EP4031098A1

EP4031098A1 - Method for dyeing keratinous material, comprising the use of an organosilicon compound, an effect pigment and a film-forming polymer

Info

Publication number: EP4031098A1
Application number: EP20764053.3A
Authority: EP
Inventors: Rene Krohn; Thomas Hippe; Stefan Hoepfner; Jessica Brender
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2019-09-18
Filing date: 2020-08-25
Publication date: 2022-07-27
Also published as: WO2021052720A1; DE102019214205A1; US20220339089A1

Abstract

The present invention relates to a method for dyeing keratinous material, in particular human hair, comprising the following steps: applying an agent (a) to the keratinous material, said agent (a) containing at least one organosilicon compound (a1) and applying an agent (b) to the keratinous material, said agent (b) containing: (b1) at least one dyeing compound comprising at least one effect pigment comprising α) a substrate platelet comprising synthetic mica, and β) a coating comprising at least one first metal oxide (hydrate) layer, and (b2) at least one film-forming polymer. The invention also relates to a multi-component packaging unit which contains the two agents (a) and (b) in two separately fabricated containers.

Description

Patent application

Process for coloring keratinic material, comprising the use of an organosilicon compound, an effect pigment and a film-forming polymer

The present application relates to a method for coloring keratinous material, in particular human hair, which comprises the use of two different agents (a) and (b). The agent (a) contains at least one organic silicon compound. The agent (b) contains at least one coloring compound (b1), comprising at least one selected effect pigment, and a film-forming polymer (b2).

A second subject of this application is a multi-component packaging unit (kit-of-parts) for coloring keratinous material, in particular human hair, which comprises means (a) and (b) separately packaged in two different containers.

The change in the shape and color of keratinic material, in particular human 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 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 his hair to be colored for a particularly long time, the use of oxidative coloring agents has so far been his only option. But despite multiple attempts at optimization, an unpleasant ammonia odor can be left with oxidative hair coloring or do not completely avoid the smell of amine. The hair damage still associated with the use of oxidative coloring agents also has a detrimental effect on the user's hair. A challenge that still exists is therefore the search for alternative, high-performance dyeing processes.

EP 2168633 B1 deals with the task of producing long-lasting hair colorations 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 should be particularly resistant to shampooing.

Metallic luster pigments or metallic effect pigments are widely used in many areas of technology. They are used, for example, for coloring paints, printing inks, inks,

Plastics, glasses, ceramic products and preparations of decorative cosmetics such as nail polish are used. They are characterized above all by their attractive, angle-dependent color impression (goniochromy) and their metallic-like sheen.

Hair with a metallic finish or metallic reflections are trendy. The metallic tone makes the hair appear thicker and shinier.

Effect pigments based on metal-containing substrate platelets have only limited stability in an aqueous medium. For example, aluminum-based effect pigments decompose comparatively quickly in water with the formation of hydrogen and aluminum hydroxide.

There is a need to provide hair colorations with effect pigments which, on the one hand, have high wash and rub fastness and, on the other hand, do not adversely affect hair properties such as handling and haptics. For this purpose it would be desirable if the effect pigments used had a high covering power and could be applied to the hair in thin layers. The effect pigments used should also be storage-stable over a relatively long period of time, in particular insensitive to corrosion on prolonged contact with water.

Accordingly, the object of the present invention was to provide a coloring system with effect pigments which has fastness properties comparable to oxidative coloring. In particular, the wash fastness should be excellent, but the use of the oxidation dye precursors usually used for this purpose should be dispensed with.

Surprisingly, it has now been found that the aforementioned object can be achieved excellently if keratinic materials, in particular human hair, are colored with a method in which at least two agents (a) and (b) are applied to the keratinic materials (hair) . The agent (a) here contains at least one organic The silicon compound and the agent (b) contains at least one selected effect pigment (b1) and a film-forming polymer (b2).

When the two agents (a) and (b) were used in one dyeing process, it was possible to dye keratinic material with a particularly high color intensity and high fastness properties.

A first object of the present invention is a method for coloring keratinic material, in particular human hair, comprising the following steps:

Application of an agent (a) to the keratinic material, the agent (a) containing at least one organic silicon compound, and

- Application of an agent (b) on the keratinic material, the agent (b) containing:

(b1) at least one coloring compound, comprising at least one effect pigment, comprising a) a substrate platelet comprising synthetic mica, and β) a coating comprising at least one first metal oxide (hydrate) layer, and

(b2) at least one film-forming polymer.

The use of synthetic mica (fluorophlogopite) has several advantages over the traditional natural mica flakes, which are often used in effect pigments. Substrate platelets made from synthetic mica have lower levels of heavy metals and foreign matter than natural mica. Substrate platelets made of synthetic mica also have a smooth, uniform surface, which leads to a more uniform deposition of coating materials, in particular metal oxide (hydrates), and thus to high color purity and reliability. Compared to effect pigments with metal-containing substrate platelets, the effect pigments based on synthetic mica have the advantage of corrosion resistance, which leads to higher storage stabilities when the effect pigments are made up with water and more degrees of freedom in the formulation of the agent (b).

Keratinic material

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

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

Means (a) and (b)

In the context of the method, agents (a) and (b) are applied to the keratinous material, in particular the human hair. The two means (a) and (b) are different from each other. Accordingly, a method for coloring keratinic material, in particular human hair, is disclosed, comprising the following steps:

(b2) and at least one film-forming polymer, the two agents (a) and (b) being different from one another.

Medium (a)

The agent (a) is characterized by its content of at least one organic silicon compound, in particular at least one organic silane. The organic silicon compounds or organic silanes contained in the agent (a) are reactive compounds.

The agent (a) contains the organic silicon compound (s), in particular the organic silane or silanes, in a cosmetic carrier which can be water-containing, low in water or else anhydrous. In addition, the cosmetic carrier can be liquid, gel-like, creamy, pasty, powdery or solid (e.g. in the form of a tablet or a pellet). The cosmetic carrier of the agent (a) is preferably an aqueous or aqueous-alcoholic carrier. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as, for example, shampoos, foam aerosols, foam formulations or other preparations which are suitable for use on the hair.

The cosmetic carrier is preferably water-containing, which means that the carrier - based on its weight - contains at least 2% by weight of water. The water content is preferably above 5% by weight, more preferably above 10% by weight, even more preferably above 15% by weight. The cosmetic carrier can also be aqueous-alcoholic. In the context of the present invention, aqueous-alcoholic solutions are to be understood as meaning aqueous solutions containing 2 to 70% by weight of a C 1 -C ₄ alcohol, in particular ethanol or isopropanol. The agents can also contain other organic solvents such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.

The term “means for coloring” is used in the context of this invention for a coloring of the keratinic material, in particular the human hair, caused by the use of pigments and / or substantive dyes. During this coloring, the aforementioned coloring compounds are deposited in a particularly homogeneous and smooth film on the surface of the keratinous material or diffuse into the keratinous fiber. The film is formed in situ by oligomerization or polymerization of the organic Silicon compounds, as well as through the interaction of organic silicon compounds with the coloring compounds.

Organic silicon compounds

The agent (a) contains at least one organic silicon compound (a1) as an essential component of the invention. Preferred organic silicon compounds (a1) are selected from silanes having one, two or three silicon atoms.

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

The agent (a) particularly preferably contains at least one organic silicon compound (a1) selected from silanes having one, two or three 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 are wholly or partially replaced by organic groups such as, for example, (substituted) alkyl groups and / or alkoxy groups. In the organic silanes, some of the hydrogen atoms can also be replaced by hydroxyl groups.

In a particularly preferred embodiment, the method is characterized by the use of an agent (a) on the keratinous material, the agent (a) containing at least one organic silicon compound selected from silanes with one, two or three silicon atoms.

The agent (a) particularly preferably contains at least one organic silicon compound selected from silanes having one, two or three silicon atoms, the organic silicon compound also comprising one or more basic chemical functions and one or more hydroxyl groups or hydrolyzable groups per molecule.

In a particularly preferred embodiment, the method is characterized by the use of an agent (a) on the keratinous material, the agent (a) containing at least one organic silicon compound (a1) selected from silanes with one, two or three silicon atoms wherein the organic silicon compound further comprises one or more basic chemical functions and one or more hydroxyl groups or hydrolyzable groups per molecule. This basic group can be, for example, an amino group, an alkylamino group, a dialkylamino group or a trialkylamino group, which is preferably connected to a silicon atom via a linker. The basic group is preferably an amino group, a Ci-C6-alkylamino group or a di (Ci-C6) alkylamino group.

The hydrolyzable group or groups are preferably a Ci-C6-alkoxy group, in particular an ethoxy group or a methoxy group. It is preferred if the hydrolyzable group is bonded directly to the silicon atom. If, for example, the hydrolyzable group is an ethoxy group, the organic silicon compound preferably contains a structural unit R'R "R"'Si- _{O-CH 2} -CH3. The radicals R ', R "and R"' represent the three remaining free valences of the silicon atom.

A very particularly preferred method is characterized in that the agent (a) contains at least one organic silicon compound selected from silanes with one, two or three silicon atoms, the organic silicon compound preferably having one or more basic chemical functions and one or more hydroxyl groups or comprises hydrolyzable groups per molecule.

Particularly good results could be obtained if the agent (a) contains at least one organic silicon compound (a1) of the formula (I) and / or (II).

In a further very particularly preferred embodiment, a method is characterized in that an agent (a) is applied to the keratinous material or the human hair, the agent (a) at least one organic silicon compound (a1) of the formula (I) and / or (II) contains,

RiR ₂ NL-Si (OR ₃ ) a (R4) b (I), where

- Ri, R2 independently represent a hydrogen atom or a Ci-C6-alkyl group,

- L stands for a linear or branched, divalent Ci-C2o-alkylene group,

- R3 stands for a hydrogen atom or a Ci-C6-alkyl group,

- R4 stands for a Ci-C6-alkyl group

- a, stands for an integer from 1 to 3, and

- b stands for the whole number 3 - a,

(R50) c (R6) dSi- (A) _e - [NR7- (A ') H0- (A ”)] g- [NR8- (A”')] h-Si (R6> (OR5 ') c · (II), where - R5, R5 ', R5 “independently represent a hydrogen atom or a C1-C6 alkyl group,

- R6, R6 ‘and R6“ independently represent a Ci-C6-alkyl group,

- A, A ‘, A“, A “‘ and A ““ independently of one another represent a linear or branched, divalent Ci-C2o-alkylene group,

- R7 and Rs independently of one another for a hydrogen atom, a Ci-C6-alkyl group, a hydroxy-Ci-C6-alkyl group, a C2-C6-alkenyl group, an amino-Ci-C6-alkyl group or a grouping of the formula (III ) stand

- (A ““) - Si (R6 “) d“ (OR ₅ “) c“ (III),

- c, stands for an integer from 1 to 3,

- d stands for the integer 3 - c,

- c ‘stands for an integer from 1 to 3,

- d ‘stands for the integer 3 - c‘,

- c "stands for an integer from 1 to 3,

- d "stands for the whole number 3 - c" stands,

- e stands for 0 or 1,

- f stands for 0 or 1,

- g stands for 0 or 1,

- h stands for 0 or 1,

- With the proviso that at least one of the radicals from e, f, g and h is different from 0.

The substituents Ri, R2, R3, R4, Rs, Rs ', Rs ", R6, R6', Re", R7, Rs, L, A, A ', A ", A"' and A "" in the compounds of the formula (I) and (II) are explained below by way of example:

Examples of a Ci-C6-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 C2-C6 alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C2-C6 alkenyl radicals are vinyl and allyl. Preferred examples of a hydroxy-Ci-C6-alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group; a 2-hydroxyethyl group is particularly preferred. Examples of an amino-Ci-C6-alkyl group are the aminomethyl group, the 2-aminoethyl group and the 3-aminopropyl group. The 2-aminoethyl group is particularly preferred. Examples of a linear divalent Ci-C2o-alkylene group are, for example, the methylene group (-CH2-), the ethylene group (-CH2-CH2-), the propylene group (-CH2-CH2-CH2-) and the butylene group (-CH2- CH2-CH2-CH2-). The propylene group (-CH2-CH2-CH2-) is particularly preferred. From a chain length of 3 carbon atoms, divalent alkylene groups can also be branched. Examples of branched, divalent C3-C2o-alkylene groups are (-CFh-CF CFh) -) and (-CH2-CH (CH ₃ ) -CH ₂ -).

In the organic silicon compounds (a1) of the formula (I) RiR ₂ NL-Si (OR ₃ ) a (R4) b (I), the radicals Ri and R ₂ independently of one another represent a hydrogen atom or a C1-C6-alkyl group. The radicals Ri and R ₂ are very particularly preferably both a hydrogen atom.

In the middle part of the organic silicon compound (a1) is the structural unit or the linker - L- which stands for a linear or branched, divalent Ci-C ₂ o-alkylene group.

-L- is preferably a linear, divalent Ci-C ₂ o-alkylene group. With further preference -L- stands for a linear divalent Ci-C6-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 organic silicon compounds (a1) of the formula (I)

RiR ₂ NL-Si (OR ₃ ) a (R4) b (I), each have the silicon-containing grouping -Si (OR ₃ ) _a (R4) b at one end

In the terminal structural unit -Si (OR ₃ ) _a (R4) b, the radical R _{3 stands} for a hydrogen atom or a Ci-C6-alkyl group, and the radical R4 stands for a Ci-C6-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.

Dyes with the best wash fastness could be obtained if the agent (a) contains at least one organic silicon compound (a1) of the formula (I) in which the radicals R ₃ , R4 independently of one another represent a methyl group or an ethyl group.

Furthermore, dyeings with the best wash fastness properties could be obtained if the agent (a) contains at least one organic silicon compound (a1) of the formula (I) in which the radical a stands for the number 3. In this case, the remainder b stands for the number 0.

In a further preferred embodiment, an agent (a) is characterized in that it contains at least one organic silicon compound (a1) of the formula (I), where

- R ₃ , R4 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.

In a further preferred embodiment, the method is characterized in that the agent (a) contains at least one organic silicon compound (a1) of the formula (I),

RiR ₂ NL-Si (OR ₃ ) a (R4) b (I), where

- Ri, R ₂ both stand for a hydrogen atom, and

- L stands for a linear, divalent Ci-C6-alkylene group, preferably for a propylene group (-CH ₂ - CH2-CH2-) or for an ethylene group (-CH2-CH2-),

- R3 stands for a hydrogen atom, 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.

If b stands for the number 0, the radical R ₄ does not occur in the compounds of the formula (I).

In a further preferred embodiment, the method is accordingly characterized in that the agent (a) contains at least one organic silicon compound (a1) of the formula (I),

RiR ₂ NL-Si (OR ₃ ) a (R4) b (I), where

- Ri, R ₂ both stand for a hydrogen atom, and

- L for a linear, divalent Ci-C6 alkylene group, preferably for a propylene group (-CH ₂ -

CH2-CH2-) or an ethylene group (-CH2-CH2-),

- R3 stands for a hydrogen atom, an ethyl group or a methyl group,

- a stands for the number 3 and

- b stands for the number 0.

Organic silicon compounds (a1) of the formula (I) which are particularly suitable for solving the problem are

- (3-aminopropyl) triethoxysilane

- (3-aminopropyl) trimethoxysilane - (2-aminoethyl) triethoxysilane

- (2-aminoethyl) trimethoxysilane

- (3-Dimethylaminopropyl) triethoxysilane - (3-Dimethylaminopropyl) trimethoxysilane

-1- (3-dimethylaminopropyl) silanetriol

- (2-Dimethylaminoethyl) triethoxysilane

- (2-Dimethylaminoethyl) trimethoxysilane and / or

-1- (2-dimethylaminoethyl) silanetriol

In a further preferred embodiment, the method is characterized in that the agent (a) contains at least one organic silicon compound (a1) of the formula (I) which is selected from the group of

- (3-aminopropyl) triethoxysilane

- (3-aminopropyl) trimethoxysilane

- 1- (3-aminopropyl) silanetriol

- (2-aminoethyl) triethoxysilane - (2-aminoethyl) trimethoxysilane

- 1- (2-aminoethyl) silanetriol

- (3-Dimethylaminopropyl) triethoxysilane

- (3-Dimethylaminopropyl) trimethoxysilane - 1 - (3-Dimethylaminopropyl) silanetriol

- (2-Dimethylaminoethyl) triethoxysilane.

- (2-dimethylaminoethyl) trimethoxysilane,

- 1 - (2-dimethylaminoethyl) silanetriol and mixtures thereof.

The aforementioned organic silicon compounds (a1) of the formula (I) are commercially available.

(3-Aminopropyl) trimethoxysilane can be purchased from Sigma-Aldrich, for example. (3-Aminopropyl) triethoxysilane is also commercially available from Sigma-Aldrich.

In a further embodiment, the agent (a) contains at least one organic silicon compound of the formula (II)

(R50) c (R6) dSi- (A) e- [NR7- (A ')] ^ [0- (A ”)] g- [NR8- (A”')] h-Si (R6 ^, ) d (OR5 ^, ) c • (II).

The organosilicon compounds (a1) of the formula (II) each have the silicon-containing groups (RsO) c (R6) dSi and -Si (R6 ') d' (OR5 ') c at both ends

In the middle part of the molecule of the formula (II) there are the groupings - (A) _e - and - [NR7- (A ')] _f - and - [0- (A ”)] _g - and - [NR8- (A '”)] _H - Here, each of the radicals e, f, g and h can independently represent the number 0 or 1, with the proviso that at least one of the radicals e, f, g and h is different from 0. In other words, an organic silicon compound (a1) of the formula (II) contains at least one group selected from - (A) - and - [NR7- (A ') j- and - [0- (A ”) j- and - [NR ₈ - (A '”)] -

In the two terminal structural _{units (R50) c} (R6) dSi- and - Si (R6 ') d' (OR5 ') c, the radicals R5, R5', R5 "stand independently of one another for a hydrogen atom or for a Ci-C6- Alkyl group. The radicals R6, R6 'and R6 ″ stand independently of one another for a Ci-C6-alkyl group.

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

Similarly, c 'stands for an integer from 1 to 3, and d' stands for the integer 3 - c '. If c 'stands for the number 3, then d' equals 0. If c 'stands for the number 2, then d' equals 1. If c 'stands for the number 1, then d' equals 2. Dyeings with the best wash fastness properties could be obtained if the residues c and c 'both stand for the number 3. In this case, d and d 'both stand for the number 0.

In a further preferred embodiment, the method is characterized in that the agent (a) contains at least one organic silicon compound (a1) of the formula (II),

(R50) c (R6) dSi- (A) e- [NR7- (A ') H0- (A ”)] g- [NR8- (A”')] h-Si (R6X0R5 ') c · (II ), in which

- R5 and R5 ‘independently of one another represent a methyl group or an ethyl group,

- c and c ‘both stand for the number 3 and

- d and d ‘both stand for the number 0.

If c and c ‘both stand for the number 3 and d and d‘ both stand for the number 0, the organic silicon compounds correspond to the formula (lla)

(R50) 3Si- (A) _e - [NR7- (A ') H0- (A ”)] g- [NR8- (A”')] h-Si (OR5 ') 3 (Ha).

The radicals e, f, g and h can independently represent the number 0 or 1, at least one radical from e, f, g and h being different from zero. The abbreviations e, f, g and h define which of the groupings - (A) _e - and - [NR7- (A ')] _f and - [0- (A ”)] _g - and - [NR8 - (A ”')] _h - are located in the central part of the organic silicon compound of the formula (II).

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

When e and f both stand for the number 1 and g and h both stand for the number 0, the organic silicon compound (a1) corresponds to the formula (Mb)

(R50) c (R6) dSi- (A) - [NR7- (A ')] - Si (R6> (0R5') c · (llb).

The radicals A, A ', A ", A"' and A "" stand independently of one another for a linear or branched, divalent Ci-C2o-alkylene group. The radicals A, A ', A ", A"' and A "" are preferably, independently of one another, a linear, divalent Ci-C2o-alkylene group. The radicals A, A ', A ", A"' and A "" are more preferably, independently of one another, a linear divalent Ci-C6-alkylene group. The radicals A, A ', A ", A"' and A "" are particularly preferably, independently of one another, a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2) -) or a butylene group (-CH2-CH2-CH2-CH2-). The radicals A, A ', A ", A"' and A "" very particularly preferably represent a propylene group (-CH2-CH2-CH2-).

If the remainder f stands for the number 1, then the organic silicon compound of the formula (II) contains a structural grouping - [NR7- (A ’)] -.

If the radical h stands for the number 1, then the organic silicon compound of the formula (II) contains a structural grouping - [NR8- (A "’)] -.

The radicals R7 and Rs independently of one another represent a hydrogen atom, a C1-C6-alkyl group, a hydroxy-Ci-C6-alkyl group, a C2-C6-alkenyl group, an amino-Ci-C6-alkyl group or a grouping of the Formula (III)

- (A ““) - Si (R6 “) d“ (OR ₅ “) c“ (III).

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

If the radical f stands for the number 1 and the radical h stands for the number 0, the organic silicon compound (a1) contains the grouping [NR7- (A ')], but not the grouping - [NR8- (A ”') ] If the radical R7 stands for a grouping of the formula (III), then the agent (a) contains an organic silicon compound with 3 reactive silane groups.

In a further preferred embodiment, the process is characterized in that the agent (a) contains at least one organic silicon compound (a1) of the formula (II),

(R50) c (R6) dSi- (A) e- [NR7- (A ')] ^ [0- (A ”)] g- [NR8- (A”')] h-Si (R6 ^, ) d (OR5 ^, ) c • (II), where

- e and f both stand for the number 1,

- g and h both stand for the number 0,

- A and A ‘independently represent a linear, divalent Ci-C6-alkylene group, and

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

In a further preferred embodiment, the process is characterized in that the agent (a) contains at least one organic silicon compound (a1) of the formula (II), where

- e and f both stand for the number 1,

- g and h both stand for the number 0,

- A and A 'independently of one another represent a methylene group (-CH2-), an ethylene group (-CH2-CH2-) or a propylene group (-CH2-CH2-CH2), and - R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a grouping of the formula (III).

Organic silicon compounds (a1) of the formula (II) which are very suitable for solving the problem are

- 3- (Trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine

- 3- (Triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine

- N-methyl-3- (trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine

- N-methyl-3- (triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine - 2- [bis [3- (trimethoxysilyl) propyl] amino] ethanol

- 2- [bis [3- (triethoxysilyl) propyl] amino] ethanol

- 3- (Trimethoxysilyl) -N, N-bis [3- (trimethoxysilyl) propyl] -1-propanamine

- 3- (Triethoxysilyl) -N, N-bis [3- (triethoxysilyl) propyl] -1-propanamine - N1, N1-bis [3- (trimethoxysilyl) propyl] -1, 2-ethanediamine,

- N1, N1-bis [3- (triethoxysilyl) propyl] -1, 2-ethanediamine,

- N, N-bis [3- (trimethoxysilyl) propyl] -2-propen-1-amine - N, N-bis [3- (triethoxysilyl) propyl] -2-propen-1-amine

The aforementioned organic silicon compounds (a1) of the formula (II) are commercially available. Bis (trimethoxysilylpropyl) amine with the CAS number 82985-35-1 can be purchased from Sigma-Aldrich, for example.

Bis [3- (triethoxysilyl) propyl] amine with the CAS number 13497-18-2 can be purchased from Sigma-Aldrich, for example.

N-methyl-3- (trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine is alternatively also referred to as bis (3-trimethoxysilylpropyl) -N-methylamine and can be purchased commercially from Sigma-Aldrich or Fluorochem .

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

In a further preferred embodiment, an agent (a) is characterized in that it contains at least one organic silicon compound (a1) of the formula (II) which is selected from the group from

- 3- (Trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine

- 3- (Triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine

- N-methyl-3- (triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine

- 2- [bis [3- (trimethoxysilyl) propyl] amino] ethanol

- 2- [bis [3- (triethoxysilyl) propyl] amino] ethanol

- 3- (Trimethoxysilyl) -N, N-bis [3- (trimethoxysilyl) propyl] -1-propanamine

- 3- (Triethoxysilyl) -N, N-bis [3- (triethoxysilyl) propyl] -1-propanamine

- N1, N1-bis [3- (trimethoxysilyl) propyl] -1, 2-ethanediamine,

- N1, N1-bis [3- (triethoxysilyl) propyl] -1, 2-ethanediamine,

- N, N-bis [3- (trimethoxysilyl) propyl] -2-propene-1-amine and / or

- N, N-bis [3- (triethoxysilyl) propyl] -2-propen-1-amine. In further dyeing tests it has also been found to be particularly advantageous if the agent (a) applied to the keratinous material in the process contains at least one organic silicon compound (a1) of the formula (IV)

RgSi (ORio) k (Rll) m (IV).

The organic silicon compound (s) (a1) of the formula (IV) can also be referred to as silanes of the alkylalkoxysilane or alkylhydroxysilane type,

RgSi (ORio) k (Rll) m (IV), where

- Rg stands for a Ci-Ci8-alkyl group,

- Rio stands for a hydrogen atom or a Ci-C6-alkyl group,

- R11 stands for a Ci-C6-alkyl group

- k stands for an integer from 1 to 3, and

- m stands for the integer 3 - k.

In a further preferred embodiment, the process is characterized in that the agent (a) contains at least one organic silicon compound (a1) of the formula (IV).

R ₉ Si (ORio) k (Rn) m (IV), where

- Rg stands for a Ci-Ci8-alkyl group,

- Rio stands for a hydrogen atom or a Ci-C6-alkyl group,

- R11 stands for a Ci-C6-alkyl group

- k stands for an integer from 1 to 3, and

- m stands for the integer 3 - k.

In a further preferred embodiment, the process is characterized in that the agent (a) contains at least one further organic silicon compound (a1) of the formula (IV) in addition to the organic silicon compound or compounds (a1) of the formula (I)

RgSi (ORio) k (Rn) m (IV), where

- Rg stands for a Ci-Ci8-alkyl group,

- Rio stands for a hydrogen atom or a Ci-C6-alkyl group,

- R11 stands for a Ci-C6-alkyl group

- k stands for an integer from 1 to 3, and

- m stands for the integer 3 - k. In a further preferred embodiment, the process is characterized in that the agent (a) contains at least one further organic silicon compound (a1) of the formula (IV) in addition to the organic silicon compound or compounds (a1) of the formula (II)

R ₉ Si (ORio) k (Rn) m (IV), where

- Rg stands for a Ci-Ci8-alkyl group,

- Rio stands for a hydrogen atom or a Ci-C6-alkyl group,

- R11 stands for a Ci-C6-alkyl group

- k stands for an integer from 1 to 3, and

- m stands for the integer 3 - k.

In a further preferred embodiment, the method is characterized in that the agent (a) in addition to the organic silicon compound (s) (a1) of the formula (I) and / or (II) at least one further organic silicon compound (a1) of the formula (IV) contains

RgSi (ORio) k (Rll) m (IV), where

- Rg stands for a Ci-Ci8-alkyl group,

- Rio stands for a hydrogen atom or a Ci-C6-alkyl group,

- R11 stands for a Ci-C6-alkyl group

- k stands for an integer from 1 to 3, and

- m stands for the integer 3 - k.

In the organic silicon compounds (a1) of the formula (IV), the radical Rg stands for a C1-C18-alkyl group. This Ci-Ci8-alkyl group is saturated and can be linear or branched. Rg is preferably a linear Ci-Ci8-alkyl group. Rg 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, an n-dodecyl group or an n-octadecyl group. Rg particularly preferably stands for a methyl group, an ethyl group, a propyl group, an n-hexyl group or an n-octyl group.

In the organic silicon compounds (a1) of the formula (IV), the radical R10 represents a hydrogen atom or a Ci-C6-alkyl group. R10 particularly preferably represents a methyl group or an ethyl group.

In the organic silicon compounds (a1) of the form (IV), the radical Rn stands for a C1-C6-alkyl group. R11 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, then m is 2.

Dyeings with the best wash fastness properties could be obtained if an agent (a) was used in the process which contains at least one organic silicon compound (a1) of the formula (IV) in which the remainder k stands for the number 3. In this case, the remainder m stands for the number 0.

Organic silicon compounds (a1) of the formula (IV) which are particularly suitable for solving the problem according to the invention are methyltrimethoxysilane

-

- ethyltrimethoxysilane

- ethyltriethoxysilane

- n-hexyltriethoxysilane

- n-octyltriethoxysilane - n-Dodecyltrimethoxysilane and / or

- n-dodecyltriethoxysilane.

In a further preferred embodiment, the process is characterized in that the agent (a) contains at least one organic silicon compound (a1) of the formula (IV) which is selected from the group consisting of

- methyltrimethoxysilane

- methyltriethoxysilane

- ethyltrimethoxysilane

- ethyltriethoxysilane

- propyltrimethoxysilane

- propyltriethoxysilane

- hexyltrimethoxysilane

- hexyltriethoxysilane

- Octyltrimethoxysilane

- octyltriethoxysilane

- dodecyltrimethoxysilane

- dodecyltriethoxysilane

- Octadecyltrimethoxysilane and / or

- Octadecyltriethoxysilane.

In the course of the work leading to this invention it has been found that particularly stable and uniform films could be obtained on the keratinic material even if the agent (a) contains two structurally different organic silicon compounds. In a further preferred embodiment, a method is characterized in that the agent (a) contains at least two structurally different organic silicon compounds.

In a preferred embodiment, a method is characterized in that an agent (a) is used on the keratinic material which contains at least one organic silicon compound of the formula (I) and at least one organic silicon compound of the formula (IV).

In an explicitly very particularly preferred embodiment, the method is characterized in that an agent (a) is used on the keratinic material which (a1) contains at least one organic silicon compound of the formula (I) which is selected from the group consisting of (3- Aminopropyl) triethoxysilane and (3-aminopropyl) trimethoxysilane is selected, and additionally contains at least one organic silicon compound of the formula (IV), which is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, hexoxysilane, propyltrimethoxysilane, hexoxysilane, propyltrimethoxysilane, hexoxysilane, propyltrimethoxysilane, hexoxysilane, propyltrimethoxysilane, hexoxysilane, propyltrimethoxysilane of the formula (IV) of the formula in addition of the formula (IV) in addition at least one organic silicon compound of the formula IV , Dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane is selected.

The organic silicon compounds described above are reactive compounds. In this context, it has been found to be preferred if the agent (a) - based on the total weight of the agent (a) - prefers one or more organic silicon compounds (a1) in a total amount of 0.1 to 20% by weight Contains 0.5 to 15% by weight and particularly preferably 5.0 to 10% by weight.

In this context, it has been found to be particularly preferred if the agent (a) - based on the total weight of the agent (a) - has one or more organic silicon compounds (a1) of the formula (I) and / or (II) in a total amount from 0.1 to 20% by weight, preferably 0.2 to 15% by weight and particularly preferably 0.2 to 3% by weight.

It has also been found to be particularly preferred if the agent (a) - based on the total weight of the agent (a) - has one or more organic silicon compounds (a1) of the formula (IV) in a total amount of 0.1 to 20 wt. -%, preferably 0.5 to 15% by weight and particularly preferably 2 to 8% by weight.

Even the addition of small amounts of water leads to hydrolysis of organic silicon compounds with at least one hydrolyzable group. The hydrolysis products and / or organic silicon compounds with at least one hydroxyl group can react with one another in a condensation reaction. For this reason, both the organosilicon compounds with at least one hydrolyzable group and their hydrolysis and / or condensation products can be contained in the agent (a). When using Organosilicon compounds with at least one hydroxyl group can contain both the organic silicon compounds with at least one hydroxyl group and their condensation products in the agent (a).

A condensation product is understood to mean a product that is formed by the reaction of at least two organic silicon compounds each with at least one hydroxyl group or hydrolyzable group per molecule with elimination of water and / or with elimination of an 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 organic silicon compounds to condensation product.

Particularly good results could be obtained if organic silicon compounds (a1) of the formula (I) and / or (II) were used in the process. Since, as already described above, hydrolysis / condensation begins even with traces of moisture, the hydrolysis and / or condensation products of the organic silicon compounds (I) and / or (II) are also included in this embodiment.

Particularly resistant colorations could be obtained when using an alkaline agent (a). The agent (a) preferably contains water and has a pH of from 7 to 11.5, preferably from 7.5 to 11 and particularly preferably from 8 to 10.5.

In a further very particularly preferred embodiment, the method is characterized in that the agent (a) has a pH of 7 to 11.5, preferably from 7.5 to 11 and particularly preferably from 8 to 10.5.

Medium (bl

The agent (b) is characterized by the presence of at least one coloring compound (b1) and at least one film-forming polymer (b2). The coloring compound (b1) comprises at least one effect pigment, comprising a) a substrate platelet comprising synthetic mica, and β) a coating comprising at least one first metal oxide (hydrate) layer.

The effect pigment has a substrate platelet comprising synthetic mica.

Synthetic mica is also referred to as synthetic fluorophlogopite (INCI: Synthetic Fluorophlogopite) and is preferably a fluorophlogopite of the empirical formula KMg3 (AIS) OioF ₂ , KMg2 ^1/2 (SUOio) F2 or NaMg2 ^1/2 (SUOio) F2, particularly preferably a fluorophlogopite the empirical formula KMg3 (AISi3) OioF2.

In contrast to synthetically produced mica particles, natural mica particles have the disadvantage that they can contain impurities from embedded foreign ions. These Impurities can change the hue and / or reduce the lightness L ^* . Typical impurities in, for example, natural mica include nickel, chromium, copper, iron, manganese, lead, cadmium, arsenic and / or antimony and / or their compounds, which, for example, can give natural mica a color. The production of a synthetic mica can be controlled in a targeted manner so that the resulting synthetic mica particles have as few defects as possible. Furthermore, particle size can also be controlled and controlled in the production of a synthetic mica. In addition, synthetically produced mica particles have a smooth, uniform surface, which leads to a more uniform deposition of materials such as metal oxides (hydrate) and thus to high color purity and reliability.

One advantage over effect pigments based on metal substrate platelets, in particular aluminum substrate platelets, is that synthetically produced mica particles are corrosion-resistant, in particular when they come into contact with water.

The substrate wafer preferably has an average thickness of 50 to 1500 nm, and more preferably 90 to 1000 nm.

The size of the substrate platelet can be matched to the particular application, for example the desired effect on a keratinic material. As a rule, the substrate platelets have a mean largest diameter of about 1 to 200 μm, in particular about 5 to 100 μm and even more preferably about 5 to 25 μm.

The substrate platelets can have various shapes. For example, lamellar or lenticular substrate platelets can be used as substrate platelets. Lamellar substrate platelets are characterized by an irregularly structured edge and are also referred to as "cornflakes" due to their appearance. Lenticular substrate platelets have an essentially regular, round edge and are also referred to as "silver dollars" because of their appearance.

By means of a coating, the surface properties and / or optical properties of the effect pigment can be changed and the mechanical and chemical resistance of the effect pigments can be increased. For example, only the upper and / or lower side of the substrate platelet can be coated, with the side surfaces being cut out. The entire surface of the substrate platelets, including the side surfaces, is preferably covered with the coating. The substrate platelets are preferably completely encased by the coating.

The coating can consist of one or more metal oxide (hydrate) layers. In a preferred embodiment, the coating only has a first layer. In a likewise preferred embodiment, the coating has a total of at least two, preferably two or three, layers. It may be preferred to have the coating a first Metal oxide (hydrate) layer A and a second metal oxide (hydrate) layer B, the second metal oxide (hydrate) layer B being different from the first metal oxide (hydrate) layer A. The first metal oxide (hydrate) layer A is preferably located between the second metal oxide (hydrate) layer B and the surface of the substrate platelet. It may be preferred that the coating has three layers A, B and C. In this embodiment, the first metal oxide (hydrate) layer A is located between the second metal oxide (hydrate) layer B and the surface of the substrate platelet, and on the second metal oxide (hydrate) layer B there is a third layer C, which is from the second layer underneath B is different.

It is very particularly preferred that the coating has a first metal oxide (hydrate) layer and a second metal oxide (hydrate) layer.

Suitable materials for the at least one first metal oxide (hydrate) layer are all metal oxides or metal oxide hydrates that can be permanently applied to the substrate platelets, including synthetic mica. The materials should preferably be able to be applied in the form of a film.

In a preferred embodiment, the first metal oxide comprises (hydrate) layer, a metal oxide (hydrate) is selected from the group consisting of titanium dioxide (T1O2), iron oxide (Fe ₂ 03 and / or FE30 ₄₎ and mixtures thereof. In a very preferred embodiment, the first metal oxide (hydrate) layer comprises the first metal oxide (hydrate) layer comprises titanium dioxide (T1O2) and / or iron oxide (Fe ₂ 03). In an extremely preferred embodiment, the first metal oxide (hydrate) layer comprises the first metal oxide (hydrate) layer comprises titanium dioxide (T1O2).

The entire surface of the substrate platelets, including the side surfaces, is preferably enveloped by the at least one first metal oxide (hydrate) layer.

The at least one first metal oxide (hydrate) layer can for example be produced wet-chemically using a metal alkoxide, in particular titanium alkoxide such as titanium alkoxides such as titanium tetraethylate (tetraethyl orthotitanate) or titanium tetraisopropanolate (tetraisopropyl orthotitanate).

Alternatively, the at least one first metal oxide (hydrate) layer can be formed, for example, by hydrolytic decomposition of one or more organic metal compounds and / or by precipitation of one or more dissolved metal salts and, if necessary, subsequent aftertreatment (for example, transferring a hydroxide-containing layer that has formed into the oxide layers by tempering) getting produced.

The second metal oxide (hydrate) layer, if any, is different from the first metal oxide (hydrate) layer.

Metal oxide (hydrate) suitable for the second metal oxide (hydrate) layer are tin oxide (Sn0 ₂ ), silicon oxide (S1O2), aluminum oxide (AI2O3) and / or iron oxide (Fe2Ü3 and / or Fe304). Corresponding it is preferred that the second metal oxide (hydrate) layer is a metal oxide (hydrate) selected from the group consisting of tin oxide (SnC> 2), silicon oxide (SiC> 2), aluminum oxide (Al2O3), iron oxide (Fe2C> 3 and / or Fe30 ₄ ) and mixtures thereof. It is particularly preferred that the second metal oxide (hydrate) layer contains tin oxide (SnC> 2).

The second metal oxide (hydrate) layer can also contain a selectively absorbing dye or a selectively absorbing pigment. Suitable dyes and / or pigments include, for example, carmine, iron (l I l) hexacyanidoferrate (ll / l 11) and chromium oxide green (Cr ₂ 03).

The effect pigments can have a further layer C, which functions as a protective layer and comprises a metal oxide (hydrate) or a polymer, for example a synthetic resin. Suitable metal oxides (hydrates) 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.

It is particularly preferred that the effect pigment has a substrate platelet made of synthetic mica (INCI: Synthetic Fluorphlogopite) and a first metal oxide (hydrate) layer comprising titanium dioxide (T1O2).

It is also preferred that the effect pigment has a substrate platelet made of synthetic mica (INCI: Synthetic Fluorphlogopite) and a first metal oxide (hydrate) layer comprising iron (III) oxide (Fe 2 O 3).

It is also preferred that the effect pigment has a substrate platelet made of synthetic mica (INCI: Synthetic Fluorphlogopite), a first metal oxide (hydrate) layer comprising titanium dioxide (T1O2) and iron (III) oxide (Fe ₂ 03), and a second metal oxide ( hydrate) layer comprising tin dioxide (Sn0 ₂ ).

It is extremely preferred that the effect pigment has a substrate platelet made of synthetic mica (INCI: Synthetic Fluorphlogopite), a first metal oxide (hydrate) layer, comprising titanium dioxide (T1O2), and a second metal oxide (hydrate) layer, comprising tin dioxide (Sn0 ₂ ), having.

As a rule, the effect pigments have a mean largest diameter of from about 1 to 200 μm, in particular from about 5 to 100 μm and even more preferably from about 5 to 25 μm.

The effect pigments preferably have an average particle size D50 of 3 to 150 μm, preferably 5 to 45 μm and particularly preferably 10 to 30 μm.

Very particularly preferred effect pigments have a substrate platelet made of synthetic mica (INCI: Synthetic Fluorphlogopite), a first metal oxide (hydrate) layer comprising titanium dioxide (T1O2), a second metal oxide (hydrate) layer, comprising tin dioxide (Sn0 ₂ ), and an average particle size D50 of 10 to 14 μm.

Effect pigments comprising a) a substrate platelet comprising synthetic mica, and β) a coating comprising at least one first metal oxide (hydrate) layer, are available, for example, under the name Timiron® from Merck or under the name SYNCRYSTAL from Eckart.

The adhesion and abrasion resistance of effect pigments, comprising a) a substrate platelet, comprising synthetic mica, and ß) a coating comprising at least one first metal oxide (hydrate) layer, in the keratinous material can be increased even further by adding organic to the outermost layer Compound such as silanes, phosphoric acid esters, titanates, borates or carboxylic acids is modified. The organic compounds are bound to the surface of the outermost, preferably metal oxide-containing, layer. The outermost layer denotes the layer which is spatially furthest away from the substrate plate. The organic compounds are preferably functional silane compounds which can bind to the outermost layer, which is preferably a metal oxide. These can be either mono- or bifunctional compounds. Examples of bifunctional organic compounds are methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxy propyltriethoxysilane, 3- acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3- methacryloxypropyltris (methoxyethoxy) silane, 3-methacryloxypropyltris ( butoxyethoxy) silane, 3-methacryloxypropyltris (propoxy) silane, 3-methacryloxypropyltris (butoxy) silane, 3-acryloxypropyltris (methoxyethoxy) silane, 3-acryloxypropyltris (butoxyethoxy) silane, 3-acryloxypropyltris, butoxy) silane Viny itrimethoxysilane, 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 is covalently attached to the surface of the effect pigment, comprising a) a substrate platelet comprising synthetic mica, and β) a coating comprising at least one first metal oxide (hydrate) layer, or, if it is not completely covered, can bind to the mica surface. The hydrocarbon residue of the silane points 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. The effect pigments are particularly preferably surface-modified with a monofunctional silane. Octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane and hecadecyltriethoxysilane are particularly preferred. The modified surface properties / hydrophobicity can improve adhesion, abrasion resistance and alignment in the application. It has been shown that effect pigments with such a coating show even better compatibility with the film formed by means (a).

Particularly good results could be obtained if the agent (b) - based on the total weight of the agent (b) - has one or more effect pigments in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight .-%, more preferably from 0.2 to 6% by weight and very particularly preferably from 0.5 to 4.5% by weight.

In addition to the effect pigment, the agent (b) can comprise further coloring compounds selected from the group consisting of pigments and / or substantive dyes.

The agent (b) is further characterized in that it contains at least one film-forming polymer (b2).

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.

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 polymer (b) 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.

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

The film-forming polymers (b2) in means (b) can be hydrophilic or hydrophobic.

In a first embodiment, it can be preferred to use at least one hydrophobic, film-forming polymer in the means (b). A hydrophobic polymer is understood to mean a polymer that has a solubility in water at 25 ° C. (760 mmHg) of less than 1% by weight.

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

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

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

In a further preferred embodiment, an agent (b) is characterized in that it contains at least one film-forming, hydrophobic polymer (b2) selected from the group consisting of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters , homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinyl pyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and / or polyamides.

In particular, the film-forming hydrophobic polymers which are selected from the group of synthetic polymers, polymers obtainable by free radical polymerization or natural polymers have proven to be particularly suitable for achieving the object of the invention. Further particularly suitable film-forming hydrophobic polymers can be selected from the homopolymers or copolymers of olefins, such as cycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinyl amides, the esters or amides of (meth) acrylic acid with at least one Ci-C2o-alkyl group, an aryl group or a C2-Cio-hydroxyalkyl group.

Further film-forming hydrophobic polymers can be selected from the homo- or copolymers of isooctyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate), isopentyl (meth) acrylate, n-butyl (meth) acrylate), isobutyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, tert-butyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methacrylate) , 3-hydroxypropyl (meth) acrylate and / or mixtures thereof.

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

Further preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their Ci-C6-alkyl esters, as sold under the INCI declaration Acrylates Copolymers. A suitable commercial product is, for example Aculyn ^® 33 from Rohm & Haas. However, copolymers of acrylic acid, methacrylic acid or their Ci-C6-alkyl esters and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol are also preferred. Suitable ethylenically unsaturated acids are in particular acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20.

Particularly preferred polymers on the market are, for example, Aculyn® 22 (Acrylates / Steareth-20 Methacrylate Copolymer), Aculyn® 28 (Acrylates / Beheneth-25 Methacrylate Copolymer), Structure 2001® (Acryla-tes / 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 / C10-30 Alkyl Acrylate Crosspolymer), Synthalen W2000® (Acrylates / Palmeth-25 Acrylate Copolymer) or the Soltex OPT (Acrylates / C 12-22 Alkyl methacrylate Copolymer) sold by Rohme and Haas.

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

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

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

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

Surprisingly, it has been found that particularly intense and washfast colors could be obtained if the agent (b) contained at least one film-forming polymer (b2) selected from the group of homopolymers and copolymers of acrylic acid, homopolymers and copolymers of methacrylic acid, homopolymers and copolymers of acrylic acid esters, homopolymers and copolymers of methacrylic acid esters, homopolymers and copolymers of acrylic acid amides, homopolymers and copolymers of methacrylic acid amides, homopolymers and copolymers of vinyl pyrrolidone, homopolymers and copolymers of vinyl alcohol , homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of ethylene, homopolymers and copolymers of propylene, homopolymers and copolymers of styrene, polyurethanes, polyesters and polyamides.

In a further preferred embodiment, a method is characterized in that the agent (b) contains at least one film-forming polymer (b2) which is selected from the group of homopolymers and copolymers of acrylic acid, the homopolymers and copolymers of methacrylic acid, the homopolymers and copolymers of Acrylic acid esters, homopolymers and copolymers of methacrylic acid esters, homopolymers and copolymers of acrylic acid amides, homopolymers and copolymers of methacrylic acid amides, homopolymers and copolymers of vinyl pyrrolidone, homopolymers and copolymers of vinyl alcohol, homopolymers and copolymers of vinyl acetate homopolymers and copolymers of ethylene, homopolymers and copolymers of propylene, homopolymers and copolymers of styrene, polyurethanes, polyesters and polyamides.

In the context of a further embodiment, it can be preferred to use at least one hydrophilic, film-forming polymer (b2) in the means (b).

A hydrophilic polymer is understood to mean a polymer that has a solubility in water at 25 ° C. (760 mmHg) of more than 1% by weight, preferably more than 2% by weight. The water solubility of the film-forming hydrophilic polymer can be determined, for example, in the following way. 1 g of the polymer is placed in a beaker. Make up to 100 g with water. A stir bar is added and the mixture is warmed to 25 ° C on a magnetic stirrer while stirring. It is stirred for 60 minutes. The aqueous mixture is then assessed visually. A completely dissolved polymer appears macroscopically homogeneous. If the polymer-water mixture cannot be assessed visually due to the high turbidity of the mixture, the mixture is filtered. If no undissolved polymer remains on the filter paper, then the solubility of the polymer is more than 1% by weight.

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

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

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

In a further very particularly preferred embodiment, an agent (b) is characterized in that it contains at least one film-forming, hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone (PVP) and the copolymers of polyvinylpyrrolidone.

It is also preferred if the agent contains polyvinylpyrrolidone (PVP) as the film-forming, hydrophilic polymer. Surprisingly, the washfastness of the dyeings that could be obtained with PVP-containing agents (b9) was also very good.

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

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

Other particularly suitable polyvinylpyrrolidones are the substances known under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60, LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115 and available from BASF. The use of film-forming hydrophilic polymers (b2) from the group of copolymers of polyvinylpyrrolidone has also led to particularly good and washable color results.

Especially suitable film-forming, hydrophilic polymers Vinylester vinylpyrrolidone copolymers can be mentioned, as they are sold for example under the trademark Luviskol ^® (BASF) in this context. Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinyl pyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

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

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

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

In a further very particularly preferred embodiment, an agent (b) is characterized in that it contains at least one film-forming, hydrophilic polymer (b2) selected from the group consisting of polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / styrene Copolymers, vinyl pyrrolidone / ethylene copolymers, vinyl pyrrolidone / propylene copolymers, vinyl pyrrolidone / vinyl caprolactam copolymers, vinyl pyrrolidone / vinyl formamide copolymers and / or vinyl pyrrolidone / vinyl alcohol copolymers.

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

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

In a further embodiment, the agent (b) can contain at least one nonionic, film-forming, hydrophilic polymer (b2). According to the invention, a nonionic polymer is understood to mean a polymer which in a protic solvent - such as, for example, water - does not carry structural units with permanently cationic or anionic groups under standard conditions which have to be compensated by counterions while maintaining electrical neutrality. Cationic groups include, for example, quaternized ammonium groups but not protonated amines. Anionic groups include, for example, carboxyl and sulfonic acid groups.

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

Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acids with 2 to 18 carbon atoms, in particular of N-vinylpyrrolidone and vinyl acetate,

Copolymers of N-vinylpyrrolidone and N-vinylimidazole and methacrylamide,

Copolymers of N-vinylpyrrolidone and N-vinylimidazole and acrylamide,

Copolymers of N-vinylpyrrolidone with N, N-di (C1 to C4) -alkylamino- (C2 to C4) -alkylacrylamide.

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

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

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

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

Further suitable film-forming, hydrophilic polymers are, for example Vinylpyrrolidone-vinylimidazolium methochloride copolymers, as offered under the names Luviquat ^® FC 370, FC 550 and the INCI name Polyquaternium-16 as well as FC 905 and HM 552,

Vinylpyrrolidone-vinyl caprolactam-acrylate terpolymers, such as those offered by Acrylsäureestern and acrylamides as the third monomer commercially, for example under the name Aqua Flex ^® SF 40th

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

Polyquaternium-46 is the reaction product of vinyl caprolactam and vinyl pyrrolidone with methyl vinyl imidazolium methosulfate and is available, for example, under the name Luviquat® Hold from BASF SE. Polyquaternium-46 is preferably used in an amount of 1 to 5% by weight, based on the total weight of the cosmetic composition. It is very particularly preferred that Polyquaternium-46 is used in combination with a cationic guar compound. It is even highly preferred that Polyquaternium-46 is used in combination with a cationic guar compound and Polyquaternium-11.

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

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

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

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

Preferred polymers of the poly (meth) arylamido-C1-C4-alkyl-sulfonic acids are crosslinked and at least 90% neutralized. These polymers can be crosslinked or also uncrosslinked. Crosslinked and completely or partially neutralized polymers of the poly-2-acrylamido-2-methylpropanesulfonic acid type are known under the INCI names "Ammonium Polyacrylamido-2-methylpropanesulphonate" or "Ammonium Polyacryldimethyltauramide".

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

In a further explicitly very particularly preferred embodiment, a method is characterized in that the agent (b) contains at least one anionic, film-forming polymer (b2).

In this context, the best results could be obtained when the agent (b) contains at least one film-forming polymer (b2) which comprises at least one structural unit of the formula (P-I) and at least one structural unit of the formula (P-II) in which

M stands for a hydrogen atom or for ammonium (NH4), sodium, potassium, 14 magnesium or 14 calcium.

In a further preferred embodiment, a method is characterized in that the agent (b) contains at least one film-forming polymer (b2) which comprises at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II) in which

M stands for a hydrogen atom or for ammonium (NH4), sodium, potassium, 1 magnesium or 1 calcium.

If M stands for a hydrogen atom, the structural unit of the formula (P1) 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.

When M stands for a sodium counterion, the structural unit of the formula (P-1) is based on the sodium salt of acrylic acid.

If M stands for a potassium counterion, the structural unit of the formula (P-1) is based on the potassium salt of acrylic acid.

When M stands for half an equivalent of a magnesium counterion, the structural unit of the formula (P-1) is based on the magnesium salt of acrylic acid.

When M stands for half an equivalent of a calcium counterion, the structural unit of the formula (P-1) is based on the calcium salt of acrylic acid.

The film-forming polymer (s) (b2) are preferably used in certain quantity ranges in the agent (b). In this context, it has proven to be particularly preferred to solve the problem according to the invention if the agent (b) - based on the total weight of the agent (b) - has one or more film-forming polymers (b2) in a total amount of 0.1 to 18 % By weight, preferably from 1 to 16% by weight, more preferably from 5 to 14.5% by weight and very particularly preferably from 8 to 12% by weight.

In a further preferred embodiment, a method is characterized in that the agent (b) - based on the total weight of the agent (b) - prefers one or more film-forming polymers (b2) in a total amount of 0.1 to 18% by weight from 1 to 16% by weight, more preferably from 5 to 14.5% by weight and very particularly preferably from 8 to 12% by weight.

Further ingredients in means (a) and (b)

The means (a) and (b) described above can also contain one or more optional ingredients.

It is particularly preferred that the agent (a) used in the coloring process comprises at least one coloring compound (a2) selected from the group of pigments and / or substantive dyes.

The use of pigments has proven to be very particularly preferred in this context.

In a further very particularly preferred embodiment, a method is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of pigments.

Pigments in the context of the present invention are understood to mean coloring compounds which, at 25 ° C., have a solubility in water of less than 0.5 g / l, preferably of less than 0.1 g / L, even more preferably less than 0.05 g / L. The water solubility can be achieved, for example, 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 visually assessed 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 pigments can be of inorganic and / or organic origin.

In a preferred embodiment, a method is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of inorganic and / or organic pigments.

Preferred pigments are selected from synthetic or natural inorganic pigments. Inorganic 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 pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI77289 ), Iron blue (Ferric Ferrocyanide, CI77510) and / or carmine (Cochineal).

Colored pearlescent pigments are also particularly preferred pigments. These are usually based on 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.

Accordingly, a preferred method is characterized in that the agent (a) contains at least one coloring compound (a2) 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 based on colored pigments of natural mica coated with at least one metal oxide and / or a metal oxychloride.

In a further preferred embodiment, the method is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of pigments, which is selected from pigments based on natural mica 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.

Further suitable pigments are based on metal oxide-coated platelet-shaped borosilicates. These are coated, for example, with tin oxide, iron oxide (s), silicon dioxide and / or titanium dioxide. Such borosilicate-based pigments are available, for example, under the name MIRAGE from Eckart or Reflecks from BASF SE.

Examples of particularly suitable 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, Flamenco®, Cellini®, Cloisonne®, Duocrome®, Gemtone®, Timica®, MultiReflections, Chione are available from BASF SE and Sunshine® from Sunstar.

Very particularly preferred pigments with the trade name Colorona® are, for example: Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

Colorona Passion Orange, Merck, Mica, CI 77491 (Iran 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 DIOXIDES) 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 (Iran 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 (Iran oxides), Mica, CI 77891 (Titanium dioxide)

Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iran oxides)

Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

Colorona SynCopper, Merck, Synthetic Fluorphlogopite (and) Iran Oxides Colorona SynBronze, Merck, Synthetic Fluorphlogopite (and) Iran Oxides

Other particularly preferred 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.

Xirona Le Rouge, Merck, Iran Oxides (and) Silica

In addition, particularly preferred pigments with the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI 77491 (Iran Oxides), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iran Oxides), Silica Unipure Yellow LC 182 EM, Sensient , CI 77492 (Iran Oxides), Silica

Pigments with the trade name Flamenco® are also particularly preferred:

Flamenco® Summit Turquoise T30D, BASF, Titanium Dioxide (and) Mica Flamenco® Super Violet 530Z, BASF, Mica (and) Titanium Dioxide In a further embodiment, the agent (a) used in the process can also contain one or more coloring compounds (a2) from the group of organic pigments.

The organic pigments 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, the method is characterized in that the agent (a) contains at least one coloring compound (a2) from the group of organic pigments, which is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum and 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,

73915, CI 75470 and mixtures thereof.

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

The alizarin color varnish, for example, can be used as the color varnish. Likewise suitable coloring compounds (a2) from the group of the pigments are inorganic and / or organic pigments which have been modified with a polymer. The polymer modification can, for example, increase the affinity of the pigments for the respective material of the at least one layer.

Further effect pigments can also be used as further coloring compounds (a2).

The further effect pigments can contain, for example, pigments based on a lamellar substrate platelet, pigments based on lenticular substrate platelets, pigments based on substrate platelets which comprise “vacuum metallized pigments” (VMP). In these effect pigments, the substrate platelets comprise a metal, preferably aluminum, or an alloy. Metal substrate platelet-based effect pigments preferably have a coating which, inter alia, acts as a protective layer.

Suitable effect pigments include, for example, the pigments Alegrace® Marvelous, Alegrace® Gorgeous or Alegrace® Aurous from Schlenk Metallic Pigments.

Also suitable effect pigments are the aluminum-based pigments of the SILVERDREAM series as well as the pigments of the VISIONAIRE series from Eckart based on aluminum or on copper / zinc-containing metal alloys.

Further suitable effect pigments are based on metal oxide-coated platelet-shaped borosilicates. These are coated, for example, with tin oxide, iron oxide (s), silicon dioxide and / or titanium dioxide. Such borosilicate-based pigments are available, for example, under the name MIRAGE from Eckart or Reflecks from BASF SE.

In a further embodiment of the process, the agent (a) can also contain one or more coloring compounds from the group of organic pigments.

In a further particularly preferred embodiment, a method is characterized in that the agent (a) contains at least one coloring compound (a2) 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. Because of their excellent light and temperature stability, the use of the aforementioned pigments in the agent (a) 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 D50 of 1 to 50 μm, preferably 5 to 45 μm, more preferably 10 to 40 μm, in particular 14 to 30 μm. The mean particle size D50 can be determined using dynamic light scattering (DLS), for example.

In a further preferred embodiment, the method is characterized in that the agent (a) - based on the total weight of the agent (a) - one or more coloring compound (s) (a2) in the form of pigments in a total amount of 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, more preferably from 0.2 to 6% by weight and very particularly preferably from 0.5 to 4.5% by weight.

The agents (a) used in the process can also contain one or more substantive dyes as coloring compound (s) (a2). 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 g / l.

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

In a further preferred embodiment, the method is characterized in that the agent (a) also contains at least one anionic, cationic and / or nonionic substantive dye as coloring compound (a2).

In a further preferred embodiment, the method is characterized in that the agent (a) furthermore contains at least one coloring compound (a2) 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 e and 2-chloro-6-ethylamino-4-nitrophenol.

In the course of the work leading to this invention it has been found that, in particular with agents (a) which contain at least one anionic substantive dye, dyeings with particularly high color intensity can be produced.

In an explicitly very particularly preferred embodiment, the process is therefore characterized in that the agent (a) also contains at least one anionic substantive dye as the coloring compound (a2).

Anionic substantive dyes are also referred to as acid dyes. Acid dyes are understood to mean substantive dyes which have at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H). Depending on the pH, the protonated forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups are in equilibrium ^{with their deprotonated forms (-COO-, -S03 _).} 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. The acid dyes 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 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 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 are 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.

In the context of one embodiment, a method for coloring keratinic material is therefore preferred, which is characterized in that the agent (a) furthermore contains at least one anionic substantive dye as coloring compound (a2), which is selected from the group of nitrophenylenediamines, the Nitroaminophenols, the azo dyes, the anthraquinone dyes, the triarylmethane dyes, the xanthene dyes, the rhodamine dyes, the oxazine dyes and / or the indophenol dyes, the dyes from the aforementioned group each having at least one carboxylic acid group (-COOH), one sodium carboxylate group (-COONa) , a potassium carboxylate group (-COOK), a sulfonic acid group (-SO3H), a sodium sulfonate group (-SOsNa) and / or a potassium sulfonate group (-SO3K).

One or more compounds from the following group can be selected as particularly suitable acid dyes: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n ° B001), Acid Yellow 3 (COLIPA n °: C 54, D&C Yellow N ° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n ° C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA n ° C015), Acid Orange 10 (Cl 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1; CI 20170; KATSU201; nosodiumsalt; Brown No.201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D & C Brown No.1), Acid Red 14 (CI14720), acid red 18 (E124, red 18; CI 16255), Acid Red 27 (E 123, CI 16185, C-Red 46, Echtrot D, FD&C Red Nr.2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CI Cl18065), 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, Cl 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 Blue 9 (E 133, Patent Blue AE, Amido Blue AE, Erioglaucin A, CI 42090, Cl 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, Foodgreenl), 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, Cl 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n ° 401, Naphthalene Black 10B, Amido Black 10B, CI 20470, COLIPA n ° B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1.

The water solubility of the anionic substantive dyes can be determined, for example, in the following way. 0.1 g of the anionic substantive dye are placed in a beaker. A stir bar is added. Then 100 ml of water are added. This mixture is heated to 25 ° C. on a magnetic stirrer while stirring. It is stirred for 60 minutes. The aqueous mixture is then assessed visually. If there are still undissolved residues, the amount of water is increased - for example in steps of 10 ml. Water is added until the amount of dye used has completely dissolved. If the dye-water mixture cannot be assessed visually due to the high intensity of the dye, the mixture is filtered. If a portion of undissolved dyes remains on the filter paper, the solubility test is repeated with a larger amount of water. If 0.1 g of the anionic substantive dye dissolves in 100 ml of water at 25 ° C., the solubility of the dye is 1 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 disulfonic 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 trisodium 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 disodium 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).

A particularly preferred method is therefore characterized in that the agent (a) contains at least one first coloring compound (a2) from the group of anionic substantive dyes, which is selected from the group of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43 , Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11 , D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1.

The substantive dyestuff or dyes, in particular the anionic substantive dyestuffs, can be used in various amounts in the means (a) depending on the desired color intensity. Particularly good results could be obtained if the agent (a) - based on its total weight - has one or more substantive dyes (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight. -%, more preferably from 0.2 to 6% by weight and very particularly preferably from 0.5 to 4.5% by weight.

In a further preferred embodiment, the method is characterized in that the agent (a) - based on the total weight of the agent (a) - also has one or more substantive dyes as the coloring compound (a2) in a total amount of 0.01 to 10 wt %, preferably from 0.1 to 8% by weight, more preferably from 0.2 to 6% by weight and very particularly preferably from 0.5 to 4.5% by weight.

The agents can additionally contain one or more surfactants. The term surfactants is understood to mean surface-active substances. A distinction is made between anionic surfactants consisting of a hydrophobic residue and a negatively charged hydrophilic head group, amphoteric surfactants, which carry both a negative and a compensating positive charge, cationic surfactants, which have a positively charged hydrophilic group in addition to a hydrophobic residue, and nonionic surfactants, which have no charges but rather strong dipole moments and are strongly hydrated in aqueous solution.

Zwitterionic surfactants are surface-active compounds which have at least one quaternary ammonium group and at least one -COO <-> - or -S0 ₃ ⁽⁾ - group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example coconut alkyl dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines, each with 8 to 18 carbon atoms in the alkyl or acyl group, and that

Cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a Cs-C24 -alkyl or -acyl group, contain at least one free amino group and at least one —COOH or —SOsH group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 24 C. Atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12-Cis -acylsarcosine.

The agents can also additionally contain at least one nonionic surfactant. Suitable nonionic surfactants are alkyl polyglycosides and alkylene oxide addition products with fatty alcohols and fatty acids with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with good properties are also obtained if, as nonionic surfactants, they contain fatty acid esters of ethoxylated glycerol which have been reacted with at least 2 moles of ethylene oxide.

Furthermore, the agents can also contain at least one cationic surfactant. Cationic surfactants are understood as meaning surfactants, that is to say surface-active compounds, each with one or more positive charges. Cationic surfactants only contain positive charges. These surfactants are usually made up of a hydrophobic part and a hydrophilic head group, the hydrophobic part usually consisting of a hydrocarbon structure (e.g. consisting of one or two linear or branched alkyl chains), and the positive charge (s) are located in the hydrophilic head group. Examples of cationic surfactants are

- Quaternary ammonium compounds which can carry one or two alkyl chains with a chain length of 8 to 28 carbon atoms as hydrophobic radicals,

- Quaternary phosphonium salts, substituted with one or more alkyl chains with a chain length of 8 to 28 carbon atoms or

- tertiary sulfonium salts. Furthermore, the cationic charge can also be part of a heterocyclic ring (for example an imidazolium ring or a pyridinium ring) in the form of an onium structure. In addition to the functional unit that carries the cationic charge, the cationic surfactant can also contain other uncharged functional groups, as is the case, for example, with ester quats. The cationic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 1 to 15% by weight, based on the total weight of the respective agent.

Furthermore, the agents can also contain at least one anionic surfactant. Anionic surfactants are surface-active agents with exclusively anionic charges (neutralized by a corresponding counter cation). Examples of anionic surfactants are fatty acids, alkyl sulfates, alkyl ether sulfates and ether carboxylic acids with 12 to 20 carbon atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

The anionic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight and very particularly preferably 1 to 15% by weight, based on the total weight of the agent in question.

To set the desired pH, the agents (a) and (b) can also contain at least one alkalizing agent and / or acidifying agent. The pH values in the context of the present invention are pH values that were measured at a temperature of 22 ° C.

The alkalizing agents (a) and (b) can contain, for example, ammonia, alkanolamines and / or basic amino acids.

The alkanolamines that can be used in the agents are preferably selected from primary amines with a C2-C6-alkyl parent structure which carries at least one hydroxyl group. Preferred alkanolamines are selected from the group which is formed from 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropane -2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1 - Amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol.

Particularly preferred alkanolamines are selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol. A particularly preferred embodiment is therefore characterized in that an agent (a) and / or (b) contains an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol as the alkalizing agent.

An amino acid in the context of the invention is an organic compound which in its structure contains at least one protonatable amino group and at least one —COOH or one —SOsH group. Preferred amino acids are aminocarboxylic acids, especially a- (alpha) - Aminocarboxylic acids and w-aminocarboxylic acids, α-aminocarboxylic acids being particularly preferred.

According to the invention, basic amino acids are to be understood as meaning those amino acids which have an isoelectric point p1 of greater than 7.

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

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

In addition, agents (a) and / or (b) can contain further alkalizing agents, in particular inorganic alkalizing agents. Inorganic alkalizing agents which can be used are preferably selected from the group formed from sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

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

Acidifying agents familiar to the person skilled in the art are, for example, organic acids such as citric acid, acetic acid, maleic acid, lactic acid, malic acid or tartaric acid, and dilute mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.

The agent (a) and / or the agent (b) can also contain a matting agent. Suitable matting agents include, for example, (modified) starches, waxes, talc and / or (modified) silicas. The amount of matting agent is preferably between 0.1 and 10% by weight based on the total amount of agent (a) or agent (b). Agent (b) preferably contains a matting agent. The agents (a) and / or (b) can also contain other active ingredients, auxiliaries and additives, such as solvents, fatty components such as C8-C30 fatty acid triglycerides, C8-C30 fatty acid monoglycerides, C8-C3o -Fatty acid diglycerides and / or the hydrocarbons; Polymers; Structurants such as glucose or sodium chloride, hair conditioning compounds such as phospholipids, for example lecithin and cephalins; Perfume oils, dimethyl isosorbide and cyclodextrins; fiber structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fruit sugar and lactose; Dyes for coloring the agent; Anti-dandruff ingredients such as Piroctone Olamine, Zinc Omadine and Climbazole; Amino acids and oligopeptides; Protein hydrolysates based on animals and / or plants, and in the form of their fatty acid condensation products or optionally anionically or cationically modified derivatives; vegetable oils; Sunscreens and UV blockers; Active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acids and their salts and bisabolol; Polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols; Ceramides or pseudoceramides; Vitamins, provitamins and vitamin precursors; Plant extracts; Fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; Swelling and penetration substances such as glycerine, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates; Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers; Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; as well as propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

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. The additional active ingredients and auxiliaries are preferably used in agents (a) and / or (b) in amounts of from 0.0001 to 25% by weight, in particular from 0.0005 to 15% by weight, based on the total weight of the respective agent.

Process for coloring keratinic materials

In the context of the method, agents (a) and (b) are applied to the keratinic materials, in particular to human hair. Thus, means (a) and (b) are the means ready for use. The means (a) and (b) are different from each other.

The means (a) and (b) can in principle be applied simultaneously or successively, with successive application being preferred.

The best results could be obtained when the agent (a) was added to the keratinic materials as a pretreatment agent and then the agent (b) was applied as a coloring agent. A method for coloring keratinic material, in particular human hair, is therefore very particularly preferred, comprising the following steps in the order given:

- In a first step, using an agent (a) on the keratinous material, the agent (a) containing at least one organic silicon compound (a1), and

- In a second step, application of an agent (b) on the keratinic material, the agent (b) containing:

(b1) at least one coloring compound, comprising at least one effect pigment, comprising a) a substrate platelet comprising synthetic mica, and ß) a coating comprising at least one first metal oxide (hydrate) layer, and (b2) at least one film-forming polymer.

In order to give the colored keratinic material a high resistance to washout over a longer period of time, the agents (a) and (b) are also particularly preferably used within one and the same dyeing process, which means that between the application of the agents (a) and ( b) there is a period of a maximum of a few hours.

In a further preferred embodiment, the method is characterized in that the agent (a) is applied first and then the agent (b) is applied, the period between the application of the agents (a) and (b) being a maximum of 24 hours , preferably a maximum of 12 hours and particularly preferably a maximum of 6 hours.

As part of the process, the keratinic materials, in particular the human hair, are first treated with agent (a).

The pretreatment agent (a) is characterized by its content of at least one reactive organic silicon compound. The reactive organic silicon compound (s) (a1) functionalize the hair surface as soon as they come into contact with it. In this way, a first film is formed. In the second step of the process, a coloring agent (b) is then applied to the hair. During the application of the coloring agent (b), the coloring compounds interact with the film formed by the organosilicon compounds and are bound in this way to the keratinic materials.

In a particularly preferred embodiment of the process, the agent (a) contains, in addition to the reactive organic silicon compound (s) (a1), a coloring compound (a2). In this way, upon contact with the keratin material, a first colored film is formed on the keratin material. In the second step of the method, agent (b) is applied to the keratinic material, which comprises an effect pigment as a coloring compound (b1). During the application of the agent (b), the coloring compounds (b1) interact with that formed by the organosilicon compounds (a1) and with the coloring compounds (a2) colored film. The coloring compounds (b1) are bound in this way to the keratinic material and, together with the coloring compounds (a2), produce particularly intense and resistant color effects.

In a further embodiment, a method comprising the following steps in the specified order is very particularly preferred

(1) Application of the agent (a) on the keratin material,

(2) Allowing agent (a) to act for a period of 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes,

(3) if necessary, rinsing the keratinous material with water,

(4) Application of the agent (b) on the keratinic material,

(5) allowing the agent (b) to act for a period of from 30 seconds to 30 minutes, preferably from 30 seconds to 10 minutes, and

(6) Rinse the keratinous material with water.

Rinsing out the keratinic 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 means other than means (a) and (b) would be used.

In a step (1), the agent (a) is first applied to the keratinic materials, in particular the human hair.

After application, the agent (a) is allowed to act on the keratinic 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 keratinic materials, in particular on human hair, have proven to be particularly advantageous.

In a preferred embodiment of the method, the agent (a) can now be rinsed out of the keratinic materials before the agent (b) is applied to the hair in the subsequent step.

Dyeings with likewise good wash fastness properties were obtained when the agent (b) was applied to the keratinic materials to which the agent (a) was still applied.

In step (4), the agent (b) is now applied to the keratinic materials. After application, the agent (b) is now allowed to act on the hair.

Even if the agent (b) is left to act for a short time, the process allows dyeings to be produced with particularly good intensity and washfastness. Contact times from 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes and very particularly preferably from 30 seconds to 3 minutes Minutes on the keratinic materials, especially on human hair, have proven particularly beneficial.

In step (6), the agent (b) (and any agent (a) that is still present) is then rinsed out of the keratinic material with water.

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

As part of the process, means (a) and (b) are applied to the keratinic materials, i.e. the two means (a) and (b) are each the ready-to-use means.

In order to increase the user comfort, all the necessary means are preferably made available to the user in the form of a multi-component packaging unit (kit-of-parts).

A second subject of the present invention is therefore a multi-component packaging unit (kit-of-parts) for coloring keratinic material, comprehensively packaged separately from one another

- A first container with a means (a), the means (a) containing at least one organic silicon compound (a1), and

- a second container with a means (b), the means (b) containing:

The organic silicon compounds contained in the middle (a) of the kit correspond to the organic silicon compounds which were also used in the middle (a) of the method described above.

The coloring compounds from the group of effect pigments contained in the agent (b) of the kit, comprising a) a substrate platelet comprising synthetic mica, and β) a coating comprising at least one first metal oxide (hydrate) layer, correspond to the coloring compounds from the group the effect pigments, comprising a) a substrate platelet comprising synthetic mica, and β) a coating comprising at least one first metal oxide (hydrate) layer, which was also used in means (b) of the method described above.

The agent (a) contains with the organic silicon compound or compounds a class of reactive compounds which, as described above, can undergo hydrolysis and / or oligomerization and / or polymerization in the presence of water. As a result of their high reactivity, these organic silicon compounds form a film on the keratinous material. In order to avoid premature hydrolysis, oligomerization and / or polymerization, it can be preferred that the ready-to-use agent (a) be prepared shortly before use.

In the context of a further embodiment, a multi-component packaging unit (kit-of-parts) for coloring keratinic material is packaged comprehensively separately from one another

- A first container with a means (a ‘), the means (a‘) containing at least one organic silicon compound,

- a second container with an agent (a “), the agent (a“) containing water, and

- a third container with a means (b), the means (b) containing:

In order to be able to provide a formulation that is as stable as possible in storage, the agent (a ‘) itself is preferably formulated with a low water content or anhydrous.

In a preferred embodiment, a multi-component packaging unit (kit-of-parts) is characterized in that the agent (a ') - based on the total weight of the agent (a') - preferably has a water content of less than 10% by weight of less than 5% by weight, more preferably of less than 1% by weight, even more preferably of less than 0.1% by weight and very particularly preferably of less than 0.01% by weight.

The agent (a “) contains water. In a preferred embodiment, a multi-component packaging unit (kit-of-parts) is characterized in that the agent (a ") - based on the total weight of the agent (a") - has a water content of 15 to 100% by weight, preferably 35 to 100% by weight, more preferably from 55 to 100% by weight, even more preferably from 65 to 100% by weight and very particularly preferably from 75 to 100% by weight.

Within this embodiment, the ready-to-use agent (a) is now produced by mixing the agents (a ‘) and (a“).

For example, the user can first stir or spill the agent (a ‘) which contains the organic silicon compound (s) with the water-containing agent (a“). This mixture of (a ‘) and (a“) can now be applied to the keratinic materials by the user - either directly after its preparation or after a short reaction time of 10 seconds to 20 minutes. Subsequently, the user can apply the means (b) as described above.

In this embodiment of the multicomponent packaging unit, it can be preferred that the agent (a ”) also contains at least one coloring compound (a2). This is preferable 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 colored pigments based on natural mica which are coated with at least one metal oxide and / or a metal oxychloride.

- A second container with an agent (a “), the agent (a“) containing water and at least one coloring compound (a2), and

- a third container with a means (b), the means (b) containing:

Alternatively, the multi-component packaging unit can furthermore comprise an agent (a ”‘) which contains at least one coloring compound (a2).

Within this embodiment, the ready-to-use agent (a) is now produced by mixing the agents (a ‘), (a“) and (a “‘). The agent (a ”‘) preferably also contains a solvent.

It can furthermore be preferred to also produce the ready-to-use agent (b) shortly before use. In a further advantageous embodiment, the ready-to-use agent (b) is produced by mixing an agent (b ‘) and an agent (b ″).

- a second container with an agent (a "), the agent (a") containing water,

- A third container with a means (b ‘), the means (b) containing:

(b1) at least one coloring compound, comprising at least one effect pigment, comprising a) a substrate platelet comprising synthetic mica, and ß) a coating comprising at least one first metal oxide (hydrate) layer, and ^'

- a fourth container with a means (b "), the means (b") containing:

(b2) at least one film-forming polymer. With regard to the further preferred embodiments of the multi-component packaging unit, what has been said about the method applies mutatis mutantis.

Examples

1. Formulations

The following formulations were prepared (unless otherwise stated, all data are in% by weight)

The silanes were mixed with some of the water, this mixture was allowed to stand for 30 minutes. The pH was then adjusted to the desired value by adding citric acid / ammonia. It was then made up to 100 g with water.

2. Application

One strand of hair in each case (Kerling, European natural hair, white) was dipped into the agent (a) and left in it for 1 minute. Thereafter, excess agent (a) was stripped from each strand of hair. Each strand of hair was briefly washed out with water. Excess water was wiped off each strand of hair.

Subsequently, the strands of hair were each dipped into the agent (b) and left in it for 1 minute. Thereafter, excess agent (b) was stripped from each strand of hair. Each strand of hair was briefly washed out with water. Excess water was wiped off each strand of hair.

The tresses were then assessed visually.

Claims

1. A method for coloring keratinic material, in particular human hair, comprising the following steps:

Application of an agent (a) to the keratinous material, the agent (a) containing: (a1) at least one organic silicon compound, and

Application of an agent (b) to the keratinous material, the agent (b) comprising: (b1) at least one coloring compound comprising at least one effect pigment comprising a) a substrate platelet comprising synthetic mica, and β) a coating comprising at least one first metal oxide (hydrate) layer, and

(b2) at least one film-forming polymer.

2. The method according to claim 1, characterized in that the agent (a) contains at least one organic silicon compound which is selected from silanes having one, two or three silicon atoms, the organic silicon compound preferably having one or more basic chemical functions and one or more Includes hydroxyl groups or hydrolyzable groups per molecule.

3. The method according to any one of claims 1 to 2, characterized in that the agent (a) contains at least one organic silicon compound of the formula (I) and / or (II)

RiR ₂ NL-Si (OR ₃ ) a (R4) b (I), where

Ri, R2 independently represent a hydrogen atom or a Ci-C6-alkyl group,

L stands for a linear or branched, divalent Ci-C2o-alkylene group,

R3 represents a hydrogen atom or a Ci-C6-alkyl group,

R4 stands for a Ci-C6-alkyl group, a stands for an integer from 1 to 3, and b stands for the integer 3 - a, and where in the organic silicon compound of the formula (II)

(R50) c (R6) dSi- (A) e- [NR7- (A ')] ^ [0- (A ”)] g- [NR8- (A”')] h-Si (R6 ^, ) d (OR5 ^, ) c (II),

- R5, R5 ‘, R5“ independently represent a hydrogen atom or a Ci-C6-alkyl group,

- R6, R6 ‘and R6“ independently represent a Ci-C6-alkyl group,

A, A ', A “, A“' and A ““ stand independently of one another for a linear or branched, divalent Ci-C2o-alkylene group, R7 and Re independently represent a hydrogen atom, a Ci-C6-alkyl group, a hydroxy-Ci-C6-alkyl group, a C2-C6-alkenyl group, an amino-Ci-C6-alkyl group or a grouping of the formula (III) stand

- (A ““) - Si (R6 “) d“ (OR ₅ “) c“ (III),

- c, stands for an integer from 1 to 3,

- d stands for the integer 3 - c,

- c ‘stands for an integer from 1 to 3,

- d ‘stands for the integer 3 - c‘,

- c "stands for an integer from 1 to 3,

- d "stands for the whole number 3 - c" stands,

- e stands for 0 or 1,

- f stands for 0 or 1,

- g stands for 0 or 1,

- h stands for 0 or 1, with the proviso that at least one of the radicals from e, f, g and h is different from 0.

4. The method according to any one of claims 1 to 3, characterized in that the agent (a) contains at least one organic silicon compound of the formula (I),

RiR ₂ NL-Si (OR ₃ ) a (R4) b (I), where

- Ri, R2 both stand for a hydrogen atom, and

- L stands for a linear, divalent Ci-C6-alkylene group, preferably for a propylene group (-CH2-CH2-CH2-) or for an ethylene group (-CH2-CH2-),

- R3 stands for a hydrogen atom, an ethyl group or a methyl group,

- R4 stands for a methyl group or for an ethyl group,

- a stands for the number 3 and

- b stands for the number 0.

5. The method according to any one of claims 1 to 4, characterized in that the agent (a) contains at least one organic silicon compound of the formula (I) which is selected from the group consisting of

- (3-aminopropyl) triethoxysilane

- (3-aminopropyl) trimethoxysilane

- 1- (3-aminopropyl) silanetriol

- (2-aminoethyl) triethoxysilane

- (2-aminoethyl) trimethoxysilane

- 1- (2-aminoethyl) silanetriol

- (3-Dimethylaminopropyl) triethoxysilane

- (2-Dimethylaminoethyl) triethoxysilane.

- (2-dimethylaminoethyl) trimethoxysilane,

- 1- (2-dimethylaminoethyl) silanetriol and

- Mixtures of it.

6. Agent according to one of claims 1 to 5, characterized in that the agent (a) contains at least one organic silicon compound of the formula (II),

- e and f both stand for the number 1,

- g and h both stand for the number 0,

- A and A ‘independently represent a linear, divalent Ci-C6-alkylene group and

7. Agent according to one of claims 1 to 6, characterized in that it (a) contains at least one organic silicon compound of the formula (II) which is selected from the group consisting of

- 3- (Trimethoxysilyl) -N- [3- (trimethoxysilyl) propyl] -1-propanamine

- 3- (Triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine

- N-methyl-3- (triethoxysilyl) -N- [3- (triethoxysilyl) propyl] -1-propanamine

- 2- [bis [3- (trimethoxysilyl) propyl] amino] ethanol

- 2- [bis [3- (triethoxysilyl) propyl] amino] ethanol

- 3- (Trimethoxysilyl) -N, N-bis [3- (trimethoxysilyl) propyl] -1-propanamine

- 3- (Triethoxysilyl) -N, N-bis [3- (triethoxysilyl) propyl] -1-propanamine

- N1, N1-bis [3- (trimethoxysilyl) propyl] -1, 2-ethanediamine,

- N1, N1-bis [3- (triethoxysilyl) propyl] -1, 2-ethanediamine,

- N, N-bis [3- (trimethoxysilyl) propyl] -2-propen-1-amine,

- N, N-bis [3- (triethoxysilyl) propyl] -2-propen-1-amine and

- Mixtures of it.

8. The method according to any one of claims 1 to 7, characterized in that the agent (a) contains at least one organic silicon compound of the formula (IV).

R ₉ Si (ORio) k (Rn) m (IV), where

- Rg stands for a Ci-Ci8-alkyl group,

- Rio stands for a hydrogen atom or a Ci-C6-alkyl group, - R11 stands for a Ci-C6-alkyl group

- k stands for an integer from 1 to 3, and

- m stands for the integer 3 - k.

9. The method according to any one of claims 1 to 8, characterized in that the agent (a) contains at least one organic silicon compound of the formula (IV) which is selected from the group consisting of

- methyltrimethoxysilane

- methyltriethoxysilane

- ethyltrimethoxysilane

- ethyltriethoxysilane

- propyltrimethoxysilane

- propyltriethoxysilane

- hexyltrimethoxysilane

- hexyltriethoxysilane

- Octyltrimethoxysilane

- octyltriethoxysilane

- dodecyltrimethoxysilane,

- dodecyltriethoxysilane,

- octadecyltrimethoxysilane,

- Octadecyltriethoxysilane and

- Mixtures of it.

10. The method according to any one of claims 1 to 9, characterized in that the first metal oxide (hydrate) layer comprises titanium dioxide (TiC> 2).

11. The method according to any one of claims 1 to 10, characterized in that the coating further comprises a second metal oxide (hydrate) layer.

12. The method according to claim 11, characterized in that the second metal oxide (hydrate) layer is a metal oxide (hydrate) selected from the group consisting of tin oxide (Sn02), silicon oxide (Si02), aluminum oxide (Al2O3), iron oxide (Fe203 and / or Fe304) and mixtures thereof.

13. The method according to any one of claims 1 to 12, characterized in that the method according to claim 11 or 12, characterized in that the second metal oxide (hydrate) layer comprises tin oxide (Sn02).

14. The method according to any one of claims 1 to 13, characterized in that the agent (a) further contains at least one coloring compound (a2), 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 coated with at least one metal oxide and / or a metal oxychloride.

15. Multi-component packaging unit (kit-of-parts) for coloring keratinic material, comprehensively packaged separately from one another

- A first container with a means (a), the means (a) at least one organic silicon compound (a1) and, optionally, at least one coloring compound (a2),

- a second container with a means (b), the means (b) containing:

- (b1) at least one coloring compound, comprising at least one effect pigment, comprising a) a substrate platelet comprising synthetic mica, and ß) a coating comprising at least one first metal oxide (hydrate) layer, and

(b2) at least one film-forming polymer.