DE102020202676A1 - A method for coloring keratin material, comprising the use of two structurally different silanes and two structurally different polymers - Google Patents

Abstract

The present invention relates to a method for treating keratinous material, in particular human hair, in which a first composition (A) which contains (A1) one or more organic C1-C6-alkoxy-silanes is applied to the keratinous material Formula (SI) and / or their condensation products, R1R2N-L-Si (OR3) a (R4) b (SI) (A2) one or more organic C1-C12-alkyl-C1-C6-alkoxy-silanes of the formula (S. -II) and / or their condensation products, R5Si (OR6) k (R7) m (S-II), - a second composition (B) which contains (B1) at least one nonionic polymer and (B2) at least one anionic polymer.

Description

The present application is in the field of cosmetics and relates to a method for treating keratinous 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 -alkoxy-silane of a certain formula (SI) and a second C _{1 that is structurally different from the silanes of the formula (SI)} -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silane of the formula (S-II) contains. The composition (B) contains at least one nonionic polymer (B1) and furthermore at least one anionic polymer (B2).

A second subject matter 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 keratin fibers, in particular 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, intensive 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 dyeing 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 short-term color changes on the hair and / or the skin. Color pigments are generally understood to mean insoluble, coloring substances. These are undissolved in the form of small particles in the dye formulation and are only deposited on the outside of the hair fibers and / or the surface of the skin. 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 a detrimental 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.

With those 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 amounts of alkoxy-silane and water used in each case - 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 is shown, 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 is formed 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. 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. In this way, good staining results can be achieved after a short application period of just a few minutes. 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 that use the formation of colored films or coatings, however, are still in need of optimization. In particular, the color intensities and the fastness properties of the dyeings achieved with this dyeing system can still be further improved. The manageability, the consistency and the applicability of the formulations also still require optimization.

It was therefore the object of the present application to find a method for coloring keratinic materials, in particular human hair, which has improved color intensities and improved fastness properties, in particular improved wash fastness and improved rub fastness. Furthermore, the formulations applied in the context of this process should have improved handleability, consistency and applicability.

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. Here, the first composition (A) contains at least one organic C ₁ -C ₆ -alkoxy-silane of a certain formula (SI) and a second, structurally different from the silanes (SI), C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silane of the formula (S-II). The composition (B) contains at least one nonionic polymer (B1) and furthermore at least one anionic polymer (B2).

• - eine erste Zusammensetzung (A), die enthält (A1) ein oder mehrerer organische C₁-C₆-Alkoxy-Silane der Formel (S-I) und/oder deren Kondensationsprodukte, R₁R₂N-L-Si(OR₃)_a(R₄)_b (S-I)

wobei

• - R₁, R₂ unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe stehen,
• - L für eine lineare oder verzweigte, zweiwertige C₁C₂₀-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 (A2) ein oder mehrere organische C₁-C₁₂-Alkyl-C₁-C₆-Alkoxy-Silane der Formel (S-II) und/oder deren Kondensationsprodukte, R₅Si(OR₆)_k(R₇)_m (S-II),

wobei

• - R₅ für eine C₁-C₁₂-Alkylgruppe steht,
• - R₆ für eine C₁-C₆-Alkylgruppe steht,
• - R₇ 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,
• - eine zweite Zusammensetzung (B), die enthält (B1) mindestens ein nichtionisches Polymer und (B2) mindestens ein anionisches Polymer.

A first object of the present invention is a method for treating 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 of the formula (SI) and / or their condensation products, R ₁ R ₂ NL-Si (OR ₃ ) _a (R ₄ ) _b (SI)

whereby

• - 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 (A2) one or more organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes of the formula (S-II) and / or their condensation products, R ₅ Si (OR ₆ ) _k (R ₇ ) _m (S-II),

whereby

• - R _{5 represents} a C ₁ -C ₁₂ -alkyl group,
• - R _{6 stands} for a C ₁ -C ₆ -alkyl group,
• - R _{7 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,
• - A second composition (B) which contains (B1) at least one nonionic polymer and (B2) at least one anionic polymer.

If the composition (A) was applied to the keratin material as part of a dyeing process, an improvement in the color intensity, the wash fastness and the rub fastness could be determined, for example, if the compositions (A) and (B) were mixed with one another before use and in their blending were placed on the keratin material. Even if the composition (B) was applied to the keratin material in the form of an aftertreatment agent after the application of the composition (A), it was possible to obtain very good color results which were distinguished by good fastness properties and greatly improved rubbing fastness.

Coloring of keratinic material

Keratinic material is to be understood as meaning hair, the skin, and the 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.

Compositions (A) and (B)

The method according to the invention comprises the use of the compositions (A) and (B) on keratinic material, in particular on human hair. The two compositions are different preparations which are preferably made available to the user in separate containers.

Both compositions (A) and (B) contain the ingredients (A1) and (A2) or (B1) and (B2) essential to the invention, each preferably in a cosmetic carrier. The cosmetic carrier can be water, a cosmetically acceptable solvent or mixtures thereof. Furthermore, it is also possible and preferred if the compositions are concentrates which contain the respective ingredients (A1) / (A2) or (B1) / (B2) as main components.

Silanes of the formulas (S-I) and (S-II) in the composition (A)

The composition (A) is characterized in that it contains one or more organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (SI) and / or their condensation products and also one or more organic C ₁ -C ₁₂ - Alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II) and / or their condensation products.

The work leading to this invention has shown that the resistance of the films or coatings formed on the keratinous material can be influenced by the nature and amount of the silanes (S-I) and (S-II) used. The silanes of the formula (S-I) are aminosilanes which, due to the amino group present in their structure, have a particularly high affinity for the keratin material.

If silanes of the type (S-I) are used in the composition (A), the films formed when this composition is used are distinguished by particularly good adhesion to the keratin material. On the other hand, the films that can be obtained with the use of the silanes (SI) alone are too soft or pliable - presumably also due to the amino group contained in the structure - and lack a sufficiently high degree of rigidity, which is evident when mechanical forces are applied is reflected on the keratin material in a rubbing fastness that still needs to be optimized. Tests have now shown that the rigidity and the rubbing fastness of the coatings can be further improved if the composition (A) contains a further type of silane of the formula (S-II) in addition to the silanes of the type (S-I).

When using a composition (A) which, in addition to one or more silanes of the formula (SI), also contained one or more silanes of the formula (S-II), it was consequently possible to obtain very durable coatings with good wash fastnesses and at the same time good rub fastness will.

Organic C ₁ -C ₆ -alkoxy-silanes are organic, non-polymeric silicon compounds which are preferably selected from the group of silanes with 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 skeleton 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.

Particularly good results could be obtained if, in the process according to the invention, C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (SI) and furthermore C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2 ) of the formula (S-II) were used. Since, as already described above, hydrolysis / condensation starts even with traces of moisture, the condensation products of the C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (SI) and the condensation products of the C ₁ -C ₁₂ -alkyl C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II) are included in this embodiment.

• - R₁, R₂ unabhängig voneinander für ein Wasserstoffatom oder eine C₁-C₆-Alkylgruppe stehen,
• - L für eine lineare oder verzweigte, zweiwertige C₁C₂₀-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.

As already described above, 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 their condensation products, R ₁ R ₂ NL-Si (OR ₃ ) _a (R ₄ ) _b (SI) whereby

• - 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 whole number 3 - a.

• Beispiele für eine C₁-C₆-Alkylgruppe sind die Gruppen Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, s-Butyl und t-Butyl, n-Pentyl und n-Hexyl. Propyl, Ethyl und Methyl sind bevorzugte Alkylreste. Beispiele für eine lineare zweiwertige C₁C₂₀-Alkylengruppe sind beispielsweise die Methylen-gruppe (-CH₂-), die Ethylengruppe (-CH₂-CH₂-), die Propylengruppe (-CH₂-CH₂-CH₂-) und die Butylengruppe (-CH₂-CH₂-CH₂-CH₂-). Die Propylengruppe (-CH₂-CH₂-CH₂-) ist besonders bevorzugt. Ab einer Kettenlänge von 3 C-Atomen können zweiwertige Alkylengruppen auch verzweigt sein. Beispiele für verzweigte, zweiwertige C₃-C₂₀-Alkylengruppen sind (-CH₂-CH(CH₃)-) und (-CH₂-CH(CH₃)-CH₂-).

The substituents R ₁ , R ₂ , R ₃ , R ₄ and L in the compounds of the formula (SI) are explained below by way of example:

• Examples of a C ₁ -C ₆ -alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of a 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. Particularly preferably -L- stands for 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 methylene group (-CH ₂ -) can alternatively also be referred to as a methanediyl group. The ethylene group (-CH ₂ -CH ₂ -) can alternatively also be referred to as ethane-1,2-diyl group. The propylene group (-CH ₂ -CH ₂ -CH ₂ -) can alternatively also be referred to as the propane-1,3-diyl group. The butylene group (-CH ₂ -CH ₂ -CH ₂ -CH ₂ -) can alternatively also be referred to as the butane-1,4-diyl group.

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. _{R 3} and R ₄ are particularly preferably, independently of one another, 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),
whereby

• - 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), where

• - R ₁ , R ₂ both represent a hydrogen atom, and
• - L represents 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 (SI) which are particularly suitable for solving the problem according to 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 (S-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.

• - R₅ für eine C₁-C₁₂-Alkylgruppe steht,
• - R₆ für eine C₁-C₆-Alkylgruppe steht,
• - R₇ 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.

As described above, it has been found in further dyeing tests that the rubbing fastness of the films obtained with the silanes of the type (SI) could be further improved if a composition (A) was used in the process according to the invention which additionally contained one or more organic C ₁ - C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II) and / or their condensation products, R ₅ Si (OR ₆ ) _k (R ₇ ) _m (S-II), whereby

• - R _{5 represents} a C ₁ -C ₁₂ -alkyl group,
• - R _{6 stands} for a C ₁ -C ₆ -alkyl group,
• - R _{7 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.

The compounds of the formula (S-II) are organic silicon compounds selected from silanes having a silicon atom, the organic silicon compound comprising one or more hydrolyzable groups per molecule.

• Beispiele für eine C₁-C₆-Alkylgruppe sind die Gruppen Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, s-Butyl und t-Butyl, n-Pentyl und n-Hexyl. Propyl, Ethyl und Methyl sind bevorzugte Alkylreste. Beispiele für die höherkettigen Mittglieder der C₁-C₁₂-Alkylgruppe sind weiterhin die n-Heptylgruppe, die n-Octylgruppe, die n-Nonylgruppe, die n-Decylgruppe, die n-Undedcangruppe und die n-Dodecangruppe.

The substituents R ₅ , R ₆ and R ₇ in the compounds of the formula (S-II) are explained below by way of example:

• Examples of a C ₁ -C ₆ -alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of the higher-chain members of the C ₁ -C ₁₂ -alkyl group are furthermore the n-heptyl group, the n-octyl group, the n-nonyl group, the n-decyl group, the n-undedcan group and the n-dodecane group.

In the organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II), the radical R5 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 5} is preferably a linear C ₁ -C ₈ -alkyl group. _{R 5} 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 5} particularly preferably represents a methyl group, an ethyl group or an n-octyl group.

In the organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II), the radical R _{6 stands} for a C ₁ -C ₆ -alkyl group. _{R 6} particularly preferably represents a methyl group or an ethyl group.

In the organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II), the radical R _{7 stands} for a C ₁ -C ₆ -alkyl group. _{R 7} 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 3, then m is 0. If k is 2, then m is 1. If k is 1, m is 2.

Dyeings with the best rub fastness properties could be obtained if the composition (A) contains at least one organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silane (A2) of the formula (S-II), in which the Remainder 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-II) which are particularly suitable for solving the problem according to 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 referred to as hexyltriethoxysilane)
  
• - n-Octyltrimethoxysilane (also called octyltrimethoxysilane)
  
• - n-Octyltriethoxysilane (also called octyltriethoxysilane)
  
• - n-Dodecyltrimethoxysilane (also referred to as dodecyltrimethoxysilane) and / or
  
• - n-Dodecyltriethoxysilane (also referred to 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 _{12 -alkyl-C 1} -C ₆ -alkoxy-silane (A2) of the formula (S-II) that is selected from the group

• - 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. Here, the condensation products represent a maximum of oligomeric compounds, but not polymers.

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 (SI) with water (reaction scheme using the example of 3-aminopropyltriethoxysilane):

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

respectively.

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

bzw.

Hydrolysis of organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II) 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:

respectively.

und/oder

und/oder

und/oder

und/oder

und/oder

und/oder

Possible condensation reactions are for example (shown on the basis of 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 more extensive condensation to form oligomers with several silane atoms are also possible and also preferred.

In these condensation reactions can both partially hydrolyzed and fully hydrolyzed C ₁ -C ₆ -alkoxysilanes the formula (SI) participate in the condensation-reacted with not, partially or completely hydrolyzed C ₁ -C ₆ -Alkoxysilanen the formula (SI) run through. In this case, the C ₁ -C ₆ -alkoxysilanes of the formula (SI) react with themselves.

In addition, both partially hydrolyzed and fully hydrolyzed C ₁ -C ₆ -alkoxysilanes of the formula (SI), which cause condensation with unreacted, partially or completely hydrolyzed C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II) run through. 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-II).

In addition, both partially hydrolyzed and fully hydrolyzed C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II), which condensation with not yet reacted, can also take part in the condensation reactions. pass through partially or completely hydrolyzed C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II). In this case, the C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II) 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 dyeing results during use and high fastness properties could be obtained if the composition (A) - based on its total weight - has one or more organic C ₁ -C ₆ -alkoxysilanes (A1) of the formula (SI) and / or the condensation products thereof in a total amount of 5.0 to 50.0% by weight, preferably 7.5 to 45% by weight, more preferably 10.0 to 35% by weight and very particularly preferably 15 Contains 0 to 25% by weight.

In a further embodiment, a very particularly preferred method is characterized in that the composition (A) - based on the total weight of the composition (A) - has one or more organic C ₁ -C ₆ alkoxysilanes (A1) of the formula (SI) in a total amount of 5.0 to 50.0% by weight, preferably from 7.5 to 45% by weight, more preferably from 10.0 to 35% by weight and very particularly preferably from 15.0 to 25% by weight .-% contains.

The tests carried out have shown that these dyeing results could be improved particularly greatly with regard to their rubfastness if the composition (A) - based on its total weight - also includes the C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy- Contains silanes (A2) of the formula (S-II) in the optimum quantity ranges. Particularly good results could be obtained when the composition (A) - based on the total weight of the composition (A) - has one or more organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II) in a total amount of from 20 to 80% by weight, preferably from 30 to 70% by weight, more preferably from 35 to 60% by weight and very particularly preferably from 40 to 55% by weight .

In a further embodiment, a very particularly preferred method is characterized in that the composition (A) - based on the total weight of the composition (A) - has one or more organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy- Silanes (A2) of the formula (S-II) in a total amount of from 20 to 80% by weight, preferably from 30 to 70% by weight, more preferably from 35 to 60% by weight and very particularly preferably from 40 to Contains 55% by weight.

As already described above, the properties of the coating produced by the application of the composition (A) on the keratin material in terms of its adhesiveness and its brittleness can be achieved particularly well by using the two silanes of the formulas (SI) and (S-II) coordinated proportions can be optimized. For this reason, it has been found to be particularly preferable if the weight ratio of the total amount of the organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (SI) contained in the composition (A) to the total amount in the composition (A) contained organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II), ie the weight ratio (A1) / (A2), at a value of 0, 1 to 5.0, preferably from 0.1 to 2.5, more preferably from 0.1 to 1.5, even more preferably from 0.1 to 1.0 and very particularly preferably from 0.1 to 0.45 lies.

In a further embodiment, a very particularly preferred method is characterized in that the weight ratio of the total amount of the organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (SI) contained in the composition (A) to the total amount of the _{Organic C 1} -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II) contained in composition (A), ie the weight ratio (A1) / (A2), at a value of 0 , 1 to 5.0, preferably from 0.1 to 2.5, more preferably from 0.1 to 1.5, even more preferably from 0.1 to 1.0 and very particularly preferably from 0.1 to 0, 45 lies.

Further cosmetic ingredients in composition (A)

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

The cosmetic ingredients that 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, one or more surface-active compounds 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 fatty components can be used in composition (A) 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, plant extracts and protein hydrolysates.

The person skilled in the art will select these additional substances in accordance with 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.

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.

To ensure a sufficiently high storage stability, the composition (A) can be characterized in that it is low in water, preferably essentially free of water. The composition (A) therefore preferably contains less than 15% by weight of water, based on the total weight of the composition (A).

With a water content of just below 15% by weight, the compositions (A) are storage-stable over long periods of time. In order to improve the storage stability even further and to ensure a sufficiently high reactivity of the silanes of the formulas (S-I) and (S-II), however, it has been found to be particularly preferred to lower the water content in the composition (A) even further. For this reason, the first composition (A) contains - based on the total weight of the composition (A) - preferably 0.01 to 15.0% by weight, preferably 0.1 to 13.0% by weight, more preferably 0, 5 to 11.0 and very particularly preferably 1.0 to 9.0 wt .-% water.

In the context of a very particularly preferred embodiment, a method according to the invention is characterized in that the first composition (A) - based on the total weight of the composition (A) - 0.01 to 15.0% by weight, preferably 0.1 to 13 , 0% by weight, more preferably 0.5 to 11.0 and very particularly preferably 1.0 to 9.0% by weight of water.

In a further embodiment, however, a water-containing composition (A) can also be applied to the keratin material. In the context of this 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 99.0% by weight, preferably 60.0 to 98.0% by weight. -%, more preferably 65.0 to 97.0 and very particularly preferably 70.0 to 96.0% 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, for example, pH value measurement using glass electrodes using combination electrodes 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.

Polymers in the composition (B)

• (B1) mindestens ein nichtionisches Polymer und
• (B2) mindestens ein anionisches Polymer.

The method according to the invention is characterized by the use of a cosmetic composition (B) on the keratinic material, in particular on human hair, this second composition B) containing

• (B1) at least one nonionic polymer and
• (B2) at least one anionic polymer.

In the course of the process according to the invention, the composition (B) can either be mixed with the composition (A) shortly before use. In this case, the application mixture produced from (A) and (B) is applied to the keratin material. Furthermore, it is according to the invention to apply the preparations (A) and (B) one after the other to the keratin material in the form of a sequential method, i.e. first the preparation (A) is applied and then the preparation (B) is applied.

In both cases, the application of the two polymers or polymer groups (B1) and (B2) forms a further film on the keratin material. If the two preparations (A) and (B) are mixed before use, the film formed comprises both the silanes (A1) and (A2) (or theirs Condensates) as well as the polymers (B1) and (B2). When compositions (A) and (B) are applied in succession, a first film is initially generated by composition (A), which is then covered by a second film as a result of the subsequent application of composition (B).

In both applications, the keratin material is covered by a film or a layer system of films after use, the active substances (A1), (A2), (B1) and (B2) being responsible for the formation of the films (or the coating) are. The tests leading to this invention have shown that the interaction of these four active ingredients (A1) / (A2) / (B1) / (B2) leads to very resistant films that are resistant to external environmental influences such as mechanical forces, combing, washing and shampooing show particularly good resistance.

The second composition (B) is characterized in that it contains (B1) at least one nonionic polymer and (B2) at least one anionic 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 homo-polymer. If structurally different types of monomers are used in the polymerization, the resulting polymer is referred to as a copolymer.

Furthermore, the polymers according to the invention can also be natural polymers and / or the derivatives of natural polymers.

In the context of the process according to the invention, it has been found to be preferred if the at least one nonionic polymer (B1) is the derivative of a natural polymer, and if the at least one anionic polymer (B2) is a synthetically produced polymer.

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 to.

As the first ingredient essential to the invention, the composition (B) contains at least one nonionic polymer (B1).

According to the invention, a nonionic polymer (B1) is understood to mean a polymer which, in a protic solvent - such as 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.

It is very particularly preferred if the second composition (B) contains at least one natural polymer and / or the nonionic derivative of a natural polymer as the nonionic polymer (B1).

Cellulose derivatives, for example, which are used as thickeners, can be used as natural nonionic polymer (B1). Examples are agar-agar, scleroglucangum or polyoses, guar gums, locust bean gum, dextrans, starch fractions and derivatives such as amylose, amylopectin and dextrins, gelatin and casein and, in particular, cellulose derivatives such as methyl cellulose and hydroxyalkyl celluloses such as hydroxyethyl cellulose.

Natural polymers from the substance classes mentioned are commercially available and are, for example, sold under the trade names Deuteron®-XN (nonionic polysaccharide, Schoener GmbH), Cekol (cellulose gum, Kelco).

The method according to the invention very particularly preferably comprises the use of a second composition (B) on the keratin material, the composition (B) containing at least one nonionic cellulose and / or at least one nonionic cellulose derivative (B1).

A cellulose in the context of this invention is understood to mean both cellulose itself and a derivative thereof, i.e. a chemically or physically modified cellulose.

Cellulose is made up of β-1,4-glycosidically linked D-glucopyranose units. In the solid state, crystalline regions in cellulose alternate with those of low order (amorphous regions). Natural and production-related impurities, such as in particular the presence of carboxy groups, are typically in the region of approx. 1%. According to the invention, cellulose itself is therefore not regarded as an anionic polysaccharide.

Cellulose which can be used according to the invention preferably has a degree of polymerization (DP), that is to say a chain length composed of glucopyranose units, of 10 to about 8,000.

In particular, so-called microcrystalline cellulose can also show advantageous effects here. Microcrystalline cellulose is obtained by partial alkaline or acidic hydrolysis of celluloses, in which only the amorphous areas of the partially crystalline cellulose are attacked and completely dissolved. The first result is microfine cellulose, which is disaggregated into microcrystalline cellulose in an aqueous suspension under the action of mechanical force.

The degree of polymerization (also leveling-off degree of polymerization = LODP) of the microcrystalline cellulose remaining after hydrolysis is in the range from approx. 30-400.

Preferred celluloses are therefore microcrystalline celluloses and have a degree of polymerization of 30 to 400.

In the context of this invention, a nonionic cellulose (B1) is also understood to mean a nonionic derivative of a cellulose, i.e. the cellulose can be provided with substituents by reaction with a chemical agent and / or carry further uncharged chemical functional groups.

The nonionic cellulose derivatives and the definition of the nonionic celluloses fall within the meaning of the present invention. Corresponding chemically modified celluloses (B1) are nonionic.

The nonionic celluloses are very particularly preferred. These can be selected, for example, from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxypropyl methyl cellulose, methyl ethyl cellulose and ethyl cellulose.

The nonionic celluloses from the group of cellulose ethers, from the group of hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose are particularly well suited for achieving the object of the invention. These are sold, for example, under the trademarks Culminal® and Benecel® and Natrosol® types by the companies Aqualon, Hercules or Ashland.

A hydroxypropyl cellulose with a molecular weight of 30,000 to 50,000 g / mol, which is sold, for example, under the trade name Nisso Sl® by the company Lehmann & Voss, Hamburg, is also very particularly suitable.

The best results could be obtained with the use of non-ionic celluloses (B1). For this reason, it is very particularly preferred if a composition (B) is used in the process according to the invention which contains at least one nonionic polysaccharide (B1), preferably at least one nonionic cellulose derivative.

In the context of a further very particularly preferred embodiment, a method according to the invention is thus characterized in that the second composition (B) contains at least one nonionic polysaccharide (B1), preferably at least one nonionic cellulose derivative.

Within the group of celluloses, in particular within the group of nonionic cellulose derivatives, celluloses which have been modified _{with a hydroxy-C 1} -C _{6 -alkyl group have proven to be particularly suitable.}

Celluloses which have at least one 2-hydroxyethyl group, at least one 2-hydroxypropyl group and / or which carry at least one 3-hydroxypropyl group have proven particularly suitable for achieving the object of the invention.

In a further embodiment, a very particularly preferred method is characterized in that the second composition (B) contains at least one nonionic cellulose (B1) selected from the group consisting of 2-hydroxyethyl cellulose, 2-hydroxypropyl cellulose and 3-hydroxypropyl -Cellulose, 2-hydroxypropyl-methyl-cellulose and / or 3-hydroxypropyl-methyl-cellulose.

In addition, very good color results could be obtained if a composition (B) was applied to the keratin material in the context of the method according to the invention, which composition contained two different nonionic cellulose derivatives (B1 ') and (B1 ").

In a further particularly preferred embodiment, a method according to the invention is characterized in that the second composition (B) contains
(B1 ') a first nonionic cellulose which carries at least one hydroxyethyl group and (B1 ") a second nonionic cellulose which carries at least one hydroxypropyl group.

In the context of a further very particularly preferred embodiment, a method according to the invention is characterized in that the second composition (B) contains
(B1 ') 2-hydroxyethyl cellulose and
(B1 ″) at least one cellulose from the group of 2-hydroxypropyl cellulose, 3-hydroxypropyl cellulose, 2-hydroxypropyl methyl cellulose and / or 3-hydroxypropyl methyl cellulose.

The two celluloses (B1 ') and (B1 ") are structurally different from one another.

A particularly suitable cellulose with a 2-hydroxyethyl group is 2-hydroxethyl cellulose, CAS no. 9004-62-0, which can be obtained commercially from Ashland (Herkules) under the trade name Natrosol 250 HR.

A particularly suitable cellulose with a hydroxypropyl group is hydroxypropyl cellulose, CAS no. 9004-64-2, which can be purchased from Hercules under the trade name Klucel H CS.

A particularly suitable cellulose with a hydroxypropyl group is hydroxypropyl methyl cellulose, CAS no. 9004-65-3, which can be purchased under the trade name Benecel K 4 M from Ashland (or Hercules) or under the trade name Methocel 267 from Dow.

To optimize the consistency and applicability, the nonionic cellulose (B1) (or the nonionic celluloses (B1 ') and (B1 ")), in particular the aforementioned preferred and particularly preferred representatives, are preferably used in certain quantity ranges in the composition ( B) used.

In a further embodiment, a very particularly preferred method is characterized in that the second composition (B) - based on the total weight of the composition (B) - has one or more nonionic polymers (B1) in a total amount of 0.1 to 10.0 % By weight, preferably 0.1 to 8.0% by weight, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4.0% by weight.

In a further embodiment, a very particularly preferred method is characterized in that the second composition (B) - based on the total weight of the composition (B) - has one or more nonionic celluloses (B1) in a total amount of 0.1 to 10.0 % By weight, preferably 0.1 to 8.0% by weight, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4.0% by weight.

Furthermore, it is very particularly preferred if the composition (B) - based on the total weight of the composition (B) - (B1) 0.1 to 10.0% by weight, preferably 0.1 to 8.0% by weight %, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4.0% by weight of 2-hydroxyethyl cellulose.

In a further embodiment, a very particularly preferred method is characterized in that the second composition (B) - based on the total weight of the composition (B) - contains
(B1) 0.1 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4 , 0% by weight 2-hydroxyethyl cellulose.

In a further embodiment, a particularly preferred method is characterized in that the second composition (B) - based on the total weight of the composition (B) - has one or more celluloses (B1) from the group of 2-hydroxypropyl cellulose, 3- Hydroxypropyl cellulose, 2-hydroxypropyl methyl cellulose and / or 3-hydroxypropyl methyl cellulose in a total amount of 0.1 to 8.0% by weight, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4.0% by weight.

Furthermore, it is very particularly preferred if the composition (B) - based on the total weight of the composition (B) -
(B1) one or more celluloses from the group of 2-hydroxypropyl cellulose, 3-hydroxypropyl cellulose, 2-hydroxypropyl methyl cellulose and / or 3-hydroxypropyl methyl cellulose in a total amount of 0.1 to 8, 0% by weight, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4.0% by weight.

In addition, it was also possible to achieve very good effects if the celluloses (B1 ') and (B1 ") are used in the composition (B) in certain weight ratios to one another.

In a further embodiment, a very particularly preferred method is characterized in that the second composition (B) - based on the total weight of the composition (B) - contains
(B1 ') 0.1 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4.0% by weight of 2-hydroxyethyl cellulose and (B1 ") one or more celluloses from the group of 2-hydroxypropyl cellulose, 3-hydroxypropyl cellulose, 2-hydroxypropyl methyl cellulose and / or 3-hydroxypropyl -Methyl cellulose in a total amount of 0.1 to 8.0% by weight, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4.0% by weight.

In a further embodiment, a particularly preferred method is characterized in that the weight ratio of all celluloses (B1 ') contained in composition (B) to all celluloses (B1 ") contained in composition (B), ie the weight ratio (B1 ') / (B1 "), at a value from 0.2 to 5.0, preferably from 0.3 to 3.0, more preferably from 0.5 to 2.0 and very particularly preferably from 0.8 to 1, 5 lies.

In a further embodiment, a particularly preferred method is characterized in that the weight ratio of all the hydroxyethyl celluloses (B1 ') contained in the composition (B) to all the hydroxypropyl celluloses contained in the composition (B), (B1 "), ie the weight ratio ( B1 ') / (B1 "), at a value from 0.2 to 5.0, preferably from 0.3 to 3.0, more preferably from 0.5 to 2.0 and very particularly preferably from 0.8 to 1 , 5 lies.

As a second ingredient essential to the invention, the composition (B) contains at least one anionic polymer (B2).

An anionic polymer (B2) is understood according to the invention to mean a polymer which, in a protic solvent, in particular in an aqueous environment, carries structural units with anionic groups under standard conditions. While maintaining electrical neutrality, these anionic groups are neutralized by stoichiometric equivalents of counterions, such as alkali metal cations, alkaline earth metal cations or ammonium ions (NH ₄ ⁺ ). The group of anionic groups present in the polymer includes carboxy groups, sulfonic acid groups and phosphonic acid groups, in particular carboxy and sulfonic acid groups. When the polymer is used, the carboxylic acid and sulfonic acid groups can also initially still be present in protonated (uncharged) form and then converted into the corresponding anionic form on contact with the water-containing environment by splitting off a proton.

1. (i) Polymeren der Acrylsäure und/oder der Methacrylsäure,
2. (ii) Polymeren der 2-Acrylamido-2-methyl-1-propansulfonsäure,
3. (iii) anionischen Polysacchariden,
4. (iv) Polymeren der Itaconsäure und/oder der Crotonsäure und/oder
5. (v) Polymeren des Maleinsäureanhydrids.

In one possible embodiment, the anionic polymer (B2) can be selected from

1. (i) Polymers of acrylic acid and / or methacrylic acid,
2. (ii) polymers of 2-acrylamido-2-methyl-1-propanesulfonic acid,
3. (iii) anionic polysaccharides,
4. (iv) Polymers of itaconic acid and / or of crotonic acid and / or
5. (v) Polymers of maleic anhydride.

1. (i) Polymeren der Acrylsäure und/oder der Methacrylsäure,
2. (ii) Polymeren der 2-Acrylamido-2-methyl-1-propansulfonsäure,
3. (iii) anionischen Polysacchariden,
4. (iv) Polymeren der Itaconsäure und/oder der Crotonsäure und/oder
5. (v) Polymeren des Maleinsäureanhydrids.

In a further embodiment, a preferred method is characterized in that the second composition (B) contains at least one anionic polymer (B2) which is selected from the group of

1. (i) Polymers of acrylic acid and / or methacrylic acid,
2. (ii) polymers of 2-acrylamido-2-methyl-1-propanesulfonic acid,
3. (iii) anionic polysaccharides,
4. (iv) Polymers of itaconic acid and / or of crotonic acid and / or
5. (v) Polymers of maleic anhydride.

The anionic polymers (B2) have proven to be very particularly suitable for solving the problem according to the invention,

In one embodiment, the agents according to the invention can contain at least (i) one polymer of acrylic acid and / or methacrylic acid as anionic polymer (B2). The definition of polymer also includes both the homopolymers and the copolymers of acrylic acid and / or methacrylic acid. By definition, homopolymers are polymers that have arisen from polymers of only one type. In contrast, copolymers are built up from several different monomers.

In a further embodiment, a very particularly preferred method is characterized in that the second composition (B) contains at least one anionic polymer (B2) selected from the group of homopolymers of acrylic acid, copolymers of acrylic acid, homopolymers of methacrylic acid and the copolymers of methacrylic acid.

worin

Ra

für ein Wasserstoffatom oder eine Methylgruppe steht und

M

für ein Wasserstoffatom oder für Natrium, Kalium, ½ Magnesium oder ½ Calcium steht.

The homopolymers and copolymers of (meth) acrylic acid are characterized in that they contain at least one structural unit of the formula (P-I '),

wherein

Ra

represents a hydrogen atom or a methyl group and

M.

stands for a hydrogen atom or for sodium, potassium, ½ magnesium or ½ calcium.

A preferred homopolymer is polyacrylic acid, such as those from 3V Sigma under the trade names Synthalen K or Synthalen M or from Lubrizol under the trade names Carbopol (for example Carbopol 980, 981, 954, 2984 and 5984), respectively with the INCI name Carbomer is available. The acrylic acid homopolymer marketed by BASF under the trade name Cosmedia SP (INCI name: SODIUM POLYACRYLATE) can also be mentioned in this context as a preferred acrylic acid homopolymer.

Also under the name Simulgel® ^® EC as a compound with isohexadecane and polysorbate-80 marketed sodium acrylate / sodium copolymers (INCI name: SODIUM ACRYLATE / SODIUM ACRYLOYLDIMETHYL TAURATE COPOLYMER, ISOHEXADECANE, POLYSORBATE 80) have proven to be particularly effective according to the invention.

At least one copolymer of acrylic acid and / or methacrylic acid can also be used as the anionic polymer. A suitable polymer in this context is the polymer known under the INCI name Acrylates / C10-30 Alkyl Acrylate Crosspolymer, which is available under the trade name Carbopol 1382 from Noveon. Another suitable polymer is the polymer known under the INCI name Acrylates / Steareth-20 Methacrylate Crosspolymer, which, for example, has the trade name Aculyn® 88 from Rohm & Haas in the form of a 28 to 30% by weight dispersion in water is distributed. Furthermore, polymers according to the INCI nomenclature can be used as Acrylates / Palmeth-25 Acrylate Copolymers or Acrylates / Palmeth-20 Acrylate Copolymers. Such polymers are available, for example, under the trade name Synthalen® W2000 as a 30 to 32% by weight emulsion in water from 3 V Sigma.

Within this embodiment, it can also be preferred to use a copolymer of at least one anionic acrylic acid or methacrylic acid monomer and at least one nonionic monomer. In this context, preferred nonionic monomers are acrylamide, methacrylamide, acrylic acid esters, methacrylic acid esters, vinyl pyrrolidone, vinyl ethers and vinyl esters.

Further preferred anionic copolymers are, for example, copolymers of acrylic acid and / or methacrylic acid and their C ₁ -C ₆ -alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas. However, copolymers of acrylic acid and / or methacrylic acid, the C ₁ -C ₆ -alkyl esters of acrylic acid and / or methacacrylic acid 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. Such copolymers are sold by Rohm & Haas under the tradename Aculyn ^® 22 (INCI Name: / Acrylates Steareth-20 Methacrylate Copolymer) expelled.

Further preferred anionic acrylic acid or methacrylic acid copolymers are acrylic acid-acrylamide copolymers.

• - Carbomer (Polyacrylsäure),
• - Sodium Polyacrylate,
• - Sodium Acrylate/Sodium Acryloyldimethyl Taurate Copolymer,
• - Acrylates / C10-30 Alkyl Acrylate Crosspolymer,
• - Acrylates / Steareth-20 Methacrylate Crosspolymer,
• - Acrylates/Palmeth-25 Acrylate Copolymer,
• - Acrylates / Palmeth-20 Acrylate Copolymer,
• - Acrylates Copolymere und/oder
• - Acrylates/Steareth-20 Methacrylate Copolymer).

In a further embodiment, a method according to the invention can also be characterized in that the second composition (B) contains as anionic polymer (B2) at least (i) one polymer of acrylic acid and / or methacrylic acid, which is preferably selected from among the INCI - Names of known substances

• - carbomer (polyacrylic acid),
• - Sodium polyacrylate,
• - Sodium Acrylate / Sodium Acryloyldimethyl Taurate Copolymer,
• - Acrylates / C10-30 Alkyl Acrylate Crosspolymer,
• - Acrylates / Steareth-20 Methacrylate Crosspolymer,
• - Acrylates / Palmeth-25 Acrylate Copolymer,
• - Acrylates / Palmeth-20 Acrylate Copolymer,
• - Acrylates copolymers and / or
• - Acrylates / Steareth-20 Methacrylate Copolymer).

In a further embodiment, a method according to the invention can also be characterized in that the second composition (B) contains at least one polymer (ii) of 2-acrylamido-2-methyl-1-propanesulfonic acid as anionic polymer (B2). In the case of the polymers in this category, the homo- and copolymers of 2-acrylamido-2-methyl-1-propanesulfonic acid are also included in the invention.

worin

M

für ein Wasserstoffatom oder für Natrium, Kalium, ½ Magnesium oder ½ Calcium steht.

Polymers of type (ii) are characterized in that they contain at least one structural unit of the formula (P-II ') as a structural component,

wherein

M.

stands for a hydrogen atom or for sodium, potassium, ½ magnesium or ½ calcium.

Polymers of this type have anionic sulfonic acid groups which are introduced into the polymer by polymerizing the monomer 2-methyl-2 - [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid (AMPS). Anionic polymers have proven to be particularly effective which contain 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid (AMPS) as the sole monomer, the sulfonic acid group being wholly or partly as sodium, Potassium, ammonium, mono- or triethanolammonium salt can be present.

Homopolymers of 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid are very suitable for use in the agents according to the invention. Particularly suitable substances can be those in the application EP 0815828 A1 compounds disclosed under the name Cosmedia® HSP 1160 polymer known as well under the name Rheothik ^® 11-80 product is available commercially are called. Polymers which are obtained by copolymerization of the 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid building block with further monomers are also encompassed by the invention and are preferred.

Another highly suitable anionic copolymer consists of 70 to 55 mol% acrylamide and 30 to 45 mol% 2-acrylamido-2-methylpropanesulfonic acid, the sulfonic acid group being completely or partially as sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer can also be present in crosslinked form, the crosslinking agents used being preferably polyolefinically unsaturated compounds such as tetraallyloxythane, allyl sucrose, allyl pentaerythritol and methylene bisacrylamide.

Further preferred sulfonic acid polymers of this type are copolymers of 2-methyl-2 [(1-oxo-2-propenyl) amino] -1-propanesulfonic acid (AMPS) and sodium acrylate, which are available, for example, as a commercial product Simulgel® EG (INCI name: Sodium Acrylates / Sodium Acryloyldimethyl Taurate Copolymer, Isohexadecane, Polysorbate 80) from Seppic are available.

It can also be preferred if the agent for dyeing and optionally simultaneous lightening of keratinic fibers contains exclusively at least one homo- and / or copolymer of 2-acrylamido-2-methyl-1-propanesulfonic acid as anionic polymer (b).

In a further embodiment, the agents according to the invention can contain at least one (iii) anionic polysaccharide as anionic polymer (B2). The group of (iii) anionic polysaccharides includes xanthans, alginates, carboxyalkyl celluloses and hyaluronic acids.

Xanthan is an anionic polysaccharide, which is composed of the structural components D-glucose, D-mannose, D-glucuronic acid, acetate and pyruvate and which is also known under the INCI name Xanthan Gum.

The salts of alginic acid are referred to as alginates (INCI name Algin). Alginates are acidic polysaccharides containing carboxy groups, consisting of D-mannuronic acid and D-guluronic acid in different ratios, which are linked with 1-4-glycosidic bonds. Both the alkali and the alkaline earth salts of the aligning acids are in accordance with the invention. The use of alginic acid, sodium alginate, potassium alginate, ammonium alginate and / or calcium alginate in the agents according to the invention has proven to be particularly advantageous. Carboxyalkyl celluloses are cellulose ethers in which the hydrogen atoms of the hydroxyl groups of the cellulose are partially or completely substituted by carboxyalkyl groups. One preferred carboxyalkyl cellulose is carboxymethyl cellulose, which can preferably be used as an anionic polymer in the form of its sodium salt (sodium carboxymethyl cellulose). The basic building blocks of hyaluronic acid (INCI name Hyaluronic acid, Sodium Hyaluronat) is an aminodisaccharide made up of D-glucuronic acid and N-acetylglucsoamine in a 1-3-glycosidic bond, which is linked to the next β-1-4-glycosidic unit. In the context of the work leading to this invention, sodium and potassium salts of hyaluronic acid have proven to be particularly suitable for producing intensely coloring formulations which are optimized with regard to their viscosity.

• - Xanthan (Xanthan Gum),
• - Alginat (Algin),
• - Carboxymethylcellulose und/oder deren physiologisch verträglichen Salzen und/oder
• - Hyaluronsäure und/oder deren physiologisch verträglichen Salzen

enthält.Another preferred embodiment is an agent for dyeing and optionally simultaneous lightening of keratinic fibers, which is characterized in that it contains at least (iii) one anionic polysaccharide, preferably selected from as anionic polymer (B2)

• - xanthan gum (xanthan gum),
• - alginate (algin),
• - Carboxymethyl cellulose and / or its physiologically compatible salts and / or
• - Hyaluronic acid and / or its physiologically compatible salts

contains.

worin

M, M', M''

jeweils unabhängig voneinander für ein Wasserstoffatom oder für Natrium, Kalium, ½ Magnesium oder ½ Calcium steht.

In a further embodiment, a method according to the invention can also be characterized in that the second composition (B) contains at least one polymer (iv) of itaconic acid and / or crotonic acid as anionic polymer (B2). Both the homopolymers and the copolymers of itaconic acid and / or of crotonic acid are encompassed by the invention. Polymers of this type are characterized in that they contain at least one unit of the formula (P-III ') and / or the formula (P-IV') as structural components,

wherein

M, M ', M''

each independently represents a hydrogen atom or sodium, potassium, ½ magnesium or ½ calcium.

A preferred copolymer belonging to this class is, for example, the terpolymer which can be produced by the copolymerization of vinyl chloride, vinyl acetate and itaconic acid, which is also commercially available under the trade name Vinnol E 15/45 M from Wacker Polymer Systems.

worin

M', M''

unabhängig voneinanderfür ein Wasserstoffatom oder für Natrium, Kalium, ½ Magnesium oder ½ Calcium stehen.

It can furthermore be preferred if the composition (B) used in the process according to the invention contain at least one polymer (v) of maleic anhydride as anionic polymer (B2). This group includes homopolymers and copolymers containing at least one structural component of the formula (P-V '), which is formed by the polymerization and hydrolysis of the maleic anhydride monomer unit,

wherein

M ', M''

independently stand for a hydrogen atom or for sodium, potassium, ½ magnesium or ½ calcium.

Anionic polymers suitable in this connection are copolymers of maleic anhydride and methyl vinyl ether, in particular those with crosslinks. A crosslinked with 1,9-decadiene maleic acid-methyl copolymer available under the name Stabileze® ^® QM.

The very best results were obtained when the composition (B) contained at least one anionic polymer (B2) selected from the group consisting of homopolymers of acrylic acid, copolymers of acrylic acid, homopolymers of methacrylic acid and copolymers of methacrylic acid.

Another explicitly very particularly preferred embodiment is a method according to the invention characterized in that the second composition (B) contains at least one anionic polymer (B2) selected from the group of homopolymers of acrylic acid, copolymers of acrylic acid, homopolymers of Methacrylic acid and the copolymers of methacrylic acid.

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 / C1 0 -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.

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 (B) contains at least one anionic polymer (B2) which comprises at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II)

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

If M stands for a hydrogen atom, the structural unit of the formula (PI) is based on an acrylic acid unit.
If M stands for an ammonium counterion, the structural unit of the formula (PI) 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 (PI) is based on the potassium salt of acrylic acid.
If M stands for half an equivalent of a magnesium counterion, the structural unit of the formula (PI) 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 (PI) is based on the calcium salt of acrylic acid.

wobei
M für ein Wasserstoffatom oder für Ammonium (NH₄), Natrium, Kalium, ½ Magnesium oder ½ Calcium steht.In the explicitly most preferred embodiment, a method according to the invention is characterized in that the second composition (B) contains at least one anionic polymer (B2) which has at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II) includes

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

A corresponding polymer (B2) can be obtained commercially from Dow, for example, under the trade name Ecosmooth. Ecosmooth is a 24 to 27% by weight solution of a copolymer of sodium acrylate and ethylene in water.

The anionic polymer (s) according to the invention (B2) are preferably used in certain quantity ranges in the composition (B). In this context, it has proven to be particularly preferred to achieve the object of the invention if the second composition (B) - based on the total weight of the composition (B) - has one or more anionic polymers (B2) in a total amount of 0.1 to 10.0% by weight, preferably from 0.3 to 7.5% by weight, more preferably from 0.6 to 5.0% by weight and very particularly preferably from 0.7 to 3.0% by weight. -% contains.

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) - has one or more anionic polymers (B2) in a total amount of 0.1 to 10.0 wt. -%, preferably from 0.3 to 7.5% by weight, more preferably from 0.6 to 5.0% by weight and very particularly preferably from 0.7 to 3.0% by weight.

Water content of the composition (B)

The composition (B) contains the polymers (B1) and (B2) in a cosmetic carrier, preferably in an aqueous cosmetic carrier.

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% by weight, preferably 30.0 to 98.0% by weight. %, preferably 40.0 to 95.0% by weight, more preferably 45.0 to 90.0% by weight, even more preferably 50.0 to 90.0% by weight and very particularly preferably 55.0 to Contains 90.0% 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) - 30.0 to 98.0% by weight, preferably 40.0 to 95.0 % By weight, more preferably 45.0 to 90.0% by weight, even more preferably 50.0 to 90.0% by weight and very particularly preferably 55.0 to 90.0% 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 that 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 in accordance with 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.

Use of other coloring compounds

In the course of the work leading to this invention, it was observed that the films formed on the keratin material not only had good rubbing fastness but also a particularly high color intensity if a coloring compound from the group of pigments and / or direct dyes was used in the process became. 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 keratinic 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 following are applied to the keratinic material:

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

The coloring compound (s) can be selected from the group of pigments and substantive dyes, and the substantive dyes can also 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 for example take place by means of the method described below: 0.5 g of the pigment is weighed out 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, black pigments such as. 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), ultramarine (sodium Aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI77289), iron blue (Ferric Ferrocyanide, CI77510) 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 produce the pearlescent pigments in conjunction 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 a 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 which are mixed 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, for example, 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
• Timiron Synwhite Satin, Merck, Synthetic Fluorphlogopite, Titanium Dioxide,Tin Oxide
• Timiron Super Blue, Merck, Mica, CI 77891 (Titan Dioxide)
• Timiron Diamond Cluster MP 149, Merck, Mica, CI 77891 (Titan dioxide)
• Timiron Splendid Gold, Merck, CI 77891 (Titan dioxide), Mica, Silica
• Timiron Super Sulver, Merck, Mica, CI 77891 (Titan dioxide)

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
• Timiron Synwhite Satin, Merck, Synthetic Fluorphlogopite, Titanium Dioxide, Tin Oxide
• Timiron Super Blue, Merck, Mica, CI 77891 (Titan Dioxide)
• Timiron Diamond Cluster MP 149, Merck, Mica, CI 77891 (Titan dioxide)
• Timiron Splendid Gold, Merck, CI 77891 (Titan dioxide), Mica, Silica
• Timiron Super Sulver, Merck, Mica, CI 77891 (Titan dioxide)

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.

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.

For example, the alizarin color varnish can be used as the color varnish.

Because of 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 using dynamic light scattering (DLS), for example.

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 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 have a monolithic structure. 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. no concentration gradient occurs 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 platelets is understood to be the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Helos device with Quixel wet dispersion. To prepare the sample, the sample to be examined was predispersed in isopropanol for a period of 3 minutes.

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

They can be of natural origin, but they can also be manufactured synthetically. 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 keratinous material and, for example, effects analogous to natural graying can be achieved.

Lenticular (= lens-shaped) substrate platelets have an essentially regular, round edge and are also referred to 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 Called 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, on the basis of 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 rays.

Correspondingly, preferred pigments are pigments based on a coated lamellar substrate platelet. The substrate platelet preferably has at least one coating B made of a high-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 platelets 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 a plurality of 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 (α- 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 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 Coating B is in the range given 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 conversion of a hydroxide-containing layer that has formed into the oxide layers by annealing).

Although each of the coatings A, B and / or C can be composed of a mixture of two or more metal oxides (hydrate), each of the coatings is preferably composed of 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 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 keratinic 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 will. 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 bond 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 (ie to the outermost metal oxide-containing layer) or, if 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. Pigments based on silicon dioxide-coated aluminum substrate platelets are surface-modified with a monofunctional silane. Octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane and hecadecyltriethoxysilane are particularly preferred. The changed surface properties / hydrophobization 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 which comprises 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 of 0.001 to 20% by weight, in particular from 0.05 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 of 0.001 to 20% by weight, in particular from 0.05 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- et hylamino-4-nitrophenol.

Anionic substantive dyes are also referred to as acid dyes. Acid dyes are taken to mean 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 -vor).} 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 in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations 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 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 the acid dyes is their ability to form 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 W1100 (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 (C.1.14720), 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, Naphtholred 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 Blue V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blu e 9 (E 133, Patent Blue AE, Amido Blue 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 (C.1.42100), Acid Green 22 (C.1.42170), 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.

• Acid Yellow 1 trägt den Namen 8-Hydroxy-5,7-dinitro-2-naphthalenesulfonsäure Dinatriumsalz und besitzt eine Löslichkeit in Wasser von mindestens 40 g/L (25°C).
• Acid Yellow 3 ist ein Gemisch der Natriuimsalze von Mono- und Sisulfonsäuren von 2-(2-Chinolyl)-1H-indene-1,3(2H)-dion und besitzt eine Wasserlöslichkeit von 20 g/L (25 °C).
• Acid Yellow 9 ist das Dinatriumsalz der 8-Hydroxy-5,7-dinitro-2-naphthalenesulfonsäure, seine Wasserlöslichkeit liegt oberhalb von 40 g/L (25 °C).
• Acid Yellow 23 ist das Trinatriumsalz der4,5-Dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carbonsäure und bei 25 °C gut in Wasser löslich.
• Acid Orange 7 ist das Natriumsalz des 4-[(2-Hydroxy-1-naphthyl)azo]benzensulfonats. Seine Wasserlöslichkeit beträgt mehr als 7 g/L (25 °C).
• Acid Red 18 ist das Trinatirumsalz von 7-Hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonat und besitzt eine sehr hohe Wasserlöslichkeit von mehr als 20 GEw.-%.
• Acid Red 33 ist das Diantriumsalz des 5-Amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulphonats, seine Wasserlöslichkeit liegt bei 2,5 g/L (25 °C).

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 sisulphonic 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 more 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 irradiation with light, especially UV light. This can be done both by changing the intensity and / or the wavelength maximum.

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.

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.

In the context of one embodiment, it may be preferred to mix the compositions (A) and (B) with one another before use on the keratin material, so that the mixture of (A) and (B) is applied to the keratin material.

Within the scope of a further embodiment, it can also be preferred to mix the compositions (A) and (B) with a third composition (C) described above before use on the keratin material, so that the mixture from (A) and (B) and (C) is applied.

• - unmittelbar vor der Anwendung durch Vermischen der ersten Zusammensetzung (A) mit der zweiten Zusammensetzung (B) hergestellt wurde, oder die
• - unmittelbar vor der Anwendung durch Vermischen der ersten Zusammensetzung (A) mit der zweiten Zusammensetzung (B) und der dritten Zusammensetzung (C) hergestellt wurde.

In the context of a further particularly preferred embodiment, a method according to the invention is characterized in that an application mixture is applied to the keratinic material which

• - Was prepared immediately before use by mixing the first composition (A) with the second composition (B), or the
• - was prepared immediately before use by mixing the first composition (A) with the second composition (B) and the third composition (C).

The successive application of the compositions (A) and (B) is also possible and also according to the invention, i.e. in this case the composition (A) is first applied to the keratin material, left to act and, if necessary, rinsed out again. Thereafter, the composition (B) is then applied to the keratin material, left to act and, if necessary, rinsed out again.

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

In the context of this further embodiment, a method according to the invention is characterized by the following steps:

1. (1) applying the first composition (A) to the keratin material,
2. (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. (3) rinsing the composition (A) from the keratin material,
4. (4) applying the composition (B) to the keratin material,
5. (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. (6) rinsing the composition (B) from the keratin material.

The rinsing of 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 from 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 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. (1) Auftragen des ersten Zusammensetzung (A) auf das Keratinmaterial,
2. (2) Einwirkenlassen der Zusammensetzung (A) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
3. (3) Ausspülen der Zusammensetzung (A) aus dem Keratinmaterial,
4. (4) Auftragen der Zusammensetzung (B) auf das Keratinmaterial,
5. (5) Einwirkenlassen der Zusammensetzung (B) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
6. (6) Ausspülen der Zusammensetzung (B) aus dem Keratinmaterial.

In a further embodiment, a method according to the invention comprises the following steps in the order given:

1. (1) applying the first composition (A) to the keratin material,
2. (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. (3) rinsing the composition (A) from the keratin material,
4. (4) applying the composition (B) to the keratin material,
5. (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. (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, this can be applied 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 will.

1. (1) Auftragen des ersten Zusammensetzung (A) auf das Keratinmaterial,
2. (2) Einwirkenlassen der Zusammensetzung (A) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
3. (3) Ausspülen der Zusammensetzung (A) aus dem Keratinmaterial,
4. (4) Auftragen der Zusammensetzung (B) auf das Keratinmaterial,
5. (5) Einwirkenlassen der Zusammensetzung (B) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
6. (6) Ausspülen der Zusammensetzung (B) aus dem Keratinmaterial.
7. (7) Auftragen der Zusammensetzung (C) auf das Keratinmaterial,
8. (8) Einwirkenlassen der Zusammensetzung (C) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten,
9. (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. (1) applying the first composition (A) to the keratin material,
2. (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. (3) rinsing the composition (A) from the keratin material,
4. (4) applying the composition (B) to the keratin material,
5. (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. (6) rinsing the composition (B) from the keratin material.
7. (7) applying the composition (C) to the keratin material,
8. (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. (9) rinsing the composition (C) from the keratin material.

1. (1) Herstellung einer Anwendungsmischung durch Vermischen der Zusammensetzungen (A) und (B)
2. (2) Auftragen der Mischung aus (A) und (B) auf das Keratinmaterial,
3. (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. (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. (1) Preparation of an application mixture by mixing compositions (A) and (B)
2. (2) applying the mixture of (A) and (B) to the keratin material,
3. (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. (4) rinsing the mixture from the keratin material.

1. (1) Herstellung einer Anwendungsmischung durch Vermischen der Zusammensetzungen (A) und (B)
2. (2) Auftragen der Mischung aus (A) und (B) auf das Keratinmaterial,
3. (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. (4) Ausspülen der Mischung aus dem Keratinmaterial.
5. (5) Auftragen der Zusammensetzung (C) auf das Keratinmaterial
6. (6) Einwirkenlassen der Zusammensetzung (C) auf das Keratinmaterial für einen Zeitraum von 1 bis 10 Minuten, bevorzugt 1 bis 5 Minuten, und
7. (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. (1) Preparation of an application mixture by mixing compositions (A) and (B)
2. (2) applying the mixture of (A) and (B) to the keratin material,
3. (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. (4) rinsing the mixture from the keratin material.
5. (5) Applying the composition (C) to the keratin material
6. (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. (7) rinsing the composition (C) from the keratin material.

1. (1) Herstellung einer Anwendungsmischung durch Vermischen der Zusammensetzungen (A) und (B) und (C)
2. (2) Auftragen der Mischung aus (A) und (B) und (C) auf das Keratinmaterial,
3. (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. (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. (1) Preparation of an application mixture by mixing the compositions (A) and (B) and (C)
2. (2) applying the mixture of (A) and (B) and (C) to the keratin material,
3. (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. (4) rinsing the mixture from the keratin material.

The composition (A) can be a preparation which contains the two silanes (A1) and (A2) in an aqueous or water-containing carrier. In this case, the composition (A) can be applied directly to the keratin material. To optimize the storage stability, however, it may also be possible to provide the composition (A) in the form of a concentrate. This concentrated composition (A) is then to be mixed with an aqueous or water-based carrier shortly before use.

1. (1) Herstellen einer ersten Anwendungsmischung durch Vermischen der ersten Zusammensetzung (A) mit mindestens einer weiteren Zusammensetzung,
2. (2) Applizieren der in Schritt (1) hergestellten ersten Anwendungsmischung auf dem keratinischen Material,
3. (3) Einwirken lassen der in Schritt (2) applizierten ersten Anwendungsmischung,
4. (4) Auswaschen der ersten Anwendungsmischung nach dem Einwirken,
5. (5) Herstellen einer zweiten Anwendungsmischung durch Vermischen der zweiten Zubereitung (B) mit der dritten Zubereitung (C),
6. (6) Applizieren der in Schritt (5) hergestellten zweiten Anwendungsmischung auf dem keratinischen Material,
7. (7) Einwirken der in Schritt (6) applizerten zweiten Anwendungmischung, und
8. (8) Auswaschen der zweiten Anwendungsmischung nach dem Einwirken.

In a further embodiment, a method according to the invention can also comprise the following steps

1. (1) producing a first application mixture by mixing the first composition (A) with at least one further composition,
2. (2) applying the first application mixture prepared in step (1) to the keratinous material,
3. (3) Allow the first application mixture applied in step (2) to act,
4. (4) Wash out the first application mixture after it has taken effect,
5. (5) Preparation of a second application mixture by mixing the second preparation (B) with the third preparation (C),
6. (6) applying the second application mixture prepared in step (5) to the keratinic material,
7. (7) action of the second application mixture applied in step (6), and
8. (8) Wash out the second application mixture after exposure.

The further composition which is mixed with the composition (A) in step (1) is preferably a water-containing cosmetic carrier which serves to dilute the composition (A) used in the form of a concentrate.

1. (1) Herstellen einer ersten Anwendungsmischung durch Vermischen der ersten Zusammensetzung (A) mit mindestens einer weiteren Zusammensetzung, welche Wasser und mindestens ein Tensid enthält,
2. (2) Applizieren der in Schritt (1) hergestellten ersten Anwendungsmischung auf dem keratinischen Material,
3. (3) Einwirken lassen der in Schritt (2) applizierten ersten Anwendungsmischung,
4. (4) Auswaschen der ersten Anwendungsmischung nach dem Einwirken,
5. (5) Herstellen einer zweiten Anwendungsmischung durch Vermischen der zweiten Zubereitung (B) mit der dritten Zubereitung (C),
6. (6) Applizieren der in Schritt (5) hergestellten zweiten Anwendungsmischung auf dem keratinischen Material,
7. (7) Einwirken der in Schritt (6) applizerten zweiten Anwendungmischung, und
8. (8) Auswaschen der zweiten Anwendungsmischung nach dem Einwirken.

In a further embodiment, a method according to the invention can also comprise the following steps

1. (1) Preparation of a first application mixture by mixing the first composition (A) with at least one further composition which contains water and at least one surfactant,
2. (2) applying the first application mixture prepared in step (1) to the keratinous material,
3. (3) Allow the first application mixture applied in step (2) to act,
4. (4) Wash out the first application mixture after it has taken effect,
5. (5) Preparation of a second application mixture by mixing the second preparation (B) with the third preparation (C),
6. (6) applying the second application mixture prepared in step (5) to the keratinic material,
7. (7) action of the second application mixture applied in step (6), and
8. (8) Wash out the second application mixture after exposure.

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) bei der Beschreibung des erten Erfindungsgegenstands im Detail offenbart wurden,

A second subject of the present invention is a multi-component packaging unit (kit-of-parts) for treating keratinic material, comprehensively 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) being disclosed in detail in the description of the first subject of the invention,

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 matter 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]
• WO 2013068979 A2 [0008]
• EP 0815828 A1 [0154]

Claims (22)

Method for treating keratinic material, in particular human hair, in which the keratinic material is applied with a first composition (A) which contains (A1) one or more organic C ₁ -C ₆ -alkoxy-silanes of the formula (SI) and / or their condensation products, R ₁ R ₂ NL-Si (OR ₃ ) _a (R ₄ ) _b (Sl) 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, is an integer from 1 to 3, and - b is the integer 3 - a, and (A2) one or more organic C ₁ -C ₁₂ -alkyl -C ₁ -C ₆ -alkoxy-silanes of the formula (S-II) and / or their condensation products, R ₅ Si (OR ₆ ) _k (R ₇ ) _m (S-II), where - R _{5 stands} for a C ₁ -C ₁₂ -alkyl group, - R _{6 stands} for a C ₁ -C ₆ -alkyl group, - R _{7 stands} for a C ₁ -C ₆ -alkyl group - k stands for an integer of 1 to 3, and - m stands for the integer 3 - k, - a second composition (B) which contains (B1) at least one nonionic polymer and (B2) at least one anionic polymer. Procedure according to Claim 1 , 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 until 2 , characterized in that the first composition (A) contains at least one organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silane (A2) of the formula (S-II) which is selected from the group of - methyltrimethoxysilane - methyltriethoxysilane - ethyltrimethoxysilane - ethyltriethoxysilane - hexyltrimethoxysilane - hexyltriethoxysilane - octyltrimethoxysilane - octyltriethoxysilane - dodecyltrimethoxysilane, - dodecyltriethoxysilane, and / or their condensation products, and / or. Method according to one of the Claims 1 until 3 , characterized in that the composition (A) - based on the total weight of the composition (A) - one or more organic C ₁ -C ₆ -alkoxysilanes (A1) of the formula (SI) in a total amount of from 5.0 to 50.0% by weight, preferably from 7.5 to 45% by weight, more preferably from 10.0 to 35% by weight, and whole particularly preferably from 15.0 to 25% by weight. Method according to one of the Claims 1 until 4th , characterized in that the composition (A) - based on the total weight of the composition (A) - one or more organic C ₁ -C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S- II) in a total amount of from 20 to 80% by weight, preferably from 30 to 70% by weight, more preferably from 35 to 60% by weight and very particularly preferably from 40 to 55% by weight. Method according to one of the Claims 1 until 5 , characterized in that the weight ratio of the total amount of the organic C ₁ -C ₆ -alkoxy-silanes (A1) of the formula (SI) contained in the composition (A) to the total amount of the organic C ₁ - C ₁₂ -alkyl-C ₁ -C ₆ -alkoxy-silanes (A2) of the formula (S-II), ie the weight ratio (A1) / (A2), at a value of 0.1 to 5.0, preferably of 0.1 to 2.5, more preferably from 0.1 to 1.5, even more preferably from 0.1 to 1.0 and very particularly preferably from 0.1 to 0.45. Method according to one of the Claims 1 until 6th , characterized in that the first composition (A) - based on the total weight of the composition (A) - 0.01 to 15.0 wt .-%, preferably 0.1 to 13.0 wt .-%, more preferably 0 , 5 to 11.0 and very particularly preferably 1.0 to 9.0 wt .-% water. Method according to one of the Claims 1 until 7th , characterized in that the second composition (B) contains at least one nonionic polysaccharide (B1), preferably at least one nonionic cellulose derivative. Method according to one of the Claims 1 until 8th , characterized in that the second composition (B) contains at least one nonionic cellulose derivative (B1) selected from the group of 2-hydroxyethyl cellulose, 2-hydroxypropyl cellulose, 3-hydroxypropyl cellulose, 2-hydroxypropyl -Methyl cellulose and / or 3-hydroxypropyl methyl cellulose. Method according to one of the Claims 1 until 9 , characterized in that the second composition (B) contains (B1 ') 2-hydroxyethyl cellulose and (B1'') at least one cellulose from the group of 2-hydroxypropyl cellulose, 3-hydroxypropyl cellulose, 2-hydroxypropyl Methyl cellulose and / or 3-hydroxypropyl methyl cellulose. Method according to one of the Claims 1 until 10 , characterized in that the second composition (B) - based on the total weight of the composition (B) - one or more nonionic polymers (B1) in a total amount of 0.1 to 10.0 wt .-%, preferably 0.1 up to 8.0% by weight, more preferably 0.1 to 6.0% by weight and very particularly preferably 0.1 to 4.0% by weight. Method according to one of the Claims 1 until 11 , characterized in that the second composition (B) contains at least one anionic polymer (B2) selected from the group consisting of homopolymers of acrylic acid, copolymers of acrylic acid, homopolymers of methacrylic acid and copolymers of methacrylic acid. Method according to one of the Claims 1 until 12th , characterized in that the second composition (B) contains at least one anionic polymer (B2) which comprises at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II)

where M stands for a hydrogen atom or for ammonium (NH ₄ ), sodium, potassium, ½ magnesium or ½ calcium. Method according to one of the Claims 1 until 13th , characterized in that the second composition (B) - based on the total weight of the composition (B) - has one or more anionic polymers (B2) in a total amount of 0.1 to 10.0% by weight, preferably of 0, 3 to 7.5% by weight, more preferably from 0.6 to 5.0% by weight and very particularly preferably from 0.7 to 3.0% by weight. Method according to one of the Claims 1 until 14th , characterized in that - a third composition (C) is applied to the keratinic material, which contains at least one coloring compound from the group of pigments and / or substantive dyes. Method according to one of the Claims 1 until 15th , characterized in that the second composition (B) and / or the third composition (C) contains at least one inorganic pigment, which is preferably 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 colored pigments based on mica or mica, which are coated with at least one metal oxide and / or a metal oxychloride. Method according to one of the Claims 1 until 16 , characterized in that the second composition (B) and / or the third composition (C) contains at least one coloring compound from the group of organic pigments, which is preferably selected from the group of 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. Method according to one of the Claims 1 until 17th , characterized in that the second composition (B) and / or the third composition (C) contains at least one pigment selected from the group consisting of the pigments based on a lamellar substrate platelet, the pigments based on a lenticular substrate platelet and the pigments Base of a substrate plate, which comprises a vacuum metallized pigment. Method according to one of the Claims 1 until 18th , characterized in that an application mixture is applied to the keratin material, which - was prepared immediately before application by mixing the first composition (A) with the second composition (B), or which - immediately before application by mixing the first composition (A) with the second composition (B) and the third composition (C). Method according to one of the Claims 1 until 18th , comprising the following steps in the order given: (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 up 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 until 18th are defined. Multi-component packaging unit (kit-of-parts) Claim 21 , comprising packaged separately from one another - a third container with a third composition (C), the third composition (C) in one of the Claims 15 until 18th is defined.