoxy-silanes of the formula (SI) and / or (S-II) were used in the process according to the invention. Since, as already described above, hydrolysis / condensation begins even with traces of moisture, the condensation products of the C ₁ -C ₆ -alkoxy-silanes of the formula (SI) and / or (S-II) are also included in this embodiment.

• - R₁, R₂ unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe stehen,
• - L für eine lineare oder verzweigte, zweiwertige C₁-C₂₀-Alkylengruppe steht,
• - R₃, R₄ unabhängig voneinander für eine C₁-C₆-Alkylgruppe stehen,
• - a, für eine ganze Zahl von 1 bis 3 steht, und
• - b für die ganze Zahl 3 - a steht, und

(R₅O)c(R6)dSi-(A)_e-[NR7-(A')]_f-[O-(A'')]_g-[NR8-(A''')]_h-Si(R6')_d'(OR5')_c' (S-II), wobei

• - R5, R5`, R5", R6, R6' und R6'' unabhängig voneinander für eine C₁-C₆-Alkylgruppe stehen,
• - A, A', A'', A''' und A'''' unabhängig voneinander für eine lineare oder verzweigte, zweiwertige C₁-C₂₀-Alkylengruppe stehen,
• - R₇ und R₈ unabhängig voneinander für ein Wasserstoffatom, eine C₁-C₆-Alkylgruppe, eine Hydroxy-C₁-C₆-alkylgruppe, eine C₂-C₆-Alkenylgruppe, eine Amino-C₁-C₆-alkylgruppe oder eine Gruppierung der Formel (S-III) stehen,

- (A'''')-Si(R₆")_d"(OR₅")_c'' (S-III),

• - c, für eine ganze Zahl von 1 bis 3 steht,
• - d für die ganze Zahl 3 - c steht,
• - c' für eine ganze Zahl von 1 bis 3 steht,
• - d' für die ganze Zahl 3 - c' steht,
• - c" für eine ganze Zahl von 1 bis 3 steht,
• - d'' für die ganze Zahl 3 - c'' steht,
• - e für 0 oder 1 steht,
• - f für 0 oder 1 steht,
• - g für 0 oder 1 steht,
• - h für 0 oder 1 steht,
• - mit der Maßgabe, dass mindestens einer der Reste aus e, f, g und h von 0 verschieden ist,

und/oder deren Kondensationsprodukte.In a further very particularly preferred embodiment, a method according to the invention is characterized in that the first composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (SI) and / or (S-II) contains, R ₁ R ₂ NL-Si (OR ₃ ) a (R ₄ ) b (SI) in which

• - R ₁ , R ₂ independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group,
• - L stands for a linear or branched, divalent C ₁ -C ₂₀ alkylene group,
• - R ₃ , R ₄ independently of one another represent a C ₁ -C ₆ -alkyl group,
• - a, stands for an integer from 1 to 3, and
• - b stands for the integer 3 - a, and

(R ₅ O) c (R6) dSi- (A) _e - [NR7- (A ')] _f - [O- (A ")] _g - [NR8- (A"')] _h -Si (R6 ') _d' (OR5 ') _c' (S-II), in which

• - R5, R5`, R5 ", R6, R6 'and R6" independently of one another represent a C ₁ -C ₆ -alkyl group,
• - A, A ', A'',A''' and A '''' independently of one another represent a linear or branched, divalent C ₁ -C ₂₀ alkylene group,
• - R ₇ and R ₈ independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy-C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an amino-C ₁ -C ₆ - alkyl group or a grouping of the formula (S-III),

- (A '''') - Si (R ₆ ") _d " (OR ₅ ") _c '' (S-III),

• - c, stands for an integer from 1 to 3,
• - d stands for the whole number 3 - c,
• - c 'stands for an integer from 1 to 3,
• - d 'stands for the whole number 3 - c',
• - c "stands for an integer from 1 to 3,
• - d '' stands for the whole number 3 - c '',
• - e stands for 0 or 1,
• - f stands for 0 or 1,
• - g stands for 0 or 1,
• - h stands for 0 or 1,
• - with the proviso that at least one of the radicals from e, f, g and h is different from 0,

and / or their condensation products.

The substituents R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₅ ', R ₅ ", R ₆ , R ₆ ', R _6" , R ₇ , R ₈ , L, A, A ' , A ", A""andA""'in the compounds of the formula (SI) and (S-II) are explained by way of example below: 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 hydroxy-C ₁ -C ₆ -alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group ; a 2-hydroxyethyl group is particularly preferred. Examples of an amino-C ₁ -C ₆ -alkyl group are the aminomethyl group, the 2-aminoethyl group and the 3-aminopropyl group. The 2-aminoethyl group is particularly preferred. Examples of a linear divalent C ₁ -C ₂₀ alkylene group are, for example, the methylene group (-CH ₂ -), the ethylene group (-CH ₂ -CH ₂ -), the propylene group (-CH ₂ -CH ₂ -CH ₂ - ) and the butylene group (-CH ₂ -CH ₂ -CH ₂ -CH ₂ -). The propylene group (-CH ₂ -CH ₂ -CH ₂ -) is particularly preferred. From a chain length of 3 carbon atoms, divalent alkylene groups can also be branched. Examples of branched, divalent C ₃ -C ₂₀ alkylene groups are (-CH ₂ -CH (CH ₃ ) -) and (-CH ₂ -CH (CH ₃ ) -CH ₂ -).

In the organic silicon compounds of the formula (SI) R ₁ R ₂ NL-Si (OR ₃ ) _a (R ₄ ) _b (SI), the radicals R ₁ and R ₂ independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group. The radicals R ₁ and R ₂ very particularly preferably both represent a hydrogen atom.

In the middle part of the organic silicon compound is the structural unit or the linker -L- which stands for a linear or branched, divalent C ₁ -C ₂₀ -alkylene group. The divalent C ₁ -C ₂₀ alkylene group can alternatively also be referred to as a divalent or divalent C ₁ -C ₂₀ alkylene group, which means that each grouping -L- can form two bonds.

-L- is preferably a linear, divalent C ₁ -C ₂₀ alkylene group. With further preference -L- stands for a linear divalent C ₁ -C ₆ alkylene group. -L- is particularly preferably a methylene group (-CH ₂ -), an ethylene group (-CH ₂ -CH ₂ -), a propylene group (-CH ₂ -CH ₂ -CH ₂ -) or a butylene group (-CH ₂ - CH ₂ -CH ₂ -CH ₂ -). L very particularly preferably represents a propylene group (—CH ₂ —CH ₂ —CH ₂ -).

The organic silicon compounds according to the invention of the formula (SI) R ₁ R ₂ NL-Si (OR ₃ ) _a (R ₄ ) _b (SI), each carry the silicon-containing group -Si (OR ₃ ) _a (R ₄ ) _{b at one end} .

In the terminal structural unit -Si (OR ₃ ) _a (R ₄ ) _b , the radicals R3 and R4 independently of one another represent a C ₁ -C ₆ -alkyl group, particularly preferably R ₃ and R ₄ independently of one another represent a methyl group or an ethyl group .

Here a stands for an integer from 1 to 3, and b stands for the integer 3 - a. If a is 3, then b is 0. If a is 2, b is 1. If a is 1, b is 2.

Keratin treatment agents with particularly good properties could be produced if the composition (A) contains at least one organic C ₁ -C ₆ -alkoxy-silane of the formula (SI) in which the radicals R ₃ , R ₄ independently of one another represent a methyl group or for stand for an ethyl group.

Furthermore, dyeings with the best wash fastness properties could be obtained if the composition (A) contains at least one organic C ₁ -C ₆ -alkoxy-silane of the formula (SI) in which the radical a stands for the number 3. In this case, the remainder b stands for the number 0.

• - R₃, R₄ unabhängig voneinander für eine Methylgruppe oder für eine Ethylgruppe stehen und
• - a für die Zahl 3 steht und
• - b für die Zahl 0 steht.

In a further preferred embodiment, a method according to the invention is characterized in that the composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes of the formula (SI), where

• - R ₃ , R ₄ independently of one another represent a methyl group or an ethyl group and
• - a stands for the number 3 and
• - b stands for the number 0.

• - R₁, R₂ beide für ein Wasserstoffatom stehen, und
• - L für eine lineare, zweiwertige C₁-C₆-Alkylengruppe, bevorzugt für eine Propylengruppe (-CH₂-CH₂-CH₂-) oder für eine Ethylengruppe (-CH₂-CH₂-), steht,
• - R₃ für eine Ethylgruppe oder eine Methylgruppe steht,
• - R₄ für eine Methylgruppe oder für eine Ethylgruppe steht,
• - a für die Zahl 3 steht und
• - b für die Zahl 0 steht.

In a further preferred embodiment, a method according to the invention is characterized in that the composition (A) contains at least one or more organic C ₁ -C ₆ -alkoxy-silanes of the formula (SI), R ₁ R ₂ NL-Si (OR ₃ ) _a (R ₄ ) _b (SI), in which

• - R ₁ , R ₂ both represent a hydrogen atom, and
• - L is a linear, divalent C ₁ -C ₆ alkylene group, preferably a propylene group (-CH ₂ -CH ₂ -CH ₂ -) or an ethylene group (-CH ₂ -CH ₂ -),
• - R _{3 stands} for an ethyl group or a methyl group,
• - R _{4 represents} a methyl group or an ethyl group,
• - a stands for the number 3 and
• - b stands for the number 0.

• - (3-Aminopropyl)triethoxysilan
  
• - (3-Aminopropyl)trimethoxysilan
  
• - (2-Aminoethyl)triethoxysilan
  
• - (2-Aminoethyl)trimethoxysilan
  
• - (3-Dimethylaminopropyl)triethoxysilan
  
• - (3-Dimethylaminopropyl)trimethoxysilan
  
• - (2-Dimethylaminoethyl)triethoxysilan.
  
• - (2-Dimethylaminoethyl)trimethoxysilan und/oder
  

Organic silicon compounds of the formula (I) which are particularly suitable for achieving the object of the invention are

• - (3-aminopropyl) triethoxysilane
  
• - (3-aminopropyl) trimethoxysilane
  
• - (2-aminoethyl) triethoxysilane
  
• - (2-aminoethyl) trimethoxysilane
  
• - (3-Dimethylaminopropyl) triethoxysilane
  
• - (3-Dimethylaminopropyl) trimethoxysilane
  
• - (2-Dimethylaminoethyl) triethoxysilane.
  
• - (2-Dimethylaminoethyl) trimethoxysilane and / or
  

• - (3-Aminopropyl)triethoxysilan
• - (3-Aminopropyl)trimethoxysilan
• - (2-Aminoethyl)triethoxysilan
• - (2-Aminoethyl)trimethoxysilan
• - (3-Dimethylaminopropyl)triethoxysilan
• - (3-Dimethylaminopropyl)trimethoxysilan
• - (2-Dimethylaminoethyl)triethoxysilan,
• - (2-Dimethylaminoethyl)trimethoxysilan und/oder deren Kondensationsprodukten.

In a further preferred embodiment, a method according to the invention is characterized in that the first composition (A) contains at least one organic C ₁ -C ₆ -alkoxysilane (A1) of the formula (SI) which is selected from the group of

• - (3-aminopropyl) triethoxysilane
• - (3-aminopropyl) trimethoxysilane
• - (2-aminoethyl) triethoxysilane
• - (2-aminoethyl) trimethoxysilane
• - (3-Dimethylaminopropyl) triethoxysilane
• - (3-Dimethylaminopropyl) trimethoxysilane
• - (2-dimethylaminoethyl) triethoxysilane,
• - (2-Dimethylaminoethyl) trimethoxysilane and / or their condensation products.

The aforementioned organic silicon compounds of the formula (I) are commercially available. (3-Aminopropyl) trimethoxysilane can be purchased from Sigma-Aldrich, for example. (3-Aminopropyl) triethoxysilane is also commercially available from Sigma-Aldrich.

In a further embodiment of the process according to the invention, the composition (A) can also contain one or more organic C ₁ -C ₆ -alkoxy-silanes of the formula (S-II), (R ₅ O) _c (R6) _d Si- (A) _e - [NR7- (A ')] _f - [O- (A ")] _g - [NR ₈ - (A''')] _h - Si (R6 ') _d' (OR ₅ ') _c' (S-II).

The organosilicon compounds of the formula (S-II) according to the invention each have the silicon-containing groups (R ₅ O) _c (R ₆ ) _d Si and -Si (R ₆ ') _d' (OR ₅ ') at both ends _{c '} .

In the middle part of the molecule of the formula (S-II) there are the groupings - (A) _e - and - [NR ₇ - (A ')] _f - and - [O- (A'')] _g - and - [ NR ₈ - (A '')] _h -. Each of the radicals e, f, g and h can independently represent the number 0 or 1, with the proviso that at least one of the radicals e, f, g and h is different from zero. In other words, an organic silicon compound of the formula (II) according to the invention contains at least one group from the group consisting of - (A) - and - [NR ₇ - (A ')] - and - [O- (A ″)] - and - [NR ₈ - (A ''')] -.

In the two terminal structural units (R ₅ O) _c (R ₆ ) _d Si and Si (R ₆ ') _d' (OR ₅ ') _c' , the radicals R5, R5 ', R5''independently of one another represent a C ₁ -C ₆ alkyl group. The radicals R6, R6 'and R6 "independently of one another represent a C ₁ -C ₆ -alkyl group.

Here, c stands for an integer from 1 to 3, and d stands for the integer 3 - c. If c is 3, then d is 0. If c is 2, d is 1. If c is 1, d is 2.

Similarly, c 'stands for an integer from 1 to 3, and d' stands for the integer 3 - c '. If c 'stands for the number 3, then d' equals 0. If c 'stands for the number 2, then d' equals 1. If c 'stands for the number 1, then d' equals 2.

Dyeings with the best wash fastness could be obtained if the residues c and c 'both stand for the number 3. In this case, d and d 'both stand for the number 0.

• - R5 und R5' unabhängig voneinander für eine Methylgruppe oder eine Ethylgruppe stehen,
• - c und c' beide für die Zahl 3 stehen und
• - d und d' beide für die Zahl 0 stehen.

In a further preferred embodiment, a method according to the invention is characterized in that the composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes of the formula (S-II), (R ₅ O) c (R6) dSi- (A) _e - [NR7- (A ')] _f - [O- (A ")] _g - [NR8- (A'")] _h -Si (R6 ') _d' (OR5 ') _c' (S-II), in which

• - R5 and R5 'independently of one another represent a methyl group or an ethyl group,
• - c and c 'both stand for the number 3 and
• - d and d 'both stand for the number 0.

If c and c 'both stand for the number 3 and d and d' both stand for the number 0, the organic silicon compounds according to the invention correspond to the formula (S-IIa) (R ₅ O) ₃ Si- (A) _e - [NR7- (A ')] _f - [O- (A ")] _g - [NR ₈ - (A'")] _h -Si (OR ₅ ' ) ₃ (S-IIa).

The radicals e, f, g and h can independently represent the number 0 or 1, at least one radical from e, f, g and h being different from zero. The abbreviations e, f, g and h define which of the groupings - (A) _e - and - [NR ₇ - (A ')] _f - and - [O- (A'')] _g - and - [NR ₈ - (A ''')] _h - are located in the central part of the organic silicon compound of the formula (II).

In this context, the presence of certain groups has proven to be particularly advantageous with regard to achieving washfast dyeing results. Particularly good results could be obtained when at least two of the radicals e, f, g and h stand for the number 1. Very particularly preferably e and f both stand for the number 1. Furthermore, with very particular preference g and h both stand for the number 0.

If e and f both stand for the number 1 and g and h both stand for the number 0, the organic silicon compounds according to the invention correspond to the formula (S-IIb) (R ₅ O) _c (R6) _d Si (A) - [NR ₇ - (A ')] - Si (R6') _{d '} (OR ₅ ') _{c '} (S-IIb).

The radicals A, A ', A ", A""andA""" stand independently of one another for a linear or branched, divalent C ₁ -C ₂₀ alkylene group. The radicals A, A ', A ", A''' and A '''', independently of one another, are preferably a linear, divalent C ₁ -C ₂ o-alkylene group. The radicals A, A ', A' are more preferably ', A''' and A '''' independently of one another for a linear divalent C ₁ -C ₆ alkylene group.

The divalent C ₁ -C ₂₀ alkylene group can alternatively also be referred to as a divalent or divalent C ₁ -C ₂₀ alkylene group, which means that each grouping A, A ', A ", A"' and A ''''can form two bonds.

The radicals A, A ', A'',A''' and A '''' are particularly preferably, independently of one another, a methylene group (-CH ₂ -), an ethylene group (-CH ₂ -CH ₂ -), a propylene group (-CH ₂ -CH ₂ -CH ₂ -) or a butylene group (-CH ₂ -CH ₂ -CH ₂ -CH ₂ -). The radicals A, A ', A'',A''' and A '''' very particularly preferably represent a propylene group (—CH ₂ —CH ₂ —CH ₂ -).

If the radical f stands for the number 1, then the organic silicon compound of the formula (II) according to the invention contains a structural grouping - [NR ₇ - (A ')] -. If the radical h stands for the number 1, then the organic silicon compound of the formula (II) according to the invention contains a structural grouping - [NR ₈ - (A "')] -.

The radicals R ₇ and R ₈ independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy-C ₁ -C ₆ -alkyl group, a C ₂ -C ₆ -alkenyl group, an amino-C ₁ - C ₆ alkyl group or a grouping of the formula (S-III) - (A '''') - Si (R6 '') d '' (OR5 '') c '' (S-III).

The radicals R7 and R8 are very particularly preferably, independently of one another, a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a grouping of the formula (S-III).

If the radical f stands for the number 1 and the radical h stands for the number 0, the organic silicon compound according to the invention contains the grouping [NR ₇ - (A ')], but not the grouping - [NR ₈ - (A''' )]. If the radical R7 now stands for a grouping of the formula (III), the organic silicon compound comprises 3 reactive silane groups.

• - e und f beide für die Zahl 1 stehen,
• - g und h beide für die Zahl 0 stehen,
• - A und A' unabhängig voneinander für eine lineare, zweiwertige C₁-C₆-Alkylengruppe stehen und
• - R7 für ein Wasserstoffatom, eine Methylgruppe, eine 2-Hydroxyethylgruppe, eine 2-Alkenylgruppe, eine 2-Aminoethylgruppe oder für eine Gruppierung der Formel (S-III) steht.

In a further preferred embodiment, a method according to the invention is characterized in that the composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (S-II) (R ₅ O) c (R6) dSi- (A) _e - [NR7- (A ')] _f - [O- (A ")] _g - [NR8- (A"')] _h -Si (R6 ') _d' (OR5 ') _c' (S-II), in which

• - e and f both stand for the number 1,
• - g and h both stand for the number 0,
• - A and A 'independently of one another represent a linear, divalent C ₁ -C ₆ -alkylene group and
• - R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a grouping of the formula (S-III).

• - e und f beide für die Zahl 1 stehen,
• - g und h beide für die Zahl 0 stehen,
• - A und A' unabhängig voneinander für eine Methylengruppe (-CH₂-), eine Ethylengruppe (-CH₂-CH₂-) oder eine Propylengruppe (-CH₂-CH₂-CH₂) stehen,

und

• - R7 für ein Wasserstoffatom, eine Methylgruppe, eine 2-Hydroxyethylgruppe, eine 2-Alkenylgruppe, eine 2-Aminoethylgruppe oder für eine Gruppierung der Formel (S-III) steht.

In a further preferred embodiment, a method according to the invention is characterized in that the composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (S-II), where

• - e and f both stand for the number 1,
• - g and h both stand for the number 0,
• - A and A 'independently represent a methylene group (-CH ₂ -), an ethylene group (-CH ₂ -CH ₂ -) or a propylene group (-CH ₂ -CH ₂ -CH ₂ ),

and

• - R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a grouping of the formula (S-III).

• - 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamin
  
• - 3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamin
  
• 
  -N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamin
  
• - 2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol
  
• - 2-[Bis[3-(triethoxysilyl)propyl]amino]-ethanol
  
• - 3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamin
  
• - 3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamin
  
• - N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamin,
  
• - N1 ,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamin,
  
• - N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amin
  
• - N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amin
  

Organic silicon compounds of the formula (S-II) which are very suitable for achieving the object of the invention are

• - 3- (Trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine
  
• - 3- (Triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine
  
• 
  -N-methyl-3- (triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine
  
• - 2- [bis [3- (trimethoxysilyl) propyl] amino] ethanol
  
• - 2- [bis [3- (triethoxysilyl) propyl] amino] ethanol
  
• - 3- (Trimethoxysilyl) -N, N-bis [3- (trimethoxysilyl) propyl] -1-propanamine
  
• - 3- (Triethoxysilyl) -N, N-bis [3- (triethoxysilyl) propyl] -1-propanamine
  
• - N1, N1-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine,
  
• - N1, N1-bis [3- (triethoxysilyl) propyl] -1,2-ethanediamine,
  
• - N, N-bis [3- (trimethoxysilyl) propyl] -2-propen-1-amine
  
• - N, N-bis [3- (triethoxysilyl) propyl] -2-propen-1-amine
  

The aforementioned organic silicon compounds of the formula (S-II) are commercially available. Bis (trimethoxysilylpropyl) amine with the CAS number 82985-35-1 can be purchased from Sigma-Aldrich, for example.
Bis [3- (triethoxysilyl) propyl] amine with the CAS number 13497-18-2 can be purchased from Sigma-Aldrich, for example.
N-methyl-3- (trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine is alternatively referred to as bis (3-trimethoxysilylpropyl) -N-methylamine and can be purchased commercially from Sigma-Aldrich or Fluorochem .

3- (Triethoxysilyl) -N, N-bis [3- (triethoxysilyl) propyl] -1-propanamine with the CAS number 18784-74-2 can be purchased from Fluorochem or Sigma-Aldrich, for example.

• - 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamin
• - 3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamin
• - N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamin
• - N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamin
• - 2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol
• - 2-[Bis[3-(triethoxysilyl)propyl]amino]-ethanol
• - 3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-Propanamin
• - 3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-Propanamin
• - N1 ,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-Ethanediamin,
• - N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-Ethanediamin,
• - N,N-Bis[3-(trimethoxysilyl)propyl]-2-Propen-1-amin und/oder
• - N,N-Bis[3-(triethoxysilyl)propyl]-2-Propen-1-amin,

und/oder deren Kondensationsprodukten.In a further preferred embodiment, a method according to the invention is characterized in that the composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes of the formula (S-II) which are selected from the group of

• - 3- (Trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine
• - 3- (Triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine
• - N-methyl-3- (trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine
• - N-methyl-3- (triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine
• - 2- [bis [3- (trimethoxysilyl) propyl] amino] ethanol
• - 2- [bis [3- (triethoxysilyl) propyl] amino] ethanol
• - 3- (Trimethoxysilyl) -N, N-bis [3- (trimethoxysilyl) propyl] -1-propanamine
• - 3- (Triethoxysilyl) -N, N-bis [3- (triethoxysilyl) propyl] -1-propanamine
• - N1, N1-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine,
• - N1, N1-bis [3- (triethoxysilyl) propyl] -1,2-ethanediamine,
• - N, N-bis [3- (trimethoxysilyl) propyl] -2-propene-1-amine and / or
• - N, N-bis [3- (triethoxysilyl) propyl] -2-propen-1-amine,

and / or their condensation products.

In further dyeing tests it has also been found to be particularly advantageous if at least one organic C ₁ -C ₆ -alkoxy-silane (A1) of the formula (S-IV) was used in the process according to the invention R ₉ Si (OR ₁₀ ) k (R ₁₁ ) m (S-IV).

The compounds of formula (S-IV) are organic silicon compounds selected from silanes having one, two or three silicon atoms, the organic silicon compound comprising one or more hydrolyzable groups per molecule.

• - R₉ für eine C₁-C₁₂-Alkylgruppe steht,
• - R₁₀ für eine C₁-C₆-Alkylgruppe steht,
• - R₁₁ für eine C₁-C₆-Alkylgruppe steht
• - k für eine ganze Zahl von 1 bis 3 steht, und
• - m für die ganze Zahl 3 - k steht.

The organic silicon compound or compounds of the formula (S-IV) can also be referred to as silanes of the alkyl-C ₁ -C ₆ -alkoxysilane type, R ₉ Si (OR ₁₀ ) _k (R11) m (S-IV), in which

• - R _{9 stands} for a C ₁ -C ₁₂ -alkyl group,
• - R _{10 represents} a C ₁ -C ₆ -alkyl group,
• - R _{11 represents} a C ₁ -C ₆ alkyl group
• - k stands for an integer from 1 to 3, and
• - m stands for the integer 3 - k.

• - R₉ für eine C₁-C₁₂-Alkylgruppe steht,
• - R₁₀ für eine C₁-C₆-Alkylgruppe steht,
• - R₁₁ für eine C₁-C₆-Alkylgruppe steht
• - k für eine ganze Zahl von 1 bis 3 steht, und
• - m für die ganze Zahl 3 - k steht,

und/oder deren Kondensationsprodukte.In a further embodiment, a particularly preferred method according to the invention is characterized in that the first composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (S-IV), R ₉ Si (OR ₁₀ ) _k (R ₁₁ ) m (S-IV), in which

• - R _{9 stands} for a C ₁ -C ₁₂ -alkyl group,
• - R _{10 represents} a C ₁ -C ₆ -alkyl group,
• - R _{11 represents} a C ₁ -C ₆ alkyl group
• - k stands for an integer from 1 to 3, and
• - m stands for the integer 3 - k,

and / or their condensation products.

In the organic C ₁ -C ₆ -alkoxy-silanes of the formula (S-IV), the radical R _{9 stands} for a C ₁ -C ₁₂ -alkyl group. This C ₁ -C ₁₂ -alkyl group is saturated and can be linear or branched. R ₉ is preferably a linear C ₁ -C ₈ -alkyl group. R ₉ preferably stands for a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group or an n-dodecyl group. R ₉ particularly preferably represents a methyl group, an ethyl group or an n-octyl group.

In the organic silicon compounds of the formula (S-IV), the radical R _{10 represents} a C ₁ -C ₆ -alkyl group. R ₁₀ particularly preferably represents a methyl group or an ethyl group.

In the organic silicon compounds of the formula (S-IV), the radical R _{11 is} a C ₁ -C ₆ -alkyl group. R ₁₁ particularly preferably represents a methyl group or an ethyl group.

Furthermore, k stands for an integer from 1 to 3, and m stands for the integer 3 - k. If k is the number 3, then m is 0. If k is the number 2, then m is 1. If k is the number 1, then m is 2.

Dyeings with the best wash fastness properties could be obtained if the composition (A) contains at least one organic C ₁ -C ₆ -alkoxy-silane (A1) of the formula (S-IV) in which the radical k stands for the number 3. In this case, the remainder m stands for the number 0.

• - Methyltrimethoxysilan
  
• - Methyltriethoxysilan
  
• - Ethyltrimethoxysilan
  
• - Ethyltriethoxysilan
  
  - n-Propyltrimethoxysilan (auch bezeichnet ans Propyltrimethoxysilan)
  
• - n-Propyltriethoxysilan (auch bezeichnet als Propyltriethoxysilan)
  
• - n-Hexyltrimethoxysilan (auch bezeichnet als Hexyltrimethoxysilan)
  
• - n-Hexyltriethoxysilan (auch bezeichnet als Hexyltriethoxysilan)
  
• - n-Octyltrimethoxysilan (auch bezeichnet als Octyltrimethoxysilan)
  
• - n-Octyltriethoxysilan (auch bezeichnet als Octyltriethoxysilan)
  
• - n-Dodecyltrimethoxysilan (auch bezeichnet als Dodecyltrimethoxysilan) und/oder
  
• - n-Dodecyltriethoxysilan (auch bezeichnet als Dodecyltriethoxysilan).
  

Organic silicon compounds of the formula (S-IV) which are particularly suitable for achieving the object of the invention are

• - methyltrimethoxysilane
  
• - methyltriethoxysilane
  
• - ethyltrimethoxysilane
  
• - ethyltriethoxysilane
  
  - n-propyltrimethoxysilane (also called ans propyltrimethoxysilane)
  
• - n-propyltriethoxysilane (also known as propyltriethoxysilane)
  
• - n-Hexyltrimethoxysilane (also known as hexyltrimethoxysilane)
  
• - n-Hexyltriethoxysilane (also called hexyltriethoxysilane)
  
• - n-Octyltrimethoxysilane (also called octyltrimethoxysilane)
  
• - n-Octyltriethoxysilane (also called octyltriethoxysilane)
  
• - n-Dodecyltrimethoxysilane (also referred to as dodecyltrimethoxysilane) and / or
  
• - n-Dodecyltriethoxysilane (also known as dodecyltriethoxysilane).
  

• - Methyltrimethoxysilan
• - Methyltriethoxysilan
• - Ethyltrimethoxysilan
• - Ethyltriethoxysilan
• - Hexyltrimethoxysilan
• - Hexyltriethoxysilan
• - Octyltrimethoxysilan
• - Octyltriethoxysilan
• - Dodecyltrimethoxysilan,
• - Dodecyltriethoxysilan,

und/oder deren Kondensationsprodukten.In a further preferred embodiment, a method according to the invention is characterized in that the first composition (A) contains at least one organic C ₁ -C ₆ -alkoxysilane (A1) of the formula (S-IV) which is selected from the group of

• - methyltrimethoxysilane
• - methyltriethoxysilane
• - ethyltrimethoxysilane
• - ethyltriethoxysilane
• - hexyltrimethoxysilane
• - hexyltriethoxysilane
• - Octyltrimethoxysilane
• - octyltriethoxysilane
• - dodecyltrimethoxysilane,
• - dodecyltriethoxysilane,

and / or their condensation products.

The corresponding hydrolysis or condensation products are, for example, the following compounds. The condensation products represent a maximum of oligomeric compounds, but not polymers.

Hydrolysis of C ₁ -C ₆ -alkoxy-silane of the formula (SI) with water (reaction scheme using the example of 3-aminopropyltriethoxysilane):

bzw.

Depending on the amount of water used, the hydrolysis reaction can also take place several times per C ₁ -C ₆ -alkoxy-silane used:

or.

In Abhängigkeit von der eingesetzten Menge an Wasser kann die Hydrolyse-Reaktion auch mehrfach pro eingesetztem C₁-C₆-Alkoxy-Silan stattfinden:

bzw.

Hydrolysis of C ₁ -C ₆ -alkoxy-silane of the formula (S-IV) with water (reaction scheme using the example of methyltrimethoxysilane):

Depending on the amount of water used, the hydrolysis reaction can also take place several times per C ₁ -C ₆ -alkoxy-silane used:

or.

und/oder

und/oder

und/oder

und/oder

und/oder

und/oder

Possible condensation reactions are for example (shown using the mixture (3-aminopropyl) triethoxysilane and methyltrimethoxysilane):

and or

and or

and or

and or

and or

and or

In the above exemplary reaction schemes, the condensation to form a dimer is shown in each case, but further condensation to form oligomers with several silane atoms are also possible and also preferred.

Both partially hydrolyzed and fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (SI) can take part in these condensation reactions, which condensation with as yet unreacted, partially or completely hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (SI) run through. In this case, the C ₁ -C ₆ -alkoxysilanes of the formula (SI) react with themselves.

Furthermore, both partially hydrolyzed and fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (SI) can also take part in the condensation reactions, which condensation with as yet unreacted, partially or completely hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula ( S-IV). In this case, the C ₁ -C ₆ alkoxysilanes of the formula (SI) react with the C ₁ -C ₆ alkoxysilanes of the formula (S-IV).

In addition, both partially hydrolyzed and fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (S-IV), which undergo condensation with unreacted, partially or completely hydrolyzed C ₁ -C ₆ -alkoxysilanes, can also take part in the condensation reactions Run through formula (S-IV). In this case, the C ₁ -C ₆ -alkoxysilanes of the formula (S-IV) react with themselves.

The composition (A) according to the invention can contain one or more organic C ₁ -C ₆ -alkoxysilanes (A1) in various proportions. The person skilled in the art determines this as a function of the desired thickness of the silane coating on the keratin material and of the amount of the keratin material to be treated.

Particularly storage-stable preparations with very good coloring results on use could be obtained if the composition (A) - based on its total weight - has one or more organic C ₁ -C ₆ -alkoxysilanes (A1) and / or the condensation products thereof in a total amount of 30.0 to 85.0% by weight, preferably from 35.0 to 80.0% by weight, more preferably from 40.0 to 75.0% by weight, even more preferably from 45.0 to 70 , 0% by weight and very particularly preferably from 50.0 to 65.0% by weight.

In a further embodiment, a very particularly preferred method is characterized in that the first composition (A) - based on the total weight of the composition (A) - has one or more organic C ₁ -C ₆ alkoxysilanes (A2) and / or the condensation products thereof in a total amount of 30.0 to 85.0% by weight, preferably from 35.0 to 80.0% by weight, more preferably from 40.0 to 75.0% by weight, even more preferably from 45.0 to 70.0% by weight and very particularly preferably from 50.0 to 65.0% by weight.

Further cosmetic ingredients in composition (A)

In addition, the composition (A) can also contain one or more further cosmetic ingredients.

The cosmetic ingredients which can optionally be used in the composition (A) can be all suitable constituents in order to impart further positive properties to the agent. For example, a solvent, a surface-active compound from the group of nonionic, cationic, anionic or zwitterionic / amphoteric surfactants, the coloring compounds from the group of pigments, substantive dyes, oxidation dye precursors, and the fatty components from the group can be used in composition (A) the C ₈ -C ₃₀ fatty alcohols, the hydrocarbon compounds, fatty acid esters, the acids and bases belonging to the group of pH regulators, those of the perfumes, the preservatives, the plant extracts and the protein hydrolysates.

The person skilled in the art will select these additional substances according to the desired properties of the agents. With regard to further optional components and the amounts of these components used, express reference is made to the relevant manuals known to the person skilled in the art.

In this context, it has proven to be very particularly preferred to use a cosmetic ingredient from the group of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane in composition (A).

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the first composition (A) contains at least one cosmetic ingredient from the group consisting of hexamethyldisiloxane. Contains octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

Hexamethyldisiloxane has the CAS number 107-46-0 and can be obtained commercially from Sigma-Aldrich, for example.

Octamethyltrisiloxane has the CAS number 107-51-7 and is also commercially available from Sigma-Aldrich.

• Hexamethylcyclotrisiloxan besitzt die CAS-Nr. 541-05-9.
• Octamethylcyclotetrasiloxan besitzt die CAS-Nr. 556-67-2.
• Decamethylcyclopentasiloxan besitzt die CAS-Nr. 541-02-6.

Decamethyltetrasiloxane has the CAS number 141-62-8 and is also commercially available from Sigma-Aldrich.

• Hexamethylcyclotrisiloxane has the CAS no. 541-05-9.
• Octamethylcyclotetrasiloxane has the CAS no. 556-67-2.
• Decamethylcyclopentasiloxane has the CAS no. 541-02-6.

The use of hexamethyldisiloxane in composition (A) has proven to be very particularly preferred. Hexamethyldisiloxane is particularly preferred - based on the total weight of the composition (A) - in amounts of 1.0 to 20.0% by weight, preferably 1.3 to 10.0% by weight, more preferably 1.6 up to 5.0% by weight and very particularly preferably from 2.0 to 4.0% by weight in the composition (A).

Water content (A1) in the composition (A)

The method according to the invention is characterized by the use of a first composition (A) on the keratinic material.

In the context of the present invention, composition (A) is a ready-to-use composition which, in its present embodiment, can be applied to the keratin materials, in particular to the hair.

In the context of the process according to the invention, the composition (A) can either be provided in its present form in a container. With the C ₁ -C ₆ -alkoxy-silanes, however, the composition (A) contains very reactive compounds. In order to avoid problems in connection with the storage stability, however, it is particularly preferred to prepare the ready-to-use and reactive composition (A) shortly before use by mixing two or more storage-stable compositions. For example, the ready-to-use composition (A) can be prepared by mixing a water-free silane blend (AI), which contains the organic C ₁ -C ₆ -alkoxy-silane (s) (A1) in concentrated form, and a water-rich carrier formulation ( A-II), which can be a gel, a lotion or a surfactant system, for example.

The ready-to-use composition (A) accordingly preferably has a higher water content, which - based on the total weight of the composition (A) - is in the range from 50.0 to 90.0% by weight, preferably from 55.0 to 90.0% by weight .-%, more preferably 60.0 to 90.0% by weight and particularly preferably 70.0 to 90.0% by weight.

In a further embodiment, a method according to the invention is characterized in that the first composition (A) - based on the total weight of the composition (A) - 50.0 to 90.0% by weight, preferably from 55.0 to 90, Contains 0% by weight, more preferably 60.0 to 90.0% by weight and particularly preferably 70.0 to 90.0% by weight of water.

pH of the compositions (A)

In further experiments it has been found that the pH values of the composition (A) can have an influence on the color intensities obtained during the dyeing. It was found here that alkaline pH values in particular have an advantageous effect on the dyeing performance that can be achieved in the process.

For this reason, it is preferred that the compositions (A) have a pH of from 7.0 to 12.0, preferably from 7.5 to 11.5, more preferably from 8.0 to 11.0 and very particularly preferably from 8.0 to 10.5.

The pH value can be measured using the usual methods known from the prior art, such as measuring the pH value by means of glass electrodes using single-rod measuring chains or using pH indicator paper.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the composition (A) has a pH of from 7.0 to 12.0, preferably from 7.5 to 11.5, more preferably from 8.0 to 11.0 and very particularly preferably from 8.0 to 10.5.

To set the abovementioned pH values, it is possible to use the alkalizing agents which can also be used to set the pH value of the composition (B).

Oxidation dye precursors in composition (B)

The method according to the invention comprises the application of a second composition (B) to the keratin material. The composition (B) is characterized in that it contains at least one oxidation dye precursor (B1).

Developer components, also called developers for short, and / or coupler components, called couplers for short, can be used as oxidation dye precursors.

Primary aromatic amines with a further free or substituted hydroxyl or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its are usually used as developer components or developers Derivatives used.

wobei

• - G¹ steht für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen 4'-Aminophenylrest oder einen (C₁ bis C₄)-Alkylrest, der mit einer stickstoffhaltigen Gruppe, einem Phenyl- oder einem 4'-Aminophenylrest substituiert ist;
• - G² steht für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest oder einen (C₁ bis C₄)-Alkylrest, der mit einer stickstoffhaltigen Gruppe substituiert ist;
• - G³ steht für ein Wasserstoffatom, ein Halogenatom, wie ein Chlor-, Brom-, lod- oder Fluoratom, einen (C₁ bis C₄)-Alkylrest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Hydroxyalkoxyrest, einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Acetylaminoalkoxyrest, einen Mesylamino-(C₁ bis C₄)-alkoxyrest

oder einen (C₁ bis C₄)-Carbamoylaminoalkoxyrest;

• - G⁴ steht für ein Wasserstoffatom, ein Halogenatom, einen (C₁ bis C₄)-Alkylrest oder einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, oder
• - wenn G³ und G⁴ in ortho-Stellung zueinander stehen, können sie gemeinsam eine verbrückende α,ω-Atkytendioxogruppe, wie beispielsweise eine Ethylendioxygruppe bilden.

According to the invention, it can be preferred to use a p-phenylenediamine derivative or one of its physiologically tolerable salts as the developer component. Particularly preferred are p-phenylenediamine derivatives of the formula (E1)

in which

• - G ¹ represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy- (C ₁ to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a (C ₁ to C ₄ ) -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;
• - G ² represents a hydrogen atom, a (C ₁ to C ₄ ) alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) polyhydroxyalkyl radical, a (C ₁ to C ₄ ) - Alkoxy- (C ₁ to C ₄ ) -alkyl radical or a (C ₁ to C ₄ ) -alkyl radical which is substituted by a nitrogen-containing group;
• - G ³ stands for a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or fluorine atom, a (C ₁ to C ₄ ) -alkyl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) polyhydroxyalkyl radical, a (C ₁ to C ₄ ) hydroxyalkoxy radical, a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl radical, a (C ₁ to C ₄ ) acetylaminoalkoxy radical, a mesylamino (C ₁ to C ₄ ) alkoxy radical

or a (C ₁ to C ₄ ) carbamoylaminoalkoxy radical;

• - G ⁴ stands for a hydrogen atom, a halogen atom, a (C ₁ to C ₄ ) -alkyl radical or a (C ₁ to C ₄ ) -alkoxy- (C ₁ to C ₄ ) -alkyl radical, or
• - If G ³ and G ^{4 are} in the ortho position to one another, they can together form a bridging α, ω-Atkytendioxogruppe, such as an ethylenedioxy group.

Particularly preferred p-phenylenediamines of the formula (E1) are selected from one or more compounds of the group which is formed from p-phenylenediamine, p-tolylenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine , 2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine , N, N-dipropyl-p-phenylenediamine, 4-amino-3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N -Bis- (β-hydroxyethyl) -amino-2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) -amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- ( α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N -Dimethyl-3-methyl-p-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) - p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-Hydroxyethyloxy) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, 2- (β-acetylamino-ethyloxy) -p-phenylenediamine, N- (β-methoxyethyl) -p-phenylenediamine, N- (4-amino -3-methylphenyl) -N- [3- (1H-imidazol-1-yl) propyl] amine, 5,8-diaminobenzo-1,4-dioxane and their physiologically tolerable salts.

According to the invention very particularly preferred p-phenylenediamine derivatives of the formula (E1) are selected from at least one compound from the group p-phenylenediamine, p-tolylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (a, ß-dihydroxyethyl) - p-phenylenediamine, N, N-bis (β-hydroxyethyl) -p-phenylenediamine, 2-methoxymethyl-p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H -imidazole -1-yl) propyl] amine, and the physiologically acceptable salts of these compounds.

According to the invention, it may furthermore be preferred to use compounds as developer components which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

wobei:

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

mit der Maßgabe, dass die Verbindungen der Formel (E2) nur eine Verbrückung Y pro Molekül enthalten.Among the binuclear developer components which can be used in the dyeing compositions according to the invention, one can in particular mention the compounds which correspond to the following formula (E2), as well as their physiologically tolerable salts:

in which:

• - Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical, which is optionally substituted by a (C ₁ to C ₄ ) alkyl radical, by a (C ₁ to C ₄ ) hydroxyalkyl radical and / or by a bridge Y is substituted or which is optionally part of a bridging ring system,
• The bridge Y stands for an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is interrupted or terminated by one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms can be and may be substituted by one or more hydroxyl or (C ₁ to C ₈ ) alkoxy radicals, or a direct bond,
• - G ⁵ and G ⁶ independently represent a hydrogen or halogen atom, a (C ₁ to C ₄ ) alkyl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) polyhydroxyalkyl radical, a (C ₁ to C ₄ ) aminoalkyl radical or a direct connection to the bridge Y,
• - G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently of one another represent a hydrogen atom, a direct bond to the bridge Y or a (C ₁ to C ₄ ) -alkyl radical,

with the proviso that the compounds of the formula (E2) contain only one bridge Y per molecule.

According to the invention, the substituents used in formula (E2) are defined analogously to the above statements.

Preferred binuclear developer components of the formula (E2) are selected in particular from at least one of the following compounds: N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) -1,3-diamino -propan-2-ol, N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -ethylenediamine, N, N'-bis- (4'-aminophenyl) - tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -tetramethylenediamine, N, N'-bis- (4- (methylamino) phenyl) -tetramethylenediamine, N , N'-Diethyl-N, N'-bis- (4'-amino-3'-methylphenyl) -ethylenediamine, bis- (2-hydroxy-5-aminophenyl) -methane, N, N'-bis- (4 '-aminophenyl) -1,4-diazacycloheptane, N, N'-bis- (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p-phenylenediamine and 1,10-bis- ( 2 ', 5'-diaminophenyl) -1,4,7,10-tetraoxadecane and their physiologically acceptable salts.

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

wobei:

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

Furthermore, it can be preferred according to the invention to use a p-aminophenol derivative or one of its physiologically tolerable salts as the developer component. Particularly preferred are p-aminophenol derivatives of the formula (E3)

in which:

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

According to the invention, the substituents used in formula (E3) are defined analogously to the above statements.

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

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

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

Furthermore, the developer component can be selected from heterocyclic developer components, such as, for example, from pyrimidine derivatives, pyrazole derivatives, pyrazolopyrimidine derivatives or their physiologically tolerable salts.

worin

• - G¹⁷, G¹⁸ und G¹⁹ unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁ bis C₄)-Alkoxygruppe oder eine Aminogruppe steht und
• - G²⁰ für eine Hydroxygruppe oder eine Gruppe -NG²¹G²² steht, worin G²¹ und G²² unabhängig voneinander stehen für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe,

mit der Maßgabe, dass maximal zwei der Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ eine Hydroxygruppe bedeuten und höchstens zwei der Reste G¹⁷, G¹⁸ und G¹⁹ für ein Wasserstoffatom stehen. Dabei ist es wiederum bevorzugt, wenn gemäß Formel (E4) mindestens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Gruppe -NG²¹G²² stehen und höchstens zwei Gruppen aus G¹⁷, G¹⁸, G¹⁹ und G²⁰ für eine Hydroxygruppe stehen.Preferred pyrimidine derivatives are selected according to the invention from compounds according to formula (E4) or their physiologically tolerable salts,

wherein

• - G ¹⁷ , G ¹⁸ and G ¹⁹ independently of one another represent a hydrogen atom, a hydroxyl group, a (C ₁ to C ₄ ) alkoxy group or an amino group and
• - G ^{20 represents} a hydroxy group or a group -NG ²¹ G ²² , in which G ²¹ and G ²² independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -monohydroxyalkyl group ,

with the proviso that a maximum of two of the groups from G ¹⁷ , G ¹⁸ , G ¹⁹ and G ^{20 represent} a hydroxyl group and a maximum of two of the radicals G ¹⁷ , G ¹⁸ and G ^{19 represent} a hydrogen atom. It is again preferred if, according to formula (E4), at least two groups from G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ stand for a group -NG ²¹ G ²² and at most two groups from G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ stand for a hydroxyl group.

Particularly preferred pyrimidine derivatives are in particular the compounds 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5 , 6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyrimidine.

worin

• - G²³, G²⁴, G²⁵ stehen unabhängig voneinander für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe, eine (C₂ bis C₄)-Polyhydroxyalkylgruppe, eine gegebenenfalls substituierte Arylgruppe oder eine gegebenenfalls substituierte Aryl-(C₁ bis C₄)-alkylgruppe, mit der Maßgabe dass, wenn G²⁵ für ein Wasserstoffatom steht, G²⁶ neben den vorgenannten Gruppen zusätzlich für eine Gruppe -NH₂ stehen kann,
• - G²⁶ steht für ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₁ bis C₄)-Monohydroxyalkylgruppe oder eine (C₂ bis C₄)-Polyhydroxyalkylgruppe und
• - G²⁷ steht für ein Wasserstoffatom, eine gegebenenfalls substituierte Arylgruppe, eine (C₁ bis C₄)-Alkylgruppe oder eine (C₁ bis C₄)-Monohydroxyalkylgruppe, insbesondere für ein Wasserstoffatom oder eine Methylgruppe.

Preferred pyrazole derivatives are selected according to the invention from compounds according to formula (E5),

wherein

• - G ²³ , G ²⁴ , G ²⁵ independently represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl group, a (C ₁ to C ₄ ) monohydroxyalkyl group, a (C ₂ to C ₄ ) polyhydroxyalkyl group, a optionally substituted aryl group or an optionally substituted aryl (C ₁ to C ₄ ) alkyl group, with the proviso that, if G ^{25 stands} for a hydrogen atom, G ²⁶ can also stand for a group -NH _{2 in} addition to the aforementioned groups,
• - G ²⁶ stands for a hydrogen atom, a (C ₁ to C ₄ ) -alkyl group, a (C ₁ to C ₄ ) -monohydroxyalkyl group or a (C ₂ to C ₄ ) -polyhydroxyalkyl group and
• - G ²⁷ stands for a hydrogen atom, an optionally substituted aryl group, a (C ₁ to C ₄ ) -alkyl group or a (C ₁ to C ₄ ) -monohydroxyalkyl group, in particular a hydrogen atom or a methyl group.

In formula (E5), the radical -NG ²⁵ binds G ²⁶ to the 5 position and the radical G ²⁷ to the 3 position of the pyrazole cycle.

Particularly preferred pyrazole derivatives are, in particular, those compounds which are selected from 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5- Diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3 -phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert.-butyl-1-methylpyrazole, 4, 5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) -3-methyl-pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4 , 5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4, 5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (β-aminoethyl) amino-1,3-dimethylpyrazole, and their physiologically acceptable salts .

wobei:

• - G²⁸, G²⁹ und G³⁰, G³¹unabhängig voneinander stehen für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest einen (C₁ bis C₄)-Alkoxy-(C₁ bis C₄)-alkylrest, einen (C₁ bis C₄)-Aminoalkylrest, der gegebenenfalls durch ein Acetyl-Ureid- oder einen Sulfonyl-Rest geschützt sein kann, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)-alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Monohydroxyalkyl- oder einen Di[(C₁ bis C₄)-Hydroxyalkyl]-(C₁ bis C₄)-aminoalkylrest,
• - die X-Reste stehen unabhängig voneinander für ein Wasserstoffatom, einen (C₁ bis C₄)-Alkylrest, einen Aryl-Rest, einen (C₁ bis C₄)-Monohydroxyalkylrest, einen (C₂ bis C₄)-Polyhydroxyalkylrest, einen (C₁ bis C₄)-Aminoalkylrest, einen (C₁ bis C₄)-Alkylamino-(C₁ bis C₄)-alkylrest, einen Di-[(C₁ bis C₄)alkyl]-(C₁ bis C₄)-aminoalkylrest, wobei die Dialkyl-Reste gegebenenfalls einen Kohlenstoffzyklus oder einen Heterozyklus mit 5 oder 6 Kettengliedern bilden, einen (C₁ bis C₄)-Hydroxyalkyl- oder einen Di-[(C₁ bis C₄)-hydroxyalkyl]amino-(C₁ bis C₄)-alkylrest, einen Aminorest, einen (C₁ bis C₄)-Alkyl- oder Di-[(C₁ bis C₄)-hydroxyalkyl]aminorest, ein Halogenatom, eine Carboxylsäuregruppe oder eine Sulfonsäuregruppe,
• - i hat den Wert 0, 1, 2 oder 3,
• - p hat den Wert 0 oder 1,
• - q hat den Wert 0 oder 1 und
• - n hat den Wert 0 oder 1,

mit der Maßgabe, dass

• - die Summe aus p + q ungleich 0 ist,
• - wenn p + q gleich 2 ist, n den Wert 0 hat, und die Gruppen NG²⁸G²⁹ und NG³⁰G³¹ belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);
• - wenn p + q gleich 1 ist, n den Wert 1 hat, und die Gruppen NG²⁸G²⁹ (oder NG³⁰G³¹) und die Gruppe OH belegen die Positionen (2,3); (5,6); (6,7); (3,5) oder (3,7);

Preferred pyrazolopyrimidine derivatives are in particular the derivatives of pyrazolo [1,5-a] pyrimidine of the following formula (E6) and its tautomeric forms, provided there is a tautomeric equilibrium:

in which:

• - G ²⁸ , G ²⁹ and G ³⁰ , G ³¹ independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) -alkyl radical, an aryl radical, a (C ₁ to C ₄ ) -monohydroxyalkyl radical, a (C ₂ to C ₄ ) polyhydroxyalkyl radical a (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl radical, a (C ₁ to C ₄ ) aminoalkyl radical, which is optionally replaced by an acetyl ureide or a sulfonyl Rest can be protected, a (C ₁ to C ₄ ) -alkylamino- (C ₁ to C ₄ ) -alkyl radical, a di - [(C ₁ to C ₄ ) -alkyl] - (C ₁ to C ₄ ) -aminoalkyl radical , the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain members, a (C ₁ to C ₄ ) monohydroxyalkyl or a di [(C ₁ to C ₄ ) hydroxyalkyl] - (C ₁ to C) ₄ ) aminoalkyl radical,
• the X radicals independently of one another represent a hydrogen atom, a (C ₁ to C ₄ ) alkyl radical, an aryl radical, a (C ₁ to C ₄ ) monohydroxyalkyl radical, a (C ₂ to C ₄ ) polyhydroxyalkyl radical, a (C ₁ to C ₄ ) -aminoalkyl radical, a (C ₁ to C ₄ ) -alkylamino- (C ₁ to C ₄ ) -alkyl radical, a di - [(C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl radical, the dialkyl radicals optionally forming a carbon cycle or a heterocycle with 5 or 6 chain members, a (C ₁ to C ₄ ) -hydroxyalkyl or a di- [(C ₁ to C ₄ ) -hydroxyalkyl] amino- (C ₁ to C ₄ ) -alkyl radical, an amino radical, a (C ₁ to C ₄ ) -alkyl or di - [(C ₁ to C ₄ ) -hydroxyalkyl] amino radical, a halogen atom, a carboxylic acid group or a sulfonic acid group ,
• - i has the value 0, 1, 2 or 3,
• - p has the value 0 or 1,
• - q has the value 0 or 1 and
• - n has the value 0 or 1,

with the proviso that

• - the sum of p + q is not equal to 0,
• - if p + q is equal to 2, n has the value 0, and the groups NG ²⁸ G ²⁹ and NG ³⁰ G ³¹ occupy the positions (2,3); (5.6); (6.7); (3.5) or (3.7);
• if p + q is equal to 1, n has the value 1, and the groups NG ²⁸ G ²⁹ (or NG ³⁰ G ³¹ ) and the group OH occupy the positions (2,3); (5.6); (6.7); (3.5) or (3.7);

According to the invention, the substituents used in formula (E7) are defined analogously to the above statements.

If that Pyrazolo [1,5-a] pyrimidine of the above formula (E6) contains a hydroxyl group at one of positions 2, 5 or 7 of the ring system, there is a tautomeric equilibrium, which is shown for example in the following scheme:

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

sowie ihre physiologisch verträglichen Salze und ihre tautomeren Formen, wenn ein tautomers Gleichgewicht vorhanden ist.Among the pyrazolo [1,5-a] pyrimidines of the above formula (E7) one can mention in particular:

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

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

The pyrazolo [1,5-a] pyrimidines of the above formula (E6) can be prepared, as described in the literature, by cyclization starting from an aminopyrazole or from hydrazine.

Very particularly preferred developer components are selected from at least one compound from the group formed by p-phenylenediamine, p-tolylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p -phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1 H-imidazol-1-yl) propyl] amine, N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2-hydroxy-5-aminophenyl) - methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1,10-bis (2, 5-diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine , 2-Hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds.

In a further particularly preferred embodiment, a method according to the invention is characterized in that the second composition (B) contains one or more oxidation dye precursors (B1) selected from the group consisting of p-phenylenediamine, p-tolylenediamine, 2- (β- Hydroxyethyl) -p-phenylenediamine, 2- (a, ß-dihydroxyethyl) -p-phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N - [3- (1H-imidazol-1-yl) propyl] amine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) -1, 3-diaminopropane-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- (a, ß-dihydroxyethyl) -phenol and 4-amino-2- (diethylaminomethyl) -phenol, 4,5-diamino-1- (β-hydroxyethyl) -pyrazole, 2,4,5, 6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4 , 5,6-triaminopyrimidine, and the physiologically compatible salts of these compounds.

Examples of the radicals mentioned as substituents of the compounds of the formulas (E1) to (E6) are listed below: Examples of (C ₁ to C ₄ ) -alkyl radicals are the groups —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ . Examples according to the invention of (C ₁ to C ₄ ) alkoxy radicals are -OCH ₃ , -OCH ₂ CH ₃ , -OCH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) ₂ , -OCH ₂ CH ₂ CH ₂ CH ₃ , - OCH ₂ CH (CH ₃ ) ₂ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OC (CH ₃ ) ₃ , in particular a methoxy or an ethoxy group. Furthermore, as preferred examples of a (C ₁ to C ₄ ) monohydroxyalkyl group —CH ₂ OH, —CH ₂ CH ₂ OH, —CH ₂ CH ₂ CH ₂ OH, —CHCH (OH) CH ₃ , —CH ₂ CH ₂ CH ₂ CH ₂ OH, the - CH ₂ CH ₂ OH group being preferred. A particularly preferred example of a (C ₂ to C ₄ ) polyhydroxyalkyl group is the 1,2-dihydroxyethyl group.
Examples of halogen atoms are F, Cl or Br atoms, Cl atoms are very particularly preferred examples.
Examples of nitrogen-containing groups are in particular -NH ₂ , (C ₁ to C ₄ ) monoalkylamino groups, (C ₁ to C ₄ ) dialkylamino groups, (C ₁ to C ₄ ) trialkylammonium groups, (C ₁ to C ₄ ) monohydroxyalkylamino groups, Imidazolinium and -NH ₃ ⁺ .
Examples of (C ₁ to C ₄ ) monoalkylamino groups are -NHCH ₃ , -NHCH ₂ CH ₃ , -NHCH ₂ CH ₂ CH ₃ ,
-NHCH (CH ₃ ) ₂ .
Examples of (C ₁ to C ₄ ) -dialkylamino groups are -N (CH ₃ ) ₂ , -N (CH ₂ CH ₃ ) ₂ .
Examples of (C ₁ to C ₄ ) -trialkylammonium groups are -N ⁺ (CH ₃ ) ₃ , -N ⁺ (CH ₃ ) ₂ (CH ₂ CH ₃ ),

-N ⁺ (CH ₃ ) (CH ₂ CH ₃ ) ₂ .
Examples of (C ₁ to C ₄ ) -hydroxyalkylamino radicals are -NH-CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ OH,
-NH-CH ₂ CH ₂ CH ₂ OH, -NH-CH ₂ CH ₂ CH ₂ OH.
Examples of (C ₁ to C ₄ ) alkoxy (C ₁ to C ₄ ) alkyl groups are the groups -CH ₂ CH ₂ -O-CH ₃ ,
-CH ₂ CH ₂ CH ₂ -O-CH ₃ , -CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₃ , -CH ₂ CH ₂ -O-CH (CH ₃ ),
-CH ₂ CH ₂ CH ₂ -O-CH (CH ₃ ).
Examples of hydroxy (C ₁ to C ₄ ) alkoxy radicals are -O-CH ₂ OH, -O-CH ₂ CH ₂ OH, -O-CH ₂ CH ₂ CH ₂ OH,
-O-C H (OH) CH _3, -O-CH ₂ CH ₂ CH ₂ CH ₂ OH.
Examples of (C ₁ to C ₄ ) acetylaminoalkoxy radicals are -O-CHzNHC (O) CH ₃ , -O-CH ₂ CH ₂ NHC (0) CH ₃ ,
-O-CH ₂ CH ₂ CH ₂ NHC (O) CH _3, -O-CH ₂ CH (NHC (O) CH ₃₎ CH _3, -O-CH ₂ CH ₂ CH ₂ CH ₂ NHC (O) CH ₃ .

Examples of (C ₁ to C ₄ ) -carbamoylaminoalkoxy radicals are -O-CHzCHz-NH-C (O) -NHz, -O-CH ₂ CH ₂ CH ₂ -NH-C (O) -NH ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₂ -NH-C (O) -NH _2.
Examples of (C ₁ to C4) aminoalkyl radicals are -CH2NH2, -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ ,
-CH ₂ CH (NH ₂ ) CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ .
Examples of (C ₁ to C4) -Cyanoalkylreste are -CH ₂ CN, -CH ₂ CH ₂ CN, -CH ₂ CH ₂ CH ₂ CN.
Examples of (C ₁ to C ₄ ) hydroxyalkylamino (C ₁ to C ₄ ) alkyl radicals are -CH ₂ CH ₂ NH-CH ₂ CH ₂ OH,
-CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ OH, -CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH, -CH ₂ CH ₂ CH ₂ NH-CH ₂ CH ₂ CH ₂ OH. Examples of di [(C ₁ to C ₄ ) -hydroxyalkyl] amino- (C ₁ to C ₄ ) -alkyl radicals are -CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ ,
-CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ , -CH ₂ CH ₂ CH ₂ N (CH ₂ CH ₂ CH ₂ OH ) ₂ .
An example of aryl groups is the phenyl group.
Examples of aryl (C ₁ to C ₄ ) alkyl groups are the benzyl group and the 2-phenylethyl group.

The composition (B) according to the invention preferably contains one or more developer components in a total amount of from 0.005 to 10% by weight, preferably from 0.1 to 5% by weight, based in each case on the total weight of the composition (B).

As a rule, m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives, and heterocyclic compounds are used as coupler components.

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

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

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

and their physiologically acceptable salts.

According to the invention particularly preferred coupler components are 2-methylresorcinol, 4-chlororesorcinol, resorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2 -Amino-3-hydroxypyridine, 2-chloro-6-methyl-3-aminophenol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically acceptable salts of the aforementioned compounds.

In a further particularly preferred embodiment, a method according to the invention is characterized in that the second composition (B) contains one or more oxidation dye precursors (B1) selected from the group consisting of 2-methylresorcinol, 4-chlororesorcinol, resorcinol and 1-naphthol , 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, 2-chloro-6-methyl-3-aminophenol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically acceptable salts of these compounds.

The composition (B) according to the invention preferably contains one or more coupler components in a total amount of from 0.005 to 10% by weight, preferably from 0.1 to 5% by weight, based in each case on the total weight of the composition (B).

Composition (B) according to the invention can also contain one or more precursors of nature-analogous dyes as oxidation dye precursor.

Indoles and indolines which have at least one hydroxyl or amino group, preferably as a substituent on the six-membered ring, are preferably used as precursors of nature-analogous dyes as oxidation dye precursors of the developer type. These groups can carry further substituents, e.g. B. in the form of an etherification or esterification of the hydroxy group or an alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

in der unabhängig voneinander

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

sowie physiologisch verträgliche Salze dieser Verbindungen mit einer organischen oder anorganischen Säure.Derivatives of 5,6-dihydroxyindoline of the formula (IVa) are particularly suitable as precursors of natural hair dyes,

in the independent

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

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

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

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially the 5, 6-dihydroxyindoline.

in der unabhängig voneinander

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

Derivatives of 5,6-dihydroxyindole of the formula (IVb) are also outstandingly suitable as precursors of hair dyes analogous to nature,

in the independent

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

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

To be emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and, in particular, 5,6 -Dihydroxyindole.

Very particularly suitable oxidation dye precursors (B1) from the group of precursors of hair dyes analogous to nature are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6- dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline, 4-aminoindoline, 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole , N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4 -Aminoindole and the physiologically acceptable salts of these compounds.

In a further particularly preferred embodiment, a method according to the invention is characterized in that the second composition (B) contains one or more oxidation dye precursors (B1) selected from the group consisting of 5,6-dihydroxyindoline and N-methyl-5,6 -dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, the 6- Aminoindoline, 4-aminoindoline, 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole and the physiologically tolerated salts of these compounds.

The best results were obtained with 2-methylresorcinol, with 5,6-dihydroxyindoline and / or with the physiologically acceptable salts of 5,6-dihydroxyindoline.

The composition (B) according to the invention preferably contains one or more precursors of nature-analogous hair dyes in a total amount of 0.005 to 10% by weight, preferably 0.1 to 5% by weight, based in each case on the total weight of the composition (B).

In the context of an explicitly very particularly preferred embodiment, a method according to the invention is characterized in that the second composition (B) contains one or more oxidation dye precursors (B1) selected from the group consisting of 2-methylresorcinol, 5,6-dihydroxyindoline and / or their physiologically compatible salts.

Water content of the composition (B)

The composition (B) contains the oxidation dye precursor or products (B1) in a cosmetic carrier, preferably in an aqueous cosmetic carrier. Like the composition (A), the composition (B) also represents a ready-to-use composition which preferably has a relatively high water content.

In this context, it has been found to be preferred if the composition (B) - based on the total weight of the composition (B) - 5.0 to 90.0 wt .-%, preferably 15.0 to 85.0 wt .-% %, more preferably 25.0 to 80.0% by weight, even more preferably 35.0 to 75.0% by weight and very particularly preferably 45.0 to 70.0% by weight of water.

In a further embodiment, a method according to the invention is characterized in that the second composition (B) - based on the total weight of the composition (B) - 5.0 to 90.0% by weight, preferably 15.0 to 85.0% by weight %, more preferably 25.0 to 80.0% by weight, even more preferably 35.0 to 75.0% by weight and very particularly preferably 45.0 to 70.0% by weight of water.

Further cosmetic ingredients in composition (B)

In addition, the composition (B) can also contain one or more further cosmetic ingredients.

The cosmetic ingredients which can optionally be used in the composition (B) can be all suitable constituents in order to impart further positive properties to the agent. For example, a solvent, a surface-active compound from the group of nonionic, cationic, anionic or zwitterionic / amphoteric surfactants, the coloring compounds from the group of pigments, the substantive dyes, the film-forming polymers, the fatty components from the Group of C ₈ -C ₃₀ fatty alcohols, hydrocarbon compounds, fatty acid esters, acids and bases belonging to the group of pH regulators, perfumes, preservatives and plant extracts.

The person skilled in the art will select these additional substances according to the desired properties of the agents. With regard to further optional components and the amounts of these components used, express reference is made to the relevant manuals known to the person skilled in the art.

pH of the compositions (B)

In further experiments it has been found that the pH values of the composition (B) can also have an influence on the color intensities and wash fastnesses obtained during dyeing. It was found here that alkaline pH values in particular have an advantageous effect on the dyeing performance that can be achieved in the process.

For this reason, it is preferred that the compositions (B) have a pH of from 7.0 to 12.0, preferably from 7.5 to 11.5, more preferably from 8.0 to 11.0 and very particularly preferably from 8.0 to 10.5.

The pH value can be measured using the usual methods known from the prior art, such as measuring the pH value by means of glass electrodes using single-rod measuring chains or using pH indicator paper.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the composition (B) has a pH of from 7.0 to 12.0, preferably from 7.5 to 11.5, more preferably from 8.0 to 11.0 and very particularly preferably from 8.0 to 10.5.

To set this alkaline pH, it may be necessary to add an alkalizing agent and / or acidifying agent to the reaction mixture. The pH values in the context of the present invention are pH values that were measured at a temperature of 22 ° C.

Ammonia, alkanolamines and / or basic amino acids, for example, can be used as alkalizing agents.

Alkanolamines can be selected from primary amines with a C ₂ -C ₆ -alkyl parent structure which carries at least one hydroxyl group. Preferred alkanolamines are selected from the group that is formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropane -2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1 -Amino-2-methyl-propan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol.

If basic amino acids are used in the composition (B), it is also possible to adjust the pH by adding the basic amino acids. According to the invention, basic amino acids are to be understood as meaning those amino acids which have an isoelectric point p1 of greater than 7.0.

Basic α-aminocarboxylic acids contain at least one asymmetric carbon atom. In the context of the present invention, both possible enantiomers can be used equally as specific compounds or mixtures thereof, in particular as racemates. However, it is particularly advantageous to use the naturally preferred isomer form, usually in the L configuration.

The basic amino acids are preferably selected from the group that is formed from arginine, lysine, ornithine and histidine, particularly preferably from arginine and lysine. In a further particularly preferred embodiment, a composition according to the invention is therefore characterized in that the alkalizing agent is a basic amino acid from the group arginine, lysine, ornithine and / or histidine.

Inorganic alkalizing agents can also be used. Inorganic alkalizing agents which can be used according to the invention are preferably selected from the group formed by sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

Particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2- methylpropan-2-ol, 3-aminopropan-1,2-diol, 2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, Sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

In addition to the alkalizing agents described above, the person skilled in the art is familiar with acidifying agents commonly used for fine adjustment of the pH. According to the invention are preferred acidifying agents Pleasure acids, such as citric acid, acetic acid, malic acid or tartaric acid, as well as diluted mineral acids.

No peroxo compounds in the process

The method according to the invention contains the proviso that in the method no composition is used on the keratinic material which contains one or more peroxo compounds.

According to the invention, the term peroxo compounds is understood to mean inorganic and organic compounds which are characterized by the presence of a peroxy group -O-O-. The oxygen atoms in these peroxo compounds usually have the oxidation state -1.

Peroxo compounds in the sense of the invention are therefore the compounds of the general formula (O-1) Ro ₁ -O-O-RO ₂ (O-1) where the radicals Ro1 and Ro2 stand for a hydrogen atom, for an inorganic radical or for an organic radical.

Peroxo compounds are oxidizing agents that are usually used in oxidative hair coloring to initiate the reaction between developer and coupler, which leads to the formation of the dyes.

The peroxo compound most frequently used in oxidative hair coloring is hydrogen peroxide (where Ro1 and Ro2 are hydrogen).

Another peroxo compound used very often in oxidative hair coloring is potassium persulfate (also known as potassium peroxodisulfate), sodium persulfate (also known as sodium peroxodisulfate) and ammonium persulfate (also known as ammonium peroxodisulfate). In the case of the persulfates, the residues Ro1 and Ro2 each represent a residue -SO3-, the negative charge being neutralized by the presence of the corresponding cations.

A peroxo compound also used in some oxidative hair dyes is percarbonates such as sodium percarbonate, potassium percarbonate and magnesium percarbonate.

Percarbonates are addition products (adducts) of hydrogen peroxide with the corresponding carbonates, for example sodium percarbonate is the addition product of hydrogen peroxide with sodium percarbonate. The percarbonates thus also represent peroxo compounds, with the percarbonates as peroxo compounds being based on hydrogen peroxide.

By using the method according to the invention, it became possible to obtain dyeings with very good gray coverage without having to resort to these oxidizing agents or peroxo compounds which are customary in oxidative dyeing.

• - eine erste Zusammensetzung (A), die enthält:
  • (A1) ein oder mehrere organische C₁-C₆-Alkoxy-Silane und/oder deren Kondensationsprodukte, und
• - eine zweite Zusammensetzung (B), die enthält
  • (B1) ein oder mehrere Oxidationsfarbstoffvorprodukte,

mit der Maßgabe, dass im Verfahren keine Zusammensetzung auf dem keratinischen Material angewendet wird, die eine oder mehrere Peroxide mit der Struktureinheit -O-O- enthält.In other words, the first subject matter of the present invention is a method for coloring keratinic material, in particular human hair, in which the keratinic material is used:

• - a first composition (A) which contains:
  • (A1) one or more organic C ₁ -C ₆ -alkoxy-silanes and / or their condensation products, and
• - a second composition (B) which contains
  • (B1) one or more oxidation dye precursors,

with the proviso that in the process no composition is applied to the keratinic material which contains one or more peroxides with the structural unit -OO-.

• - eine erste Zusammensetzung (A), die enthält:
  • (A1) ein oder mehrere organische C₁-C₆-Alkoxy-Silane und/oder deren Kondensationsprodukte, und
• - eine zweite Zusammensetzung (B), die enthält
  • (B1) ein oder mehrere Oxidationsfarbstoffvorprodukte,

mit der Maßgabe, dass im Verfahren keine Zusammensetzung auf dem keratinischen Material angewendet wird, die eine oder mehrere Peroxoverbindungen aus der Gruppe aus Wasserstoffperoxid, Natriumpersulfat, Kaliumpersulfat, Ammoniumpersulfat, Natriumpercarbonat, Kaliumpercarbonat und Magnesiumpercarbonat enthält.In other words, the first subject matter of the present invention is a method for coloring keratinic material, in particular human hair, in which the keratinic material is used:

• - a first composition (A) containing:
  • (A1) one or more organic C ₁ -C ₆ -alkoxy-silanes and / or their condensation products, and
• - a second composition (B) which contains
  • (B1) one or more oxidation dye precursors,

with the proviso that in the process no composition is applied to the keratinous material which contains one or more peroxo compounds from the group of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, sodium percarbonate, potassium percarbonate and magnesium percarbonate.

In the context of the method according to the invention, no composition is applied to the keratinic material which contains one or more peroxo compounds, which means that neither composition (A) nor composition (B) may contain a corresponding peroxo compound. In addition, the other compositions, which are optionally additionally applied to the keratin material in the context of the method according to the invention, are also free of the corresponding peroxo compounds.

The optionally additionally applicable composition can be, for example, a composition (C) which is a pretreatment agent or which is mixed with one of the compositions (A) or (B) before use. Furthermore, this optionally additionally applicable composition can also be an aftertreatment agent (D) such as, for example, a conditioner. All of these compositions are characterized in that they contain no peroxo compounds, in particular no peroxo compounds from the group consisting of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, sodium percarbonate, potassium percarbonate and magnesium percarbonate.

The method according to the invention comprises the use of all compositions which are applied to the keratin material simultaneously or successively within a period of at most 2 hours before or after the use of the compositions (A) and (B).

• - eine erste Zusammensetzung (A), die enthält:
  • (A1) ein oder mehrere organische C₁-C₆-Alkoxy-Silane und/oder deren Kondensationsprodukte, und
• - eine zweite Zusammensetzung (B), die enthält
  • (B1) ein oder mehrere Oxidationsfarbstoffvorprodukte,

wobei die Anwendung der Zusammensetzungen (A) und (B) entweder gleichzeitig oder sukzessive nacheinander erfolgt,
mit der Maßgabe, dass innerhalb eines Zeitraumes von 2 Stunden vor und nach der Anwendung der Zusammensetzungen (A) und (B) keine Zusammensetzung auf dem keratinischen Material angewendet wird, die eine oder mehrere Peroxoverbindungen aus der Gruppe aus Wasserstoffperoxid, Natriumpersulfat, Kaliumpersulfat, Ammoniumpersulfat, Natriumpercarbonat, Kaliumpercarbonat und Magnesiumpercarbonat enthält.In other words, the first subject matter of the present invention is a method for coloring keratinic material, in particular human hair, in which the keratinic material is used:

• - a first composition (A) containing:
  • (A1) one or more organic C ₁ -C ₆ -alkoxy-silanes and / or their condensation products, and
• - a second composition (B) which contains
  • (B1) one or more oxidation dye precursors,

wherein the application of the compositions (A) and (B) takes place either simultaneously or successively one after the other,
with the proviso that within a period of 2 hours before and after the application of the compositions (A) and (B) no composition is applied to the keratinous material which contains one or more peroxo compounds from the group consisting of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate , Sodium percarbonate, potassium percarbonate and magnesium percarbonate.

Use of other coloring compounds

In the course of the work leading to this invention it was observed that the colorations not only had good gray coverage, but also had a particularly high color intensity if, in addition to the oxidation dye precursors (B1), a coloring compound from the group of pigments was also used in the process and / or the substantive dyes was used. The use of pigments has proven to be very particularly preferred. These additional coloring compounds can be incorporated into the composition (A) and / or into the composition (B).

In the context of a further very particularly preferred embodiment, a method according to the invention is characterized in that the first composition (A) contains at least one coloring compound a from the group of pigments and / or substantive dyes.

In a further very particularly preferred embodiment, a method according to the invention is characterized in that the second composition (B) contains at least one color-imparting compound a from the group of pigments and / or substantive dyes.

In addition, it is also possible to incorporate the coloring compounds into a third, separately prepared composition (C) which is then applied to the keratinous material.

• - eine dritte Zusammensetzung (C), die mindestens eine farbgebende Verbindung as der Gruppe der Pigmente und/oder der direktziehenden Farbstoffe enthält.

In the context of a further embodiment, a method is preferred in which the keratin material is used:

• - A third composition (C) which contains at least one coloring compound a from the group of pigments and / or substantive dyes.

As described above, there is also the proviso for this third composition (C) that it contains no peroxo compound, in particular no peroxo compound from the group consisting of hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, sodium percarbonate, potassium percarbonate and magnesium percarbonate

The coloring compound (s) can be selected from the group of pigments and substantive dyes, it also being possible for the substantive dyes to be photochromic dyes and thermochromic dyes.

The composition (A) and / or the composition (B) and / or the optionally usable composition (C) very particularly preferably contains at least one pigment.

Pigments in the context of the present invention are understood to mean coloring compounds which at 25 ° C. in water have a solubility of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0, 05 g / L. The water solubility can be achieved, for example, using the method described below: Weigh out 0.5 g of the pigment in a beaker. A stir fry is added. Then one liter of distilled water is added. This mixture is heated to 25 ° C. for one hour while stirring on a magnetic stirrer. If undissolved constituents of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g / L. If the pigment-water mixture cannot be assessed visually due to the high intensity of the pigment which may be present in finely dispersed form, the mixture is filtered. If a proportion of undissolved pigments remains on the filter paper, the solubility of the pigment is below 0.5 g / L.

Suitable color pigments can be of inorganic and / or organic origin.

In a preferred embodiment, the agent according to the invention is characterized in that it contains at least one coloring compound from the group of inorganic and / or organic pigments.

Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be made from chalk, ocher, umber, green earth, burnt Terra di Siena or graphite, for example. Furthermore, as inorganic color pigments, black pigments such. B. iron oxide black, colored pigments such. B. ultramarine or iron oxide red and fluorescent or phosphorescent pigments can be used.

Colored metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, metal chromates and / or metal molybdates are particularly suitable. Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI77289 ), Iron blue (Ferric Ferrocyanide, CI77S10) and / or carmine (Cochineal).

Coloring compounds from the group of pigments which are likewise particularly preferred according to the invention are colored pearlescent pigments. These are usually based on mica and / or mica and can be coated with one or more metal oxides. Mica is one of the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To Production of the pearlescent pigments in connection with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.

In a particularly preferred embodiment, a method according to the invention is characterized in that the composition (A) and / or the composition (B) contains at least one coloring compound from the group of inorganic pigments, which is selected from the group of colored metal oxides, Metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored pigments based on mica or mica coated with at least one metal oxide and / or a metal oxychloride.

As an alternative to natural mica, synthetic mica coated with one or more metal oxide (s) can also be used as the pearlescent pigment. Particularly preferred pearlescent pigments are based on natural or synthetic mica (mica) and are coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be varied by varying the layer thickness of the metal oxide (s).

In a further preferred embodiment, the composition (A) and / or the composition (B) according to the invention is characterized in that it contains at least one coloring compound from the group of pigments, which is selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, Silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or from coloring compounds based on mica or mica coated with at least one metal oxide and / or a metal oxychloride.

In a further preferred embodiment, a composition (A) and / or composition (B) according to the invention is characterized in that it contains at least one coloring compound which is selected from pigments based on mica or mica, those with one or more metal oxides from the group made of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (Ferric Ferrocyanide, CI 77510) are coated.

Examples of particularly suitable color pigments are commercially available under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® available from Sunstar.

• Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina
• Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)
• Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
• Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE
• Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA
• Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA
• Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)
• Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES)
• Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)
• Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS)
• Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510)
• Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
• Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRON OXIDES (CI 77491)
• Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE
• Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES)
• Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
• Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA
• Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide), Silica, CI 77491 (Iron oxides), Tin oxide
• Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, CI 77891, CI 77491 (EU)
• Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891 (Titanium dioxide)
• Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491(Iron oxides)
• Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

Particularly preferred color pigments with the trade name Colorona® are, for example:

• Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina
• Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)
• Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
• Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE
• Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA
• Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA
• Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)
• Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)
• Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDES), MICA, CI 77891 (IRON OXIDES)
• Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)
• Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS)
• Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510)
• Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
• Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRON OXIDES (CI 77491)
• Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE
• Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES)
• Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)
• Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA
• Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES)
• Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide), Silica, CI 77491 (Iron oxides), Tin oxide
• Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, CI 77891, CI 77491 (EU)
• Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891 (Titanium dioxide)
• Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iron oxides)
• Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

• Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide
• Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide
• Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide
• Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

Other particularly preferred color pigments with the trade name Xirona® are, for example:

• Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide
• Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide
• Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide
• Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

• Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica
• Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica
• Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

In addition, particularly preferred color pigments with the trade name Unipure® are, for example:

• Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica
• Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica
• Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

In a further embodiment, the composition (A) and / or the composition (B) and / or an optionally usable composition (C) can also contain one or more coloring compounds from the group of organic pigments

The organic pigments according to the invention are correspondingly insoluble, organic dyes or color lakes, for example from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene -, Diketopyrrolopyorrol-, indigo, thioindido, dioxazine, and / or triarylmethane compounds can be selected.

Particularly suitable organic pigments are, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680 , CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 11725 , CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470 will.

In a further particularly preferred embodiment, a method according to the invention is characterized in that the composition (A) and / or the composition (B) contains at least one coloring compound from the group of organic pigments, which is selected from the group of carmine, quinacridone, Phthalocyanine, Sorgho, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040 , CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

The organic pigment can also be a colored lacquer. In the context of the invention, the term colored lacquer is understood to mean particles which comprise a layer of absorbed dyes, the unit of particles and dye being insoluble under the above-mentioned conditions. The particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate or also aluminum.

The alizarin color varnish, for example, can be used as the color varnish.

Due to their excellent light and temperature stability, the use of the aforementioned pigments in the agents according to the invention is particularly preferred. It is also preferred if the pigments used have a certain particle size. This particle size leads, on the one hand, to a uniform distribution of the pigments in the polymer film formed and, on the other hand, prevents the hair or skin feeling rough after the cosmetic agent has been applied. It is therefore advantageous according to the invention if the at least one pigment has an average particle size D ₅₀ of 1.0 to 50 μm, preferably 5.0 to 45 μm, more preferably 10 to 40 μm, in particular 14 to 30 μm. The mean particle size Dso can be determined, for example, using dynamic light scattering (DLS).

Pigments with a specific shape can also have been used to color the keratin material. For example, a pigment based on a lamellar and / or a lenticular substrate platelet can be used. Coloring on the basis of a substrate platelet which comprises a vacuum metallized pigment is also possible.

In a further embodiment, the composition (A) and / or the composition (B) and / or an optionally usable composition (C) can also contain one or more coloring compounds from the group of the pigments based on a lamellar substrate platelet, the pigments based a lenticular substrate wafer and the vacuum metallized pigments.

The substrate platelets of this type have an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred ranges for the thickness of the substrate platelets are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm and 10 to 20 nm. Each substrate plate preferably has a thickness that is as uniform as possible.

Due to the small thickness of the substrate platelets, the pigment has a particularly high hiding power.

The substrate platelets are monolithic. In this context, monolithic means consisting of a single closed unit without breaks, layers or inclusions, although changes in structure can occur within the substrate platelets. The substrate platelets are preferably constructed homogeneously, i.e. there is no concentration gradient within the platelets. In particular, the substrate platelets are not constructed in layers and have no particles or particles distributed therein.

The size of the substrate platelet can be matched to the particular application, in particular the desired effect on the keratinic material. As a rule, the substrate platelets have a mean largest diameter of about 2 to 200 μm, in particular about 5 to 100 μm.

In a preferred embodiment, the aspect ratio, expressed by the ratio of the mean size to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, particularly preferably more than 750. The mean size of the uncoated substrate flakes is understood to be the d50 value of the uncoated substrate flakes. Unless otherwise stated, the d50 value was determined using a Sympatec Helos device with Quixel wet dispersion. For sample preparation, the sample to be examined was predispersed in isopropanol for a period of 3 minutes.

The substrate platelets can be constructed from any material that can be brought into platelet form.

They can be of natural origin, but also synthetically produced. Materials from which the substrate platelets can be constructed are, for example, metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi) precious stones, as well as plastics. The substrate platelets are preferably constructed from metal (alloys).

Any metal suitable for metallic luster pigments can be considered as the metal. Such metals include iron and steel, as well as all air and water-resistant (semi) metals such as platinum, zinc, chromium, molybdenum and silicon, and their alloys such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver and gold. Preferred substrate platelets are aluminum platelets and brass platelets, with substrate platelets made of aluminum being particularly preferred.

Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as “cornflakes” due to their appearance.

Due to their irregular structure, pigments based on lamellar substrate platelets generate a high proportion of scattered light. In addition, the pigments based on lamellar substrate platelets do not completely cover the existing color of a keratinic material and effects analogous to natural graying can be achieved, for example.

Lenticular (= lens-shaped) substrate platelets have an essentially regular, round edge and are also known as "silver dollars" due to their appearance. Due to their regular structure, pigments based on lenticular substrate platelets predominate in the proportion of reflected light.

Vacuum metallized pigments (VMP) can be obtained, for example, by releasing metals, metal alloys or metal oxides from appropriately coated foils. They are distinguished by a particularly small thickness of the substrate platelets in the range from 5 to 50 nm and by a particularly smooth surface with increased reflectivity. Substrate platelets which comprise a pigment metallized in a vacuum are also referred to in this application as VMP substrate platelets. VMP substrate platelets made of aluminum can be obtained, for example, by releasing aluminum from metallized foils.

The substrate platelets made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

Uncoated lamellar, lenticular and / or VPM substrate platelets, in particular those made of metal or metal alloy, reflect the incident light to a high degree and produce a light-dark flop, but no color impression.

A color impression can be generated, for example, due to optical interference effects. Such pigments can be based on at least once coated substrate platelets. These show interference effects due to the superposition of differently refracted and reflected light beams.

Accordingly, preferred pigments are pigments based on a coated lamellar substrate platelet. The substrate plate preferably has at least one coating B of a high refractive index metal oxide with a coating thickness of at least 50 nm. A further coating A is preferably located between the coating B and the surface of the substrate platelet. If necessary, another coating C, which is different from the layer B below, is located on the layer B.

Suitable materials for the coatings A, B and C are all substances that can be applied permanently and in film form to the substrate platelets and, in the case of the layers A and B, have the required optical properties. In general, a coating of part of the surface of the substrate flakes is sufficient to obtain a pigment with a glossy effect. For example, only the upper and / or lower side of the substrate platelets can be coated, with the side surface (s) being cut out. The entire surface of the optionally passivated substrate platelets, including the side surfaces, is preferably covered by coating B. The substrate platelets are therefore completely encased by coating B. This improves the optical properties of the pigment and increases the mechanical and chemical resistance of the pigments. The foregoing also applies to layer A and preferably also to layer C, if any.

Although several coatings A, B and / or C can be present in each case, the coated substrate platelets preferably each have only one coating A, B and, if present, C.

The coating B is made up of at least one high-index metal oxide. High refractive index materials have a refractive index of at least 1.9, preferably at least 2.0 and particularly preferably at least 2.4. The coating B preferably comprises at least 95% by weight, particularly preferably at least 99% by weight, of high-index metal oxide (s).

The coating B has a thickness of at least 50 nm. The thickness of coating B is preferably not more than 400 nm, particularly preferably at most 300 nm.

Highly refractive metal oxides suitable for coating B are preferably selectively light-absorbing (ie colored) metal oxides such as iron (III) oxide (a- and γ-Fe2O3, red), cobalt (II) oxide (blue), chromium (III) oxide (green) ), Titanium (III) oxide (blue, is usually a mixture with titanium oxynitrides and titanium nitrides) and vanadium (V) oxide (orange) and their mixtures. Colorless, high-index oxides such as titanium dioxide and / or zirconium oxide are also suitable.

Coating B can contain a selectively absorbing dye, preferably 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, based in each case on the total amount of coating B. Organic and inorganic dyes that are stable in the have a metal oxide coating installed.

The coating A preferably has at least one low refractive index metal oxide and / or metal oxide hydrate. Coating A preferably comprises at least 95% by weight, particularly preferably at least 99% by weight, of low-refractive-index metal oxide (hydrate). Low refractive index materials have a refractive index of at most 1.8, preferably at most 1.6.

The low-refractive index metal oxides which are suitable for coating A include, for example, silicon (di) oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide and mixtures thereof, silicon dioxide being preferred. The coating A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, particularly preferably 5 to 20 nm.

The distance between the surface of the substrate platelets and the inner surface of coating B is preferably at most 100 nm, particularly preferably at most 50 nm, particularly preferably at most 20 nm. Because the thickness of coating A and thus the distance between the surface of the substrate platelets and Coating B is in the range specified above, it can be ensured that the pigments have a high hiding power.

If the pigment based on a lamellar substrate flake has only one layer A, it is preferred for the pigment to have a lamellar substrate flake made of aluminum and a layer A made of silicon dioxide. If the pigment based on a lamellar substrate flake has a layer A and a layer B, it is preferred for the pigment to have a lamellar substrate flake made of aluminum, a layer A made of silicon dioxide and a layer B made of iron oxide.

According to a preferred embodiment, the pigments have a further coating C made of a metal oxide (hydrate), which is different from the coating B below. Suitable metal oxides are, for example, silicon (di) oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, zinc oxide, tin oxide, titanium dioxide, zirconium oxide, iron (III) oxide and chromium (III) oxide. Silica is preferred.

The coating C preferably has a thickness of 10 to 500 nm, particularly preferably 50 to 300 nm. By providing the coating C, for example based on TiO ₂ , better interference can be achieved, with a high hiding power being ensured.

Layers A and C serve in particular as protection against corrosion and also for chemical and physical stabilization. Layers A and C particularly preferably contain silicon dioxide or aluminum oxide, which are applied by the sol-gel process. This method comprises dispersing the uncoated lamellar substrate flakes or the lamellar substrate flakes already coated with layer A and / or layer B in a solution of a metal alkoxide such as tetraethyl orthosilicate or aluminum triisopropoxide (usually in a solution of organic solvent or a mixture of organic solvent and water with at least 50% by weight organic solvent such as a C1 to C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, whereby a film of the metal oxide is formed on the surface of the (coated) substrate platelets.

Layer B can be produced, for example, by hydrolytic decomposition of one or more organic metal compounds and / or by precipitation of one or more dissolved metal salts and, if necessary, subsequent aftertreatment (for example, transferring a hydroxide-containing layer formed into the oxide layers by annealing).

Although each of the coatings A, B and / or C can be built up from a mixture of two or more metal oxides (hydrate), each of the coatings is preferably built up from a metal oxide (hydrate).

The pigments based on coated lamellar or lenticular substrate platelets or the pigments based on coated VMP substrate platelets preferably have a thickness of 70 to 500 nm, particularly preferably 100 to 400 nm, particularly preferably 150 to 320 nm, for example 180 to 290 nm, on. Due to the small thickness of the substrate platelets, the pigment has a particularly high hiding power. The small thickness of the coated substrate platelets is achieved in particular in that the thickness of the uncoated substrate platelets is small, but also in that the thicknesses of the coatings A and, if present, C are set to the smallest possible value. The thickness of coating B determines the color impression of the pigment.

The adhesion and abrasion resistance of pigments based on coated substrate platelets in the keratinous material can be significantly increased by additionally modifying the outermost layer, depending on the structure, layer A, B or C, with organic compounds such as silanes, phosphoric acid esters, titanates, borates or carboxylic acids becomes. The organic compounds are bound to the surface of the outermost layer A, B or C, preferably containing metal oxide. The outermost layer denotes the layer which is spatially furthest away from the lamellar substrate plate. The organic compounds are preferably functional silane compounds which can bind to the layer A, B or C containing metal oxide. These can be either mono- or bifunctional compounds. Examples of bifunctional organic compounds are methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-Methacryloxyethyl- triethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyltris (methox- yethoxy) silane, 3- Methacryloxypropyltris (butoxyethoxy) silane, 3-methacryloxypropyltris (propoxy) silane, 3-methacryloxypropyltris (butoxy) silane, 3-acryloxypropyltris (methoxyethoxy) silane, 3-acryloxypropyltris (butoxyethoxy) silane, 3-acrylotoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylethyl dichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, phenylvinyldiethoxysilane, or phenylallyldichlorosilane. Furthermore, a modification with a monofunctional silane, in particular an alkylsilane or arylsilane, can take place. This has only one functional group which can covalently bind pigments based on coated lamellar substrate platelets to the surface (ie to the outermost metal oxide-containing layer) or, if it is not completely covered, to the metal surface. The hydrocarbon residue of the silane faces away from the pigment. Depending on the type and nature of the hydrocarbon radical of the silane, a different degree of hydrophobicity of the pigment is achieved. Examples of such silanes are hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. are particularly preferred Pigments based on silicon dioxide-coated aluminum substrate platelets, surface-modified with a monofunctional silane. Octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane and hecadecyltriethoxysilane are particularly preferred. The changed surface properties / hydrophobicity can improve adhesion, abrasion resistance and alignment in the application.

Suitable pigments based on a lamellar substrate platelet include, for example, the pigments of the VISIONAIRE series from Eckart.

Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH.

Pigments based on a substrate platelet comprising a vacuum metallized pigment are available, for example, under the name Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

In a further embodiment, a method according to the invention is characterized in that the composition (A) - based on the total weight of the composition (A) - has one or more pigments in a total amount of 0.001 to 20% by weight, in particular 0.05 up to 5% by weight.

In a further embodiment, a method according to the invention is characterized in that the composition (B) - based on the total weight of the composition (B) - has one or more pigments in a total amount of 0.001 to 20% by weight, in particular 0.05 up to 5% by weight.

The compositions according to the invention can also contain one or more substantive dyes as coloring compounds. Substantive dyes are dyes that are absorbed directly onto the hair and do not require an oxidative process to develop the color. Substantive dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols.

The substantive dyes for the purposes of the present invention have a solubility in water (760 mmHg) at 25 ° C. of more than 0.5 g / L and are therefore not to be regarded as pigments. For the purposes of the present invention, the substantive dyes preferably have a solubility in water (760 mmHg) at 25 ° C. of more than 1.0 g / l. In the context of the present invention, the substantive dyes particularly preferably have a solubility in water (760 mmHg) at 25 ° C. of more than 1.5 g / l.

Substantive dyes can be divided into anionic, cationic and nonionic substantive dyes.

In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one anionic, cationic and / or nonionic substantive dye as the coloring compound.

In a further preferred embodiment, a method according to the invention is characterized in that the composition (B) and / or the composition (C) contains at least one coloring compound from the group of anionic, nonionic and / or cationic substantive dyes.

Suitable cationic substantive dyes are, for example, 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 Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51 Basic Red 76

Nonionic nitro and quinone dyes and neutral azo dyes, for example, can be used as nonionic substantive dyes. Suitable nonionic substantive dyes are those under the international names 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 Red 10, HC Red 11, HC Red 13, HC Red BN, 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 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, picric acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

Anionic substantive dyes are also referred to as acid dyes. Acid dyes are understood as meaning substantive dyes which have at least one carboxylic acid group (—COOH) and / or one sulfonic acid group (—SO ₃ H). Depending on the pH, the protonated forms (-COOH, -SO ₃ H) of the carboxylic acid or sulfonic acid groups are in equilibrium with their deprotonated forms (-COO ^- , -SO ₃ ^- before). The proportion of protonated forms increases with decreasing pH. If substantive dyes are used in the form of their salts, the carboxylic acid groups or sulfonic acid groups are present in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations in order to maintain electrical neutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.

The acid dyes for the purposes of the present invention have a solubility in water (760 mmHg) at 25 ° C. of more than 0.5 g / L and are therefore not to be regarded as pigments. For the purposes of the present invention, the acid dyes preferably have a solubility in water (760 mmHg) at 25 ° C. of more than 1.0 g / l.

The alkaline earth salts (such as calcium salts and magnesium salts) or aluminum salts of acid dyes often have a poorer solubility than the corresponding alkali salts. If the solubility of these salts is below 0.5 g / L (25 ° C, 760 mmHg), they do not fall under the definition of a substantive dye.

An essential feature of acid dyes is their ability to develop anionic charges, the carboxylic acid or sulfonic acid groups responsible for this usually being linked to different chromophoric systems. Suitable chromophoric systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.

One or more compounds from the following group can be selected as particularly suitable acid dyes: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n ° B001), Acid Yellow 3 (COLIPA n °: C 54, D&C Yellow N ° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n ° C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA n ° C015), Acid Orange 10 (CI 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1; CI
20170; KATSU201; nosodiumsalt; Brown No.201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D&C Brown No.1), Acid Red 14 (CI14720), Acid Red 18 (E124, Red 18; CI 16255) , Acid Red 27 (E 123, CI 16185, C-Red 46, Echtrot D, FD&C Red Nr.2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200) , Acid Red 35 (CI CI18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, lodeosin), Acid Red 52 (CI 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n ° 106 Pontacyl Brilliant Pink), Acid Red 73 (CI CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA n ° C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine, Simacid Erythrosine Y) , Acid Red 184 (CI 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext.D&C Violet n ° 2, CI 60730, COLIPA n ° C063), Acid Violet 49 (CI 42640), Acid Violet 50 ( CI 50325), Acid Blue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blau V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133, Patent Blue AE, Amidoblau AE, Erioglaucin A, CI 42090, CI Food Blue 2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585), Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI 42095), Acid Green 9 (CI42100), Acid Green 22 (CI42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, CI 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n ° 401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n ° B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI 14270), Food Blue 5, D&C

Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1.

The water solubility of the anionic substantive dyes can be determined, for example, in the following way. 0.1 g of the anionic substantive dye are placed in a beaker. A stir bar is added. Then 100 ml of water are added. This mixture is heated to 25 ° C. on a magnetic stirrer while stirring. It is stirred for 60 minutes. The aqueous mixture is then assessed visually. If there are still undissolved residues, the amount of water is increased - for example in steps of 10 ml. Water is added until the amount of dye used has completely dissolved. If the dye-water mixture cannot be assessed visually due to the high intensity of the dye, the mixture is filtered. If a portion of undissolved dyes remains on the filter paper, the solubility test is repeated with a larger amount of water. If 0.1 g of the anionic substantive dye dissolves in 100 ml of water at 25 ° C., the solubility of the dye is 1.0 g / L.

Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40 g / L (25 ° C).

Acid Yellow 3 is a mixture of the sodium salts of mono- and sisulfonic acids of 2- (2-quinolyl) -1H-indene-1,3 (2H) -dione and has a water solubility of 20 g / L (25 ° C).

Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its water solubility is above 40 g / L (25 ° C).

Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1- (4-sulfophenyl) -4 - ((4-sulfophenyl) azo) -1H-pyrazole-3-carboxylic acid and works well in water at 25 ° C soluble.

Acid Orange 7 is the sodium salt of 4 - [(2-Hydroxy-1-naphthyl) azo] benzene sulfonate. Its water solubility is more than 7 g / L (25 ° C).

Acid Red 18 is the trinity salt of 7-hydroxy-8 - [(E) - (4-sulfonato-1-naphthyl) -diazenyl)] - 1,3-naphthalenedisulfonate and has a very high solubility in water of more than 20 wt. %. Acid Red 33 is the diantrium salt of 5-amino-4-hydroxy-3- (phenylazo) -naphthalene-2,7-disulphonate, its water solubility is 2.5 g / L (25 ° C).

Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2- (1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl) benzoic acid, its water solubility is specified with greater than 10 g / L (25 ° C).

Acid Blue 9 is the disodium salt of 2 - ({4- [N-ethyl (3-sulfonatobenzyl] amino] phenyl} {4 - [(N-ethyl (3-sulfonatobenzyl) imino] -2,5-cyclohexadiene-1- ylidene} methyl) benzene sulfonate and has a water solubility of more than 20% by weight (25 ° C).

Furthermore, thermochromic dyes can also be used. Thermochromism includes the property of a material to change its color reversibly or irreversibly depending on the temperature. This can be done both by changing the intensity and / or the wavelength maximum.

Finally, it is also possible to use photochromic dyes. Photochromism includes the property of a material to change its color reversibly or irreversibly depending on the exposure to light, in particular UV light. This can be done both by changing the intensity and / or the wavelength maximum.

Film-forming polymers

To increase the wash fastness, the composition (A), the composition (B) and / or the optionally applicable composition (C) can each also contain at least one film-forming polymer.

In a further embodiment, a method according to the invention is characterized in that the composition (A), the composition (B) and / or the composition (C) contains at least one film-forming polymer.

Polymers are understood to mean macromolecules with a molecular weight of at least 1000 g / mol, preferably of at least 2500 g / mol, particularly preferably of at least 5000 g / mol, which consist of identical, repeating organic units. The polymers of the present invention can be synthetically produced polymers which are produced by polymerizing one type of monomer or by polymerizing different types of monomers which are structurally different from one another. If the polymer is produced by polymerizing one type of monomer, it is called a homo-polymer. If structurally different types of monomers are used in the polymerization, the resulting polymer is referred to as a copolymer.

The maximum molecular weight of the polymer depends on the degree of polymerisation (number of polymerised monomers) and the batch size and is also determined by the polymerisation method. For the purposes of the present invention, it is preferred if the maximum molecular weight of the film-forming, hydrophobic polymer (c) is not more than 10 ⁷ g / mol, preferably not more than 10 ⁶ g / mol and particularly preferably not more than 10 ⁵ g / mol amounts.

In the context of the invention, a film-forming polymer is understood to mean a polymer which is able to form a film on a substrate, for example on a keratinic material or a keratinous fiber. The formation of a film can be detected, for example, by viewing the keratin material treated with the polymer under a microscope.

The film-forming polymers can be hydrophilic or hydrophobic.

In a first embodiment, it may be preferred to use at least one hydrophobic, film-forming polymer in composition (B).

A hydrophobic polymer is understood to mean a polymer that has a solubility in water at 25 ° C. (760 mmHg) of less than 1% by weight.

The water solubility of the film-forming, hydrophobic polymer can be determined, for example, in the following way. 1.0 g of the polymer is placed in a beaker. Make up to 100 g with water. A stir bar is added and the mixture is warmed to 25 ° C on a magnetic stirrer while stirring. It is stirred for 60 minutes. The aqueous mixture is then assessed visually. If the polymer-water mixture cannot be assessed visually due to the high turbidity of the mixture, the mixture is filtered. If a proportion of undissolved polymer remains on the filter paper, the solubility of the polymer is less than 1% by weight.

The polymers of the acrylic acid type, the polyurethanes, the polyesters, the polyamides, the polyureas, the cellulose polymers, the nitrocellulose polymers, the silicone polymers, the polymers of the acrylamide type and the polyisoprenes can be mentioned here in particular .

Particularly suitable film-forming, hydrophobic polymers are, for example, polymers from the group of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinyl pyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and / or the polyamides.

The film-forming hydrophobic polymers which are selected from the group of synthetic polymers, the polymers obtainable by free radical polymerization or the natural polymers have proven particularly suitable for achieving the object of the invention.

Further particularly suitable film-forming hydrophobic polymers can be selected from the homopolymers or copolymers of olefins, such as cycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinyl amides, the esters or amides of (meth) acrylic acid with at least one C ₁ -C ₂₀ - Alkyl group, an aryl group or a C ₂ -C ₁₀ -hydroxyalkyl group.

Further film-forming hydrophobic polymers can be selected from the homo- or copolymers of isooctyl (meth) acrylate; Isononyl (meth) acrylate; 2-ethylhexyl (meth) acrylate; Lauryl (meth) acrylate); isopentyl (meth) acrylate; n-butyl (meth) acrylate); Isobutyl (meth) acrylate; Ethyl (meth) acrylate; Methyl (meth) acrylate; tert-butyl (meth) acrylate; Stearyl (meth) acrylate; Hydroxyethyl (meth) acrylate; 2-hydroxypropyl (methacrylate; 3-hydroxypropyl (meth) acrylate and / or mixtures thereof).

Further film-forming hydrophobic polymers can be selected from the homo- or copolymers of (meth) acrylamide; N-alkyl (meth) acrylamides, in particular those with C2-C18 alkyl groups, such as, for example, N-ethyl-acrylamide, N-tert-butyl-acrylamide, N-octyl-acrylamide; N-di (C1-C4) alkyl (meth) acrylamide.

Other preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A suitable commercial product is, for example Aculyn ^® 33 from Rohm & Haas. However, copolymers of acrylic acid, methacrylic acid or their C ₁ -C ₆ -alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol are also preferred. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20.

On the market most preferred polymers are for example Aculyn _® 22 (Acrylates / Steareth-20 Methacrylate Copolymer), Aculyn _® 28 (Acrylates / Beheneth-25 Methacrylate Copolymer), Structure 2001 _® (Acrylates / steareth-20 itaconate Copolymer), Structure 3001 _® (Acrylates / Ceteth-20 Itaconate Copolymer), Structure Plus _® (Acrylates / Aminoacrylates C10-30 Alkyl PEG-20 Itaconate Copolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates / CI0- 30 Alkyl Acrylate Crosspolymer), Synthalen W 2000® (Acrylates / Palmeth-25 Acrylate Copolymer) or the Soltex OPT (Acrylates / C12-22 Alkyl methacrylate Copolymer) sold by Rohme and Haas.

Examples of suitable polymers based on vinyl monomers are the homo- and copolymers of N-vinylpyrrolidone, vinylcaprolactam, vinyl- (C1-C6-) alkyl-pyrrole, vinyl-oxazole, vinyl-thiazole, of vinylpyrimidine, of vinylimidazole.

The copolymers octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer, such as is sold commercially by NATIONAL STARCH under the trade names AMPHOMER® or LOVOCRYL® 47, or the copolymers of acrylates / octylacrylamides under the trade name DERMACRYL® are also very particularly suitable LT and DERMACRYL® 79 are sold by NATIONAL STARCH.

Examples of suitable polymers based on olefins are the homo- and copolymers of ethylene, propylene, butene, isoprene and butadiene.

In a further embodiment, the block copolymers which comprise at least one block made of styrene or the derivatives of styrene can be used as film-forming hydrophobic polymers. These block copolymers can be copolymers which, in addition to a styrene block, contain one or more other blocks, such as, for example, styrene / ethylene, styrene / ethylene / butylene, styrene / butylene, styrene / isoprene, styrene / butadiene. Corresponding polymers are sold commercially by BASF under the trade name “Luvitol HSB”.

In a first embodiment, it can be preferred to use at least one hydrophilic, film-forming polymer in the composition (A), (B) and / or (C).

A hydrophilic polymer is understood to mean a polymer that has a solubility in water at 25 ° C. (760 mmHg) of more than 1% by weight, preferably more than 2% by weight.

The water solubility of the film-forming hydrophilic polymer can be determined, for example, in the following way. 1.0 g of the polymer is placed in a beaker. Make up to 100 g with water. A stir bar is added and the mixture is warmed to 25 ° C on a magnetic stirrer while stirring. It is stirred for 60 minutes. The aqueous mixture is then assessed visually. A completely dissolved polymer appears to be homogeneous under a markoscopy. If the polymer-water mixture cannot be assessed visually due to the high turbidity of the mixture, the mixture is filtered. If no undissolved polymer remains on the filter paper, the solubility of the polymer is more than 1% by weight.

Nonionic, anionic and cationic polymers can be used as film-forming, hydrophilic polymers.

Suitable film-forming, hydrophilic polymers can, for example, from the group of polyvinylpyrrolidone (co) polymers, polyvinyl alcohol (co) polymers, vinyl acetate (co) polymers, carboxyvinyl (co) polymers, acrylic acid (co) polymers, methacrylic acid (co) polymers, natural gums, polysaccharides and / or acrylamide (co) polymers.

Furthermore, it is very particularly preferred to use polyvinylpyrrolidone (PVP) and / or a vinylpyrrolidone-containing copolymer as the film-forming hydrophilic polymer.

It is also preferred if the composition (A), (B) and / or (C) according to the invention contains polyvinylpyrrolidone (PVP) as the film-forming, hydrophilic polymer. Surprisingly, the washfastness of the dyeings that could be obtained with agents containing PVP was also very good.

Particularly suitable polyvinylpyrrolidones are available, for example, under the name Luviskol® K from BASF SE, in particular Luviskol® K 90 or Luviskol® K 85 from BASF SE.

The polymer PVP K30, which is sold by Ashland (ISP, POI Chemical), can also be used as another polyvinylpyrrolidone (PVP) that is explicitly very particularly suitable. PVP K 30 is a polyvinylpyrrolidone which is very soluble in cold water and has the CAS number 9003-39-8. The molecular weight of PVP K 30 is approx. 40,000 g / mol.

Other particularly suitable polyvinylpyrrolidones are the substances known under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60, LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115 and available from BASF.

The use of film-forming hydrophilic polymers from the group of copolymers of polyvinylpyrrolidone has also led to particularly good and washable color results.

Particularly suitable film-forming, hydrophilic polymers that can be mentioned in this context are vinylpyrrolidone-vinyl ester copolymers, such as those marketed, for example, under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, both vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

Of the vinylpyrrolidone-containing copolymers, a styrene / VP copolymer and / or a vinylpyrrolidone-vinyl acetate copolymer and / or a VP / DMAPA acrylates copolymer and / or a VP / vinyl caprolactam / DMAPA acrylates copolymer are very particularly preferably used in the cosmetic compositions .

Vinylpyrrolidone-vinyl acetate copolymers are sold under the name Luviskol® VA by BASF SE. A VP / vinyl caprolactam / DMAPA Acrylates copolymer is sold by Ashland Inc. under the trade name Aquaflex® SF-40. A VP / DMAPA Acrylates copolymer is sold, for example, under the name Styleze CC-10 by Ashland and is a highly preferred vinylpyrrolidone-containing copolymer.

The copolymers obtained by reacting N-vinylpyrrolidone with at least one further monomer from the group consisting of V-vinylformamide, vinyl acetate, ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactone and / or vinyl alcohol can also be mentioned as further suitable copolymers of polyvinylpyrrolidone .

Another suitable copolymer of vinyl pyrrolidone is the polymer known under the INCI name maltodextrin / VP copolymer.

It was also possible to obtain intensely colored keratin material, in particular hair, with very good wash fastness properties if a nonionic, film-forming, hydrophilic polymer was used as the film-forming, hydrophilic polymer.

In a first embodiment, it can be preferred if the composition (B) contain at least one nonionic, film-forming, hydrophilic polymer.

According to the invention, a nonionic polymer is understood to mean a polymer which in a protic solvent - such as, for example, water - does not carry structural units with permanently cationic or anionic groups under standard conditions, which have to be compensated by counterions while maintaining electrical neutrality. Cationic groups include, for example, quaternized ammonium groups, but not protonated amines. Anionic groups include, for example, carboxyl and sulfonic acid groups.

• - Polyvinylpyrrolidon,
• - Copolymeren aus N-Vinylpyrrolidon und Vinylestern von Carbonsäuren mit 2 bis 18 Kohlenstoffatomen, insbesondere aus N-Vinylpyrrolidon und Vinylacetat,
• - Copolymeren aus N-Vinylpyrrolidon und N-Vinylimidazol und Methacrylamid,
• - Copolymeren aus N-Vinylpyrrolidon und N-Vinylimidazol und Acrylamid,
• - Copolymeren aus N-Vinylpyrrolidon mit N,N-Di(C₁ bis C₄)-Alkylamino-(C₂ bis C₄)-alkylacrylamid.

The agents are very particularly preferred which contain, as the nonionic, film-forming, hydrophilic polymer, at least one polymer selected from the group consisting of

• - polyvinylpyrrolidone,
• - Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids with 2 to 18 carbon atoms, in particular of N-vinylpyrrolidone and vinyl acetate,
• - copolymers of N-vinylpyrrolidone and N-vinylimidazole and methacrylamide,
• - copolymers of N-vinylpyrrolidone and N-vinylimidazole and acrylamide,
• - Copolymers of N-vinylpyrrolidone with N, N-di (C ₁ to C ₄ ) -alkylamino- (C ₂ to C ₄ ) -alkylacrylamide.

If copolymers of N-vinylpyrrolidone and vinyl acetate are used, it is again preferred if the molar ratio of the structural units contained in the monomer N-vinylpyrrolidone to the structural units of the polymer contained in the monomer vinyl acetate is in the range from 20:80 to 80:20, in particular from 30 to 70 to 60 to 40. Suitable copolymers of vinyl pyrrolidone and vinyl acetate are available, for example, under the trademarks Luviskol® VA 37, Luviskol® VA 55, Luviskol® VA 64 and Luviskol® VA 73 from BASF SE.

Another particularly preferred polymer is selected from the polymers with the INCI name VP / Methacrylamide / Vinyl Imidazole Copolymer, which are available, for example, under the trade name Luviset Clear from BASF SE.

Another very particularly preferred nonionic, film-forming, hydrophilic polymer is a copolymer of N-vinylpyrrolidone and N, N-dimethylaminiopropyl methacrylamide, which, for example, with the INCI name VP / DMAPA Acrylates Copolymer z. B. is sold under the trade name Styleze _® CC 10 by the company ISP.

A cationic polymer according to the invention is the copolymer of N-vinylpyrrolidone, N-vinylcaprolactam, N- (3-dimethylaminopropyl) methacrylamide and 3- (methacryloylamino) propyl-lauryl-dimethylammonium chloride (INCI name: Polyquaternium-69), which, for example, under the trade name AquaStyle ^® 300 (28-32% by weight of active substance in an ethanol-water mixture, molecular weight 350,000) is sold by ISP.

• - Vinylpyrrolidon-Vinylimidazoliummethochlorid-Copolymere, wie sie unter den Bezeichnungen Luviquat^® FC 370, FC 550 und der INCI-Bezeichnung Polyquaternium-16 sowie FC 905 und HM 552 angeboten werden,
• - Vinylpyrrolidon-Vinylcaprolactam-Acrylat-Terpolymere, wie sie mit Acrylsäureestern und Acrylsäureamiden als dritter Monomerbaustein im Handel beispielsweise unter der Bezeichnung Aquaflex^® SF 40 angeboten werden.

Further suitable film-forming, hydrophilic polymers are, for example

• - Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as they are offered under the names Luviquat ^® FC 370, FC 550 and the INCI name Polyquaternium-16 as well as FC 905 and HM 552,
• - Vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, as offered commercially with acrylic acid esters and acrylic acid amides as the third monomer component, for example under the name Aquaflex ^® SF 40.

Polyquaternium-11 is the reaction product of diethyl sulfate with a copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate. Suitable commercial products are available, for example under the names Dehyquart® CC 11 and Luviquat ^® PQ 11 PN by BASF SE or Gafquat 440, Gafquat 734, Gafquat 755, or Gafquat 755N from Ashland Inc..

Polyquaternium-46 is the reaction product of caprolactam and vinylpyrrolidone with methylvinylimidazolium and is for example available under the name Luviquat.RTM ^® Hold by BASF SE. Polyquaternium-46 is preferably used in an amount of 1 to 5% by weight, based on the total weight of the cosmetic composition. It is particularly preferred that Polyquaternium-46 is used in combination with a cationic guar compound. It is even most preferred that Polyquaternium-46 is used in combination with a cationic guar compound and Polyquaternium-11.

Acrylic acid polymers, for example, which can be present in uncrosslinked or crosslinked form, can be used as suitable anionic film-forming, hydrophilic polymers. Corresponding products are sold commercially, for example, under the trade names Carbopol 980, 981, 954, 2984 and 5984 by Lubrizol or also under the names Synthalen M and Synthalen K by 3V Sigma (The Sun Chemicals, Inter Harz).

Examples of suitable film-forming, hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum, carob gum.

Examples of suitable film-forming, hydrophilic polymers from the group of the polysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.

Suitable film-forming, hydrophilic polymers from the group of acrylamides are, for example, polymers which are produced starting from monomers of (meth) acrylamido-C1-C4-alkyl-sulfonic acid or the salts thereof. Corresponding polymers can be selected from the polymers of polyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid, polyacrylamidopropanesulfonic acid, poly2-acrylamido-2-methylpropanesulfonic acid, poly-2-methylacrylamido-2-methylpropanesulfonic acid and / or poly-2-methylacrylamido-n-butanesulfonic acid.

Preferred polymers of the poly (meth) arylamido-C1-C4-alkyl-sulfonic acids are crosslinked and at least 90% neutralized. These polymers can be crosslinked or else uncrosslinked.

Crosslinked and completely or partially neutralized polymers of the poly-2-acrylamido-2-methylpropanesulfonic acid type are known under the INCI names “Ammonium Polyacrylamido-2-methyl-propanesulphonate” or “Ammonium Polyacryldimethyltauramide”.

Another preferred polymer of this type is the crosslinked poly-2-acrylamido-2methyl-propanesulphonic acid polymer sold by Clamant under the trade name Hostacerin AMPS, which is partially neutralized with ammonia.

In a further explicitly very particularly preferred embodiment, a method according to the invention is characterized in that the composition (A), (B) and / or the optionally applicable composition (C) contains at least one anionic, film-forming polymer.

wobei M für ein Wasserstoffatom oder für Ammonium (NH₄), Natrium, Kalium, ½ Magnesium oder ½ Calcium steht.In this context, the best results could be obtained when the composition (A), (B) and / or the optionally applicable composition (C) contains at least one film-forming polymer which has at least one structural unit of the formula (PI) and at least one structural unit of the Formula (P-II) includes

where M stands for a hydrogen atom or for ammonium (NH ₄ ), sodium, potassium, ½ magnesium or ½ calcium.

When M stands for a hydrogen atom, the structural unit of the formula (P-I) is based on an acrylic acid unit.

When M stands for an ammonium counterion, the structural unit of the formula (P-I) is based on the ammonium salt of acrylic acid.

If M stands for a sodium counterion, the structural unit of the formula (PI) is based on the sodium salt of acrylic acid.

If M stands for a potassium counterion, the structural unit of the formula (P-I) is based on the potassium salt of acrylic acid.

When M stands for half an equivalent of a magnesium counterion, the structural unit of the formula (P-I) is based on the magnesium salt of acrylic acid.

If M stands for half an equivalent of a calcium counterion, the structural unit of the formula (P-I) is based on the calcium salt of acrylic acid.

The film-forming polymer or polymers according to the invention are preferably used in certain quantity ranges in the respective composition. In this context, it has proven to be particularly preferred to solve the problem according to the invention if the composition - based in each case on its total weight - has one or more film-forming polymers in a total amount of 0.1 to 18.0% by weight, preferably 1 , 0 to 16.0% by weight, more preferably from 5.0 to 14.5% by weight and very particularly preferably from 8.0 to 12.0% by weight.

Application of compositions (A) and (B)

The method according to the invention comprises the application of the two compositions (A) and (B) to the keratinic material. The two compositions (A) and (B) are two different compositions.

As already described above, it is particularly preferred if the composition (A) is applied to the keratin material first, and then the composition (B) is applied to the keratin material in the form of an aftertreatment agent.

• (1) Auftragen des ersten Zusammensetzung (A) auf das Keratinmaterial,
• (2) Einwirkenlassen der Zusammensetzung (A) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (3) Ausspülen der Zusammensetzung (A) aus dem Keratinmaterial,
• (4) Auftragen der Zusammensetzung (B) auf das Keratinmaterial,
• (5) Einwirkenlassen der Zusammensetzung (B) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (6) Ausspülen der Zusammensetzung (B) aus dem Keratinmaterial.

In a further embodiment, a method according to the invention comprising the following steps is particularly preferred:

• (1) applying the first composition (A) to the keratin material,
• (2) allowing the composition (A) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (3) rinsing the composition (A) from the keratin material,
• (4) applying the composition (B) to the keratin material,
• (5) allowing the composition (B) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (6) rinsing the composition (B) from the keratin material.

Rinsing out the keratinous material with water in steps (3) and (6) of the method is understood according to the invention to mean that only water is used for the rinsing process, without any further compositions different from the compositions (a) and (b) would be used.

In a step (1), the composition (A) is first applied to the keratin materials, in particular the human hair.

After application, the composition (A) is allowed to act on the keratin materials. In this context, exposure times of 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 2 minutes on the hair have proven to be particularly advantageous.

In a preferred embodiment of the method according to the invention, the composition (A) can now be rinsed out of the keratin materials before the composition (B) is applied to the hair in the subsequent step.

In step (4) the composition (B) is now applied to the keratin materials. After application, the composition (B) is now allowed to act on the hair.

The process according to the invention allows dyeings with particularly good intensity and washfastness to be produced even if compositions (A) and (B) are left to act for a short time. Contact times of 10 seconds to 10 minutes, preferably of 20 seconds to 5 minutes and very particularly preferably of 30 seconds to 3 minutes on the hair have proven to be particularly advantageous.

In step (6) the composition (B) is then rinsed out of the keratin material with water.

• (1) Auftragen des ersten Zusammensetzung (A) auf das Keratinmaterial,
• (2) Einwirkenlassen der Zusammensetzung (A) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (3) Ausspülen der Zusammensetzung (A) aus dem Keratinmaterial,
• (4) Auftragen der Zusammensetzung (B) auf das Keratinmaterial,
• (5) Einwirkenlassen der Zusammensetzung (B) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (6) Ausspülen der Zusammensetzung (B) aus dem Keratinmaterial.

In a further embodiment, a method according to the invention comprising the following steps in the order given is particularly preferred:

• (1) applying the first composition (A) to the keratin material,
• (2) allowing the composition (A) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (3) rinsing the composition (A) from the keratin material,
• (4) applying the composition (B) to the keratin material,
• (5) allowing the composition (B) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (6) rinsing the composition (B) from the keratin material.

If, in addition, the optionally applicable third composition (C) is also applied to the keratin material, it can be used in various ways.

One possibility is to mix the composition (A) with the composition (C) before use, and then to apply the mixture of (A) and (C) to the keratin material.

Another possibility is to mix the composition (B) with the composition (C) before use, and then to apply the mixture of (B) and (C) to the keratin material.

In addition, it is also encompassed by the invention if, before use, all three compositions (A), (B) and (C) are mixed with one another and then this mixture of (A), (B) and (C) is applied to the keratin material becomes.

• (1) Auftragen des ersten Zusammensetzung (A) auf das Keratinmaterial,
• (2) Einwirkenlassen der Zusammensetzung (A) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (3) Ausspülen der Zusammensetzung (A) aus dem Keratinmaterial, (4) Auftragen der Zusammensetzung (B) auf das Keratinmaterial,
• (5) Einwirkenlassen der Zusammensetzung (B) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (6) Ausspülen der Zusammensetzung (B) aus dem Keratinmaterial.
• (7) Auftragen der Zusammensetzung (C) auf das Keratinmaterial,
• (8) Einwirkenlassen der Zusammensetzung (C) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (9) Ausspülen der Zusammensetzung (C) aus dem Keratinmaterial.

In a further embodiment, a method according to the invention comprising the following steps is particularly preferred:

• (1) applying the first composition (A) to the keratin material,
• (2) allowing the composition (A) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (3) rinsing the composition (A) out of the keratin material, (4) applying the composition (B) to the keratin material,
• (5) allowing the composition (B) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (6) rinsing the composition (B) from the keratin material.
• (7) applying the composition (C) to the keratin material,
• (8) allowing the composition (C) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (9) Rinsing the composition (C) from the keratin material.

• (1) Herstellung einer Anwendungsmischung durch Vermischen der Zusammensetzungen (A) und (B)
• (2) Auftragen der Mischung aus (A) und (B) auf das Keratinmaterial,
• (3) Einwirkenlassen der Mischung aus (A) und (B) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (4) Ausspülen der Mischung aus dem Keratinmaterial.

In a further embodiment, a method according to the invention comprising the following steps is particularly preferred:

• (1) Preparation of an application mixture by mixing compositions (A) and (B)
• (2) applying the mixture of (A) and (B) to the keratin material,
• (3) allowing the mixture of (A) and (B) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (4) rinsing the mixture from the keratin material.

• (1) Herstellung einer Anwendungsmischung durch Vermischen der Zusammensetzungen (A) und (B)
• (2) Auftragen der Mischung aus (A) und (B) auf das Keratinmaterial,
• (3) Einwirkenlassen der Mischung aus (A) und (B) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (4) Ausspülen der Mischung aus dem Keratinmaterial.
• (5) Auftragen der Zusammensetzung (C) auf das Keratinmaterial
• (6) Einwirkenlassen der Zusammensetzung (C) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten, und
• (7) Ausspülen der Zusammensetzung (C) aus dem Keratinmaterial.

In a further embodiment, a method according to the invention comprising the following steps is particularly preferred:

• (1) Preparation of an application mixture by mixing compositions (A) and (B)
• (2) applying the mixture of (A) and (B) to the keratin material,
• (3) allowing the mixture of (A) and (B) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (4) rinsing the mixture from the keratin material.
• (5) Applying the composition (C) to the keratin material
• (6) allowing the composition (C) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes, and
• (7) rinsing the composition (C) from the keratin material.

• (1) Herstellung einer Anwendungsmischung durch Vermischen der Zusammensetzungen (A) und (B) und (C)
• (2) Auftragen der Mischung aus (A) und (B) und (C) auf das Keratinmaterial,
• (3) Einwirkenlassen der Mischung aus (A) und (B) und (C) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
• (4) Ausspülen der Mischung aus dem Keratinmaterial.

In a further embodiment, a method according to the invention comprising the following steps is particularly preferred:

• (1) Preparation of an application mixture by mixing compositions (A) and (B) and (C)
• (2) applying the mixture of (A) and (B) and (C) to the keratin material,
• (3) allowing the mixture of (A) and (B) and (C) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes,
• (4) rinsing the mixture from the keratin material.

Multi-component packaging unit (kit-of-parts)

To increase user comfort, all preparations necessary for the application process, in particular for the dyeing process, are made available to the user in the form of a multi-component packaging unit (kit-of-parts).

• - einen ersten Container mit einer ersten Zusammensetzung (A) und
• - einen zweiten Container mit einer zweiten Zusammensetzung (B), wobei

die Zusammensetzungen (A) und (B) in einem der Ansprüche 1 bis 13 definiert sind,
mit der Maßgabe, dass die Mehrkomponenten-Verpackungseinheit keine Zusammensetzung umfasst, die eine oder mehrere Peroxoverbindungen enthält.A second subject matter of the present invention is a multi-component packaging unit (kit-of-parts) for treating keratinous material, comprehensively packaged separately from one another

• - A first container with a first composition (A) and
• - A second container with a second composition (B), wherein

the compositions (A) and (B) are defined in any one of claims 1 to 13,
with the proviso that the multi-component packaging unit does not include a composition which contains one or more peroxo compounds.

Furthermore, the multicomponent packaging unit according to the invention can also comprise a third packaging unit containing a cosmetic preparation (C). As described above, preparation (C) very particularly preferably contains at least one coloring compound.

• - einen dritten Container mit einer dritten Zusammensetzung (C), wobei die dritte Zusammensetzung (C) mindestens eine farbgebende Verbindung as der Gruppe der Pigmente und/oder der direktziehenden Farbstoffe enthält.

In a very particularly preferred embodiment, the multicomponent packaging unit (kit-of-parts) according to the invention comprises packaged separately from one another

• - A third container with a third composition (C), the third composition (C) containing at least one coloring compound as from the group of pigments and / or substantive dyes.

The coloring compounds from the group of pigments and substantive dyes have already been disclosed in detail in the description of the first subject of the invention.

With regard to the further preferred embodiments of the multicomponent packaging unit according to the invention, what has been said about the method according to the invention applies mutatis mutantis.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was 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.

Patent literature cited

• EP 2168633 B1 [0007, 0008, 0011]
• WO 2013068979 A2 [0008]
• EP 2168633 [0011]

Claims (15)

Method for dyeing keratinic material, in particular human hair, in which the keratinic material is used: a first composition (A) which contains: (A1) one or more organic C ₁ -C ₆ -alkoxy-silanes and / or their condensation products, and a second composition (B) which contains (B1) one or more oxidation dye precursors, with the proviso that in the process no composition is applied to the keratinic material which contains one or more peroxo compounds. Procedure according to Claim 1 , characterized in that the first composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (SI) and / or (S-II), R ₁ R ₂ NL-Si (OR ₃ ) _a (R ₄ ) _b (SI) where - R ₁ , R ₂ independently of one another represent a hydrogen atom or a C ₁ -C ₆ -alkyl group, - L represents a linear or branched, divalent C ₁ -C ₂₀ -alkylene group, - R ₃ , R ₄ independently of one another represent a C ₁ -C ₆ -alkyl group, - a, stands for an integer from 1 to 3, and - b stands for the integer 3 - a, and (R ₅ O) _c (R6) _d Si- (A) _e - [NR ₇ - (A ')] _f - [O- (A ")] _g - [NR ₈ - (A"')] _h -Si (R ₆ ') _d' (OR ₅ ') c _' (S-II), where - R5, R5 ', R5 ", R6, R6' and R6" independently of one another represent a C ₁ -C ₆ -alkyl group, - A, A ', A'',A''' and A '''' independently of one another represent a linear or branched, divalent C ₁ -C ₂ o-alkylene group, R ₇ and R ₈ independently of one another represent a hydrogen atom, a C ₁ -C ₆ -alkyl group, a hydroxy-C ₁ -C ₆ -alkyl group , a C ₂ -C ₆ -alkenyl group, an amino-C ₁ -C ₆ -alkyl group or a grouping of the formula (S-III), - (A "") - Si (R6 ") d" (OR5 ") c" (S-III), - c, stands for an integer from 1 to 3, - d stands for the integer 3 - c, - c 'stands for an integer from 1 to 3, - d' stands for the integer 3 - c ', - c "stands for an integer from 1 to 3, - d" stands for the integer 3 - c ", - e stands for 0 or 1, - f stands for 0 or 1, - g stands for 0 or 1, - h stands for 0 or 1, - with the proviso that at least one of the radicals from e, f, g and h is different from 0, and / or their condensation products. Method according to one of the Claims 1 to 2 , characterized in that the first composition (A) contains at least one organic C ₁ -C ₆ -alkoxysilane (A1) of the formula (SI), which is selected from the group of - (3-aminopropyl) triethoxysilane - (3- Aminopropyl) trimethoxysilane - (2-aminoethyl) triethoxysilane - (2-aminoethyl) trimethoxysilane - (3-dimethylaminopropyl) triethoxysilane - (3-dimethylaminopropyl) trimethoxysilane - (2-dimethylaminoethyl) triethoxysilane, - (2-dimethylaminoethyl) and / or their trimethoxysilane Condensation products. Method according to one of the Claims 1 to 3 , characterized in that the first composition (A) contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (S-IV), R ₉ Si (OR10) _k (R ₁₁ ) m (S-IV), where - R _{9 stands} for a C ₁ -C ₁₂ -alkyl group, - R _{10 stands} for a C ₁ -C ₆ -alkyl group, - R _{11 stands} for a C ₁ -C ₆ -alkyl group - k stands for an integer of 1 to 3, and - m for the integer 3 - k, and / or their condensation products. Method according to one of the Claims 1 to 4th , characterized in that the first composition (A) contains at least one organic C ₁ -C ₆ -alkoxysilane (A1) of the formula (S-IV), which is selected from the group of - methyltrimethoxysilane - methyltriethoxysilane - ethyltrimethoxysilane - ethyltriethoxysilane - hexyltrimethoxysilane - Hexyltriethoxysilane - Octyltrimethoxysilane - Octyltriethoxysilane - Dodecyltrimethoxysilane, - Dodecyltriethoxysilane, and / or their condensation products. Method according to one of the Claims 1 to 5 , characterized in that the first composition (A) has at least one cosmetic ingredient from the group consisting of hexamethyldisiloxane. Contains octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. Method according to one of the Claims 1 to 6 , characterized in that the second composition (B) contains one or more oxidation dye precursors (B1) selected from the group of p-phenylenediamine, p-tolylenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- ( α, β-Dihydroxyethyl) -p-phenylenediamine, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, N- (4-amino-3-methylphenyl) -N- [3- (1H-imidazole-1 -yl) propyl] amine, N, N'-bis- (β-hydroxyethyl) -N, N'-bis- (4-aminophenyl) -1,3-diamino-propan-2-ol, bis- (2- hydroxy-5-aminophenyl) methane, 1,3-bis (2,5-diaminophenoxy) propan-2-ol, N, N'-bis (4-aminophenyl) -1,4-diazacycloheptane, 1, 10-bis (2,5-diaminophenyl) -1,4,7,10-tetraoxadecane, p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (a , ß-dihydroxyethyl) phenol and 4-amino-2- (diethylaminomethyl) phenol, 4,5-diamino-1- (ß-hydroxyethyl) pyrazole, 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, and the physiologically acceptable salts of these compounds. Method according to one of the Claims 1 to 7th , characterized in that the second composition (B) contains one or more oxidation dye precursors (B1) selected from the group consisting of 2-methylresorcinol, 4-chlororesorcinol, resorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 2.7 - Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, 2-chloro-6-methyl-3-aminophenol and 2,6-dihydroxy-3,4 dimethylpyridine and the physiologically acceptable salts of these compounds. Method according to one of the Claims 1 to 8th , characterized in that the second composition (B) contains one or more oxidation dye precursors (B1) which are selected from the group of 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6 -dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline, 4-aminoindoline, 5,6- Dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2- carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole and the physiologically tolerated salts of these compounds. Method according to one of the Claims 1 to 9 , characterized in that the first composition (A) contains at least one coloring compound from the group of pigments and substantive dyes. Method according to one of the Claims 1 to 10 , characterized in that the second composition (B) contains at least one coloring compound as from the group of pigments and substantive dyes. Method according to one of the Claims 1 to 11 , in which the keratin material is applied: a third composition (C) which contains at least one coloring compound from the group of pigments and substantive dyes. Method according to one of the Claims 1 to 12 , characterized in that the composition (A), the composition (B) and / or the composition (C) contains at least one film-forming polymer. Method according to one of the Claims 1 to 13 , comprising the following steps: (1) applying the first composition (A) to the keratin material, (2) allowing the composition (A) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes, (3) Rinsing the composition (A) out of the keratin material, (4) applying the second composition (B) to the keratin material, (5) allowing the composition (B) to act on the keratin material for a period of 1 to 10 minutes, preferably 1 to 5 minutes , (6) rinsing the composition (B) from the keratin material. Multi-component packaging unit (kit-of-parts) for treating keratinic material, comprising packaged separately from one another - a first container with a first composition (A) and - a second container with a second composition (B), the compositions (A) and (B) in one of the Claims 1 to 13 are defined, with the proviso that the multi-component packaging unit does not comprise a composition which contains one or more peroxo compounds.