Method for coloring keratinous materials comprising using an organosilicon compound, a colored effect pigment, and a sealant I

Abstract

The present invention relates to a method for dyeing keratinous materials, in particular human hair, comprising the following steps: - applying to the keratinous materials an agent (a) comprising at least one organosilicon compound (a1) selected from the group consisting of silanes containing 1, 2 or 3 silicon atoms, and at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer comprising a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments; and - applying to the keratinous materials an agent (b) comprising at least one sealant (b1).

Description

[Technical field]

[0001] The subject of the present invention is a method for treating keratinous materials, in particular human hair, which comprises the application of two agents (a) and (b). Agent (a) is characterized in that it contains at least one organosilicon compound (a1) and at least one selected coloring compound (a2). Agent (b) contains at least one sealant.

[0002] Another subject of the present invention is a multi-component packaging unit (kit) for dyeing keratinous materials, in particular human hair, comprising at least three separately prepared agents (a'), (a") and (b). To prepare agent (a) used in the above-mentioned method, agents (a') and (a") can be used. [Background technology]

[0003] Changing the shape and color of keratin fibers, especially hair, is an important area of ​​modern cosmetics. To change the color of hair, experts know a wide variety of coloring systems depending on the coloring requirements. For long-lasting, intense dyeing with good fastness properties and good gray hair coverage, oxidation dyes are usually used. Such dyes contain an oxidation dye precursor (the so-called developer component) and a color-developing component, which, under the influence of an oxidizing agent such as hydrogen peroxide, react with each other to produce the actual dye. Oxidation dyes are characterized by a very long-lasting dyeing result.

[0004] When using direct dyes, the already prepared dye diffuses from the coloring agent into the hair fiber. Compared to oxidative dyes, dyes obtained with direct dyes have a shorter color retention time and are more quickly washable. Staining with direct dyes usually remains on the hair for 5 to 20 washes.

[0005] The use of color pigments is known to change the color of hair and / or skin for a short period of time. Color pigments are understood to be insoluble coloring substances. They are present in the dye composition undissolved as small particles and are exclusively attached externally to the hair fiber and / or skin surface. Therefore, they can usually be removed without residue after several washes with detergents containing surfactants. This type of product is available in various versions under the name "hair mascara" on the market.

[0006] If users want a particularly long-lasting dye, they have had no choice but to use oxidative dyes up until now. However, despite many optimization attempts, the unpleasant odor of ammonia or amines cannot be completely avoided in oxidative dyes. In addition, the damage to hair caused by the use of oxidative dyes also has a negative effect on the user's hair.

[0007] EP 2168633 B1 deals with a method for producing long-lasting pigmented hair color, teaching that a combination of pigments, organosilicon compounds, film-forming polymers and solvents can be applied to the hair to produce colorings that are particularly resistant to shampooing.

[0008] Metallic luster pigments or metal effect pigments are widely used in many technical fields. They are used, for example, in the preparation of color coatings, printing inks, inks, plastics, glass, ceramic products, and decorative cosmetics such as nail polish. They are characterized by an attractive, angle-dependent color impression (goniochromism) and a metallic-looking luster.

[0009] Hair with a metallic finish or metallic highlights is in fashion. Metallic tones make hair look fuller and lustrous. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] EP 2168633 B1 Summary of the Invention [Problem to be solved by the invention]

[0011] It is desirable to provide effect pigment-containing hair dyes that, on the one hand, have high washability and rubbing fastness, and, on the other hand, do not adversely affect hair properties such as manageability and feel.For this purpose, it is desirable that the effect pigments used have high covering power and can be applied to the hair in a thin layer.It is desirable to be able to color hair intensively and in many different shades with the help of effect pigments.

[0012] The object of the present invention is therefore to provide a coloring system containing effect pigments, which has fastness properties comparable to oxidative coloring.Although the washing fastness properties are excellent, the use of oxidative dye precursors, which are usually used for this purpose, must be avoided.For this purpose, the coloring system must be available in many different shades. [Means for solving the problem]

[0013] Surprisingly, it has been found that this problem can be successfully solved by coloring keratinous materials (especially human hair) by applying at least two agents (a) and (b) to keratinous materials (hair). Here, the first agent (a) contains at least one organosilicon compound selected from the group consisting of silanes having 1, 2 or 3 silicon atoms, and at least one selected coloring compound. In agent (a), the organosilicon compound and the coloring compound are prepared together. The second agent (b) contains at least one sealing agent.

[0014] The two agents (a) and (b) used in the dyeing process made it possible to dye keratinous materials with particularly high colour strength and high fastness properties.

[0015] The first object of the present invention is The following process: - applying to the keratin material an agent (a) comprising at least one organosilicon compound (a1) selected from the group consisting of silanes having 1, 2 or 3 silicon atoms and at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, and - applying an agent (b) comprising at least one sealant (b1) to the keratinous material; A method for dyeing keratinous materials, particularly human hair, comprising:

[0016] In the course of the investigations leading to the present invention, it has been found that the preferential sequential application of agents (a) and (b) allows the production of a very stable, wash-resistant coloring on keratinous materials.Without being limited to this theory, the present invention believes that the simultaneous application of the organosilicon compound (a1) and the color-imparting compound (a2) forms a particularly durable first film on keratinous materials.The first layer is sealed by the application of the second agent (b).For example, a film-forming polymer is deposited in the form of a further film on this first layer as a sealant (b1).

[0017] This special type of packaging, i.e. the simultaneous application of the silane (a1) and the color-imparting compound (a2) and the separate application of the sealant (b1), allows the film system thus produced to exhibit improved resistance to external influences: the coloring compound (a2) is thus fixed in the keratinous materials in the long term, and a very wash-resistant coloration with good resistance to shampooing can be obtained.

[0018] Also, depending on the structure of the effect pigment, depending on the coloring compound (ii) from the group of pigments used, different shades can be obtained on the dyed keratin hair, for example metallic colorings or colorings with a gloss effect. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Keratin Substances Keratinous materials include hair, skin, nails (e.g., fingernails and / or toenails). Wool, fur and feathers are also included within the definition of keratinous materials.

[0020] Preferably, keratinous materials are understood to be human hair, human skin and human nails (in particular fingernails and toenails). Keratinous materials are understood to be human hair.

[0021] Agents (a) and (b) In the method of the invention, the agents (a) and (b) are applied to keratinous materials, in particular human hair. The two agents (a) and (b) are different from each other.

[0022] In other words, a first object of the present invention is to provide a method for producing a process for the preparation of a pharmaceutical composition comprising the steps of: - applying to the keratin material an agent (a) comprising at least one organosilicon compound (a1) selected from the group consisting of silanes having 1, 2 or 3 silicon atoms and at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, and - applying an agent (b) comprising at least one sealant (b1) to the keratinous material; The present invention relates to a method for treating keratinous materials, particularly human hair, comprising the steps of:

[0023] Agent (a) Preferably, agent (a) comprises the essential components (a1) and (a2) of the present invention in a cosmetic carrier, particularly preferably in an aqueous or aqueous-alcoholic cosmetic carrier. This cosmetic carrier can be liquid, gel, or cream. Paste, solid, or powdery cosmetic carriers can also be used to prepare agent (a). In the case of hair treatments, particularly hair coloring, such carriers are, for example, creams, emulsions, gels, or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations, or other preparations suitable for application to hair.

[0024] Preferably, the cosmetic carrier contains at least 2% by weight of water, based on its weight. More preferably, the water content is more than 10% by weight, even more preferably more than 20% by weight, particularly preferably more than 40% by weight. The cosmetic carrier may be aqueous-alcoholic. The aqueous / alcoholic solution according to the invention is an aqueous solution containing 2-70% by weight of a C1-C4 alcohol, more preferably ethanol or isopropanol. The agent according to the invention may further contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. All water-soluble organic solvents are preferred.

[0025] Organosilicon compounds from the group of silanes (a1) As essential component (a1) of the invention, the agent (a) contains at least one organosilicon compound from the group of the silanes containing one, two or three silicon atoms.

[0026] Particularly preferably, the agent (a) comprises at least one organosilicon compound (a1) selected from silanes containing one, two or three silicon atoms, the organosilicon compound containing one or more hydroxyl and / or hydrolyzable groups per molecule.

[0027] These organosilicon compounds (a1) or organosilanes contained in agent (a) are reactive compounds.

[0028] Organosilicon compounds, also called organosilicon compounds, are compounds with silicon-carbon direct bonds (Si-C) or compounds in which carbon is bonded to silicon atoms via oxygen, nitrogen or sulfur atoms.The organosilicon compounds of the present invention are compounds containing 1-3 silicon atoms.The organosilicon compounds preferably contain 1 or 2 silicon atoms.

[0029] According to the IUPAC method, the term "silane" is a compound based on a silicon skeleton and hydrogen. In organosilanes, the hydrogen atoms are completely or partially replaced by organic groups such as (substituted) alkyl and / or alkoxy groups. In organosilanes, some of the hydrogen atoms may be replaced by hydroxy groups.

[0030] In a particularly preferred embodiment, the method is characterized in that the agent (a) comprises at least one organosilicon compound (a1) selected from silanes containing one, two or three silicon atoms, said organosilicon compound further comprising one or more hydroxyl or hydrolyzable groups per molecule, to the keratinous material.

[0031] In a very particularly preferred embodiment, the method is characterized in that an agent (a) is applied to the keratin materials, comprising at least one organosilicon compound (a1) selected from silanes containing one, two or three silicon atoms, said organosilicon compound further comprising one or more basic chemical functions and one or more hydroxyl or hydrolyzable groups per molecule.

[0032] The basic group or basic functional group may be, for example, an amino group, an alkylamino group, or a dialkylamino group, and is preferably bonded to the silicon atom via a linker. Preferably, the basic group is an amino group, a C1-C6 alkylamino group, or a di(C1-C6) alkylamino group.

[0033] The hydrolyzable group is preferably a C1-C6 alkoxy group, in particular an ethoxy group or a methoxy group. It is preferred that the hydrolyzable group is directly bonded to the silicon atom. For example, when the hydrolyzable group is an ethoxy group, the organosilicon compound preferably comprises the structural unit R'R"R"'Si-O-CH2-CH3. The groups R', R" and R"' represent the three remaining free valences of the silicon atom.

[0034] A very particularly preferred method is characterized in that the agent (a) contains at least one organosilicon compound selected from silanes having one, two or three silicon atoms and preferably having one or more hydroxyl or hydrolyzable groups and one or more basic chemical functions per molecule.

[0035] Particularly good results have been obtained when the agent (a) contains at least one organosilicon compound (a1) of the formula (I) and / or (II).

[0036] The compounds represented by formulas (I) and (II) are organosilicon compounds selected from silanes having one, two or three silicon atoms and containing one or more hydroxyl and / or hydrolyzable groups per molecule.

[0037] In another very particularly preferred embodiment, the method comprises applying an agent (a) to keratinous materials (or human hair), the agent (a) being a compound represented by the formula (I) and / or (II): Formula (I): R1R2N-L-Si(OR3) a (R4) b (I) [In the formula, -R1 and R2 each independently represent a hydrogen atom or a C1-C6 alkyl group; -L is a linear or branched divalent C1-C 20 is an alkylene group, -R3 is a hydrogen atom or a C1-C6 alkyl group; -R4 represents a C1-C6 alkyl group; -a represents an integer from 1 to 3; -b represents the integer 3-a] Formula (II): TIFF0007657770000001.tif6134[In the formula, -R5, R 5' , R 5" each independently represents a hydrogen atom or a C1-C6 alkyl group; -R6, R 6' and R 6" each independently represents a C1-C6 alkyl group; -A, A', A", A"' and A"" are independently straight or branched chain divalent C1-C 20 represents an alkylene group, - R7 and R8 are independently a hydrogen atom, a C1-C6 alkyl group, a hydroxy C1-C6 alkyl group, a C2-C6 alkenyl group, an amino C1-C6 alkyl group, or a group of formula (III): -(A"")-Si(R6") d" (OR5") c" (III) represents a group represented by -c represents an integer from 1 to 3, -d represents the integer 3-c, -c' represents an integer from 1 to 3, -d' represents the integer 3-c', -c" represents an integer from 1 to 3, -d" represents the integer 3-c", -e represents 0 or 1, -f stands for 0 or 1, -g stands for 0 or 1, -h represents 0 or 1, - at least one of e, f, g and h is different from 0] The present invention is characterized in that it comprises at least one organosilicon compound (a) represented by the following formula:

[0038] Examples of substituents R1, R2, R3, R4, R5, R5', R5", R6, R6', R6", R7, R8, L, A, A', A", A'' and A"" in compounds of formulae (I) and (II) are set forth below.

[0039] Examples of C1-C6 alkyl groups are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl groups. Examples of C2-C6 alkenyl groups are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, and preferred C2-C6 alkenyl groups are vinyl and allyl. Preferred examples of hydroxy C1-C6 alkyl groups are hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyhexyl groups; the 2-hydroxyethyl group is particularly preferred. Examples of amino C1-C6 alkyl groups are aminomethyl, 2-aminoethyl and 3-aminopropyl groups. The 2-aminoethyl group is particularly preferred. The linear divalent C1-C 20 Examples of alkylene groups include methylene (-CH-), ethylene (-CH-CH-), propylene (-CH-CH-CH-) and butylene (-CH-CH-CH-CH-). Propylene (-CH-CH-CH-) is particularly preferred. Divalent alkylene groups may be branched due to the chain length of 3 C atoms. Branched divalent C-C 20 Examples of alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0040] Formula (I): R1R2N-L-Si(OR3) a (R4) b (I) In the organosilicon compound represented by the formula: R1 and R2 radicals, independently of one another, represent a hydrogen atom or a C1-C6 alkyl radical. Highly preferably, R1 and R2 both represent a hydrogen atom.

[0041] At the center of the organosilicon compound is a structural unit or linker -L-, which is a linear or branched divalent C1-C 20 It means an alkylene group.

[0042] Bivalent C1-C 20 The alkylene group is a divalent or divalent C-C 20 Sometimes referred to as an alkylene group, this means that each L group can form two bonds: one bond from the amino group R1R2N to the linker L, and a second bond between the linker L and the silicon atom.

[0043] Preferably, -L- is a linear divalent (i.e., bivalent) C-C 20 It means an alkylene group. More preferably, -L- means a straight-chain divalent C1-C6 alkylene group. Particularly preferred -L- means a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-) or a butylene group (-CH2-CH2-CH2-CH2-). L means a propylene group (-CH2-CH2-CH2-).

[0044] The linear propylene group (-CH2-CH2-CH2-) may also be referred to as a propane-1,3-diyl group.

[0045] Formula (I): R1R2N-L-Si(OR3) a (R4) b (I) The organosilicon compounds represented by the formula: a (R4) b has.

[0046] Terminal structural unit -Si(OR3) a (R4) b In the formula (I), R3 is hydrogen or a C1-C6 alkyl group, and R4 is a C1-C6 alkyl group. R3 and R4 each independently represent a methyl group or an ethyl group.

[0047] Here, a represents an integer between 1 and 3, and b represents an integer 3-a. When a represents the number 3, b is equal to 0. When a represents the number 2, b is equal to 1. When a represents the number 1, b is equal to 2.

[0048] Particularly resistant films have been produced when the agent (a) contains at least one organosilicon compound (a1) of formula (I) in which the radicals R3 and R4 are each independently a methyl or ethyl group.

[0049] The most washfast dyeings were obtained when agent (a) contained at least one organosilicon compound of formula (I) in which the radicals R3 and R4, independently of one another, represent a methyl or ethyl group.

[0050] Furthermore, dyeings with the best washing fastness properties have been obtained when agent (a) contains at least one organosilicon compound of formula (I) where a is the number 3, and b is the number 0.

[0051] In another preferred embodiment, the agent (a) used in the method is characterized in that it comprises at least one organosilicon compound (a1) of formula (I) in which R3 and R4 are each independently a methyl or ethyl group, a is the number 3, and b is the number 0.

[0052] In another preferred embodiment, the method comprises the step of: R1R2N-L-Si(OR3) a (R4) b (I) [In the formula, -R1 and R2 both represent hydrogen atoms; -L represents a linear divalent C1-C6 alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or an ethylene group (-CH2-CH2-), -R3 represents a hydrogen atom, an ethyl group, or a methyl group; -R4 represents a methyl group or an ethyl group; -a represents the number 3, -b represents the number 0] The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0053] Organosilicon compounds of formula (I) which are particularly suitable for solving the problems of the present invention are -(3-aminopropyl)triethoxysilane TIFF0007657770000002.tif3473-(3-aminopropyl)trimethoxysilane TIFF0007657770000003.tif3465-1-(3-aminopropyl)silanetriol TIFF0007657770000004.tif2056-(2-aminoethyl)triethoxysilane TIFF0007657770000005.tif3464-(2-Aminoethyl)trimethoxysilane TIFF0007657770000006.tif3455-1-(2-aminoethyl)silanetriol TIFF0007657770000007.tif2047-(3-Dimethylaminopropyl)triethoxysilane TIFF0007657770000008.tif3475-(3-Dimethylaminopropyl)trimethoxysilane TIFF0007657770000009.tif3466-1-(3-Dimethylaminopropyl)silanetriol TIFF0007657770000010.tif2057-(2-Dimethylaminoethyl)triethoxysilane TIFF0007657770000011.tif3566-(2-Dimethylaminoethyl)trimethoxysilane, and TIFF0007657770000012.tif3457-1-(2-Dimethylaminoethyl)silanetriol The file is TIFF0007657770000013.tif2039.

[0054] In another preferred embodiment, the method comprises the step 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 and / or -1-(2-dimethylaminoethyl)silanetriol The composition is characterized in that it comprises at least one organosilicon compound (a1) selected from the group consisting of:

[0055] The organosilicon compounds of formula (I) are commercially available. (3-aminopropyl)trimethoxysilane can be purchased, for example, from Sigma-Aldrich. (3-aminopropyl)triethoxysilane is also commercially available from Sigma-Aldrich.

[0056] In another embodiment, the composition comprises a compound of formula (II): The composition comprises at least one organosilicon compound (a1) represented by TIFF0007657770000014.tif6134.

[0057] The organosilicon compound represented by formula (II) has a silicon-containing group (RO) at each end. c (R6) d Si- and -Si(R6') d' (OR5') c' has.

[0058] The central part of the molecule represented by formula (II) contains the group -(A) e - and -[NR7-(A')] f -and-[O-(A")] g -and-[NR8-(A"')] h- is present, where e, f, g and h are each, independently of one another, the number 0 or 1, and at least one of e, f, g and h is different from 0. In other words, the organosilicon compound represented by formula (II) contains at least one atomic group selected from the group consisting of -(A)- and -[NR7-(A')]- and -[O-(A")]- and -[NR8-(A"')]-.

[0059] Two terminal structural units (RO) c (R6) d Si- and -Si(R6') d' (OR5') c' In the formula, the groups R5, R5', and R5" each independently represent a hydrogen atom or a C1-C6 alkyl group. The groups R6, R6', and R6" each independently represent a C1-C6 alkyl group.

[0060] Here, c represents an integer between 1 and 3, and d represents an integer 3-c. When c represents the number 3, d is equal to 0. When c represents the number 2, d is equal to 1. When c represents the number 1, d is equal to 2.

[0061] Similarly, c' represents an integer from 1 to 3, and d' represents the integer 3-c'. When c' represents the number 3, d' is 0. When c' represents the number 2, d' is 1. When c' represents the number 1, d' is 2.

[0062] The most stable films or the most washfast dyeings were obtained when c and c' both represent the number 3. In this case, d and d' both represent the number 0.

[0063] In another preferred embodiment, the method comprises the step of: TIFF0007657770000015.tif6134[In the formula, -R5 and R5' independently represent a methyl group or an ethyl group; -c and c' together represent the number 3, -d and d' both represent the number 0. The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0064] When c and c' are both the number 3 and d and d' are both the number 0, the organosilicon compound of the present invention has the formula (IIa): (RO)Si-(A) e -[NR7-(A')] f -[O-(A")] g -[NR8-(A"')] h -Si(OR5')3(IIa) is equivalent to.

[0065] e, f, g and h may independently represent the numbers 0 or 1, and at least one of e, f, g and h is different from 0. Thus, the symbols e, f, g and h represent the atomic group -(A) e - and -[NR7-(A')] f -and-[O-(A")] g -and-[NR8-(A"')] h - is present in the central portion of the organosilicon compound represented by formula (II).

[0066] In the present invention, it has been found that the presence of certain atomic groups is particularly advantageous for improving the washing fastness. Particularly good results have been obtained when at least two of e, f, g and h represent the number 1. Particularly preferably, e and f together represent the number 1. Furthermore, g and h together represent the number 0.

[0067] When e and f both represent the number 1 and g and h both represent the number 0, the organosilicon compound of the present invention has the formula (IIb): (R5O) c (R6) d Si-(A)-[NR7-(A')]-Si(R6') d' (OR5') c' (IIb) is equivalent to.

[0068] The groups A, A', A", A"' and A"" are independently straight or branched divalent C-C20 Preferably, the groups A, A', A", A"' and A"" are each independently a linear divalent C-C alkylene group. 20 More preferably, the groups A, A', A", A'" and A"" independently represent a straight chain divalent C1-C6 alkylene group.

[0069] In particular, the radicals A, A', A", A"' and A"" independently of one another denote a methylene radical (-CH-), an ethylene radical (-CH-CH-), a propylene radical (-CH-CH-CH-) or a butylene radical (-CH-CH-CH-CH-CH-). Particularly preferably, the radicals A, A', A", A"' and A"" denote a propylene radical (-CH-CH-CH-).

[0070] Bivalent C1-C 20 The alkylene group is a divalent or divalent C-C 20 Sometimes referred to as an alkylene group, this means that each of the atomic groups A, A', A", A"' and A"" can form two bonds.

[0071] A linear propylene group (-CH2-CH2-CH2-) may also be referred to as a propane-1,3-diyl group.

[0072] When f represents the number 1, the organosilicon compound of formula (II) contains the structural group --[NR7--(A')]--.

[0073] When h represents the number 1, the organosilicon compound of formula (II) comprises the structural group -[NR8-(A''')]-.

[0074] In the formula, R7 and R8 are independently a hydrogen atom, a C1-C6 alkyl group, a hydroxy C1-C6 alkyl group, a C2-C6 alkenyl group, an amino C1-C6 alkyl group, or a group represented by formula (III): -(A"")-Si(R6") d "(OR5") c " (III) It represents a group represented by the following formula:

[0075] Very preferably, the radicals R7 and R8 independently of one another represent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a radical of formula (III).

[0076] When f represents the number 1 and h represents the number 0, the organosilicon compound comprises the atomic group -[NR7-(A')]- but does not comprise the atomic group -[NR8-(A"')]-. When the group R7 represents the atomic group of formula (III), the agent (a) comprises an organosilicon compound having three reactive silane groups.

[0077] In another preferred embodiment, the method comprises the step of: TIFF0007657770000016.tif6134[In the formula, - e and f together represent the number 1, - g and h together represent the number 0, -A and A' are independently a linear divalent C1-C6 alkylene group; -R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group represented by formula (III). The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0078] In another preferred embodiment, the method comprises the step of: - e and f together represent the number 1, - g and h together represent the number 0, -A and A' each independently represent a methylene group (-CH-), an ethylene group (-CH-CH-) or a propylene group (-CH-CH-CH-); -R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group represented by formula (III). The present invention is characterized in that it comprises at least one organosilicon compound represented by the following formula:

[0079] The organosilicon compounds of formula (II) suitable for solving the problems of the present invention are -3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007657770000017.tif39113-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007657770000018.tif45130-N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007657770000019.tif39113-N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007657770000020.tif45130-2-[Bis[3-(trimethoxysilyl)propyl]amino]ethanol TIFF0007657770000021.tif47113-2-[Bis[3-(triethoxysilyl)propyl]amino]ethanol TIFF0007657770000022.tif53130-3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007657770000023.tif60113-3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007657770000024.tif63126-N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine TIFF0007657770000025.tif48113-N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine TIFF0007657770000026.tif54130-N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine TIFF0007657770000027.tif45113-N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The file is TIFF0007657770000028.tif51130.

[0080] Organosilicon compounds of formula (II) are commercially available.

[0081] Bis(trimethoxysilylpropyl)amine, having the CAS number 82985-35-1, can be purchased from Sigma-Aldrich.

[0082] Bis[3-(triethoxysilyl)propyl]amine, having the CAS number 13497-18-2, can be purchased, for example, from Sigma-Aldrich.

[0083] N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine, also known as bis(3-trimethoxysilylpropyl)-N-methylamine, is commercially available from Sigma-Aldrich or Fluorochem.

[0084] 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine, having the CAS number 18784-74-2, can be purchased, for example, from Fluorochem or Sigma-Aldrich.

[0085] In another preferred embodiment, the method comprises the step of: -3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -2-[Bis[3-(trimethoxysilyl)propyl]amino]ethanol -2-[Bis[3-(triethoxysilyl)propyl]amino]ethanol -3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine -N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine -N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine -N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine, and / or -N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The composition is characterized in that it comprises at least one organosilicon compound (a1) selected from the group consisting of:

[0086] In another test, specifically a dyeing test, the agent (a) applied to the keratin material in the method is a compound of formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) It has been found to be particularly advantageous when the composition contains at least one organosilicon compound of the formula:

[0087] The compound represented by formula (IV) is an organosilicon compound selected from silanes having one, two or three silicon atoms, the organosilicon compound containing one or more hydroxyl and / or hydrolyzable groups per molecule.

[0088] Formula (IV): R9Si(OR 10 )k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3; -m represents the integer 3-k] The organosilicon compounds represented by the formula: are also called alkylalkoxysilane-type or alkylhydroxysilane-type silanes.

[0089] In another preferred embodiment, the method comprises the step of: R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3; -m represents the integer 3-k] The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0090] In another preferred embodiment, the method further comprises the step of: (a) comprising, in addition to one or more organosilicon compounds of formula (I), a compound of formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3; -m represents the integer 3-k] The present invention is characterized in that it comprises at least one further organosilicon compound represented by the formula:

[0091] In another preferred embodiment, the method further comprises the step of: (a) comprising, in addition to one or more organosilicon compounds of formula (II), a compound of formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3; -m represents the integer 3-k] The present invention is characterized in that it comprises at least one further organosilicon compound represented by the formula:

[0092] In another preferred embodiment, the method further comprises the step of: (a) comprising, in addition to one or more organosilicon compounds of formula (I) and / or (II), a compound of formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3; -m represents the integer 3-k] The present invention is characterized in that it comprises at least one further organosilicon compound represented by the formula:

[0093] In the organosilicon compound of formula (IV), the group R9 is a C1-C 18 This C1-C alkyl group. 18 The alkyl group is saturated and may be linear or branched. Preferably, R is a linear C-C 18 R9 represents an alkyl group. Preferably, R9 represents 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. Particularly preferably, R9 represents a methyl group, an ethyl group, an n-propyl group, an n-hexyl group or an n-octyl group.

[0094] In the organosilicon compound of formula (IV), the group R 10 represents a hydrogen atom or a C1-C6 alkyl group. 10 represents a methyl group or an ethyl group.

[0095] In the organosilicon compound of formula (IV), the group R 11 represents a C1-C6 alkyl group. Particularly preferably, R 11 represents a methyl group or an ethyl group.

[0096] Furthermore, k represents an integer from 1 to 3, and m represents an integer 3-k. When k represents the number 3, m is equal to 0. When k represents the number 2, m is equal to 1. When k represents the number 1, m is equal to 2.

[0097] Particularly stable films, i.e. dyeings with particularly good washing fastness properties, are obtained when using an agent (a) which comprises at least one organosilicon compound (a1) of formula (IV) in which k is the number 3. In this case, m is the number 0.

[0098] Organosilicon compounds of the formula (IV) which are particularly suitable for solving the problems of the present invention are -Methyltrimethoxysilane TIFF0007657770000029.tif3430-Methyltriethoxysilane TIFF0007657770000030.tif4139-Ethyltrimethoxysilane TIFF0007657770000031.tif3439-Ethyltriethoxysilane TIFF0007657770000032.tif4147-n-Hexyltrimethoxysilane TIFF0007657770000033.tif3475-n-Hexyltriethoxysilane TIFF0007657770000034.tif4184-n-Octyltrimethoxysilane TIFF0007657770000035.tif3494-n-Octyltriethoxysilane TIFF0007657770000036.tif41102-n-Dodecyltrimethoxysilane and / or TIFF0007657770000037.tif34130-n-Dodecyltriethoxysilane TIFF0007657770000038.tif43140 n-Octadecyltrimethoxysilane and / or n-Octadecyltriethoxysilane.

[0099] In another preferred embodiment, the method comprises the step of: -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Propyltrimethoxysilane -Propyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -Dodecyltrimethoxysilane -Dodecyltriethoxysilane Octadecyltrimethoxysilane and / or -Octadecyltriethoxysilane and comprising at least one organosilicon compound (a1) represented by formula (IV).

[0100] The organosilicon compounds are reactive compounds. In this context, it has been found to be advantageous when the agent (a) contains one or more organosilicon compounds (a1) in a total amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 8% by weight, based on the total weight of the agent (a).

[0101] In another preferred embodiment, the method is characterized in that the agent (a) contains one or more organosilicon compounds (a1) in a total amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 8% by weight, based on the total weight of agent (a).

[0102] To achieve particularly good dyeing results, it is particularly advantageous to use organosilicon compounds of formula (I) and / or (II) in specific quantitative ranges on average (a).Particularly preferably, agent (a) contains one or more organosilicon compounds of formula (I) and / or (II) in a total amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the total weight of agent (a).

[0103] In another preferred embodiment, the method is characterized in that the agent (a) contains one or more organosilicon compounds of the formulae (I) and / or (II) in a total amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the total weight of agent (a).

[0104] It has also been found to be particularly preferred that the organosilicon compounds of formula (IV) are present in a specific quantitative range on average in (a). Particularly preferably, agent (a) contains one or more organosilicon compounds of formula (IV) in a total amount of 0.1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 4 to 9% by weight, based on the total weight of agent (a).

[0105] In another preferred embodiment, the method is characterized in that the agent (a) contains one or more organosilicon compounds of formula (IV) in a total amount of 0.1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3.2 to 10% by weight, based on the total weight of agent (a).

[0106] In the course of the investigations which led to the present invention, it was found that even when agent (a) contains two organosilicon compounds which are structurally different from one another, a particularly stable and uniform film is obtained on keratinous materials.

[0107] In another preferred embodiment, the method is characterized in that agent (a) comprises at least two structurally different organosilicon compounds.

[0108] In a preferred embodiment, the method is characterized in that an agent (a) comprising at least one organosilicon compound of formula (I) and at least one organosilicon compound of formula (IV) is applied to the keratinous material.

[0109] In another particularly preferred embodiment, the method comprises applying an agent (a) to the keratin material, the agent (a) comprising at least one organosilicon compound of formula (I) selected from the group consisting of (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and further comprising at least one organosilicon compound of formula (IV) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.

[0110] In another preferred embodiment, the method comprises the step of: - 0.5 to 5% by weight of at least one first organosilicon compound (a1) selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane and (2-dimethylaminoethyl)triethoxysilane, and - 3.2 to 10% by weight of at least one second organosilicon compound (a1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane and dodecyltriethoxysilane The present invention is characterized in that it comprises:

[0111] In this embodiment, agent (a) comprises one or more organosilicon compounds from a first group in a total amount of 0.5 to 3 wt.%. The organosilicon compounds of this first group are selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane and / or (2-dimethylaminoethyl)triethoxysilane.

[0112] In this embodiment, agent (a) comprises one or more organosilicon compounds from a second group in a total amount of 3.2 to 10 wt.%. The organosilicon compounds of this second group are selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane and / or dodecyltriethoxysilane.

[0113] In the case of organosilicon compounds having at least one hydrolyzable group, hydrolysis occurs even when a small amount of water is added. The organosilicon compounds having at least one hydroxyl group and / or hydrolyzates can react with each other in a condensation reaction. Therefore, in the agent (a), both the organosilicon compounds having at least one hydrolyzable group and their hydrolyzates and / or condensates can be present. When using an organosilicon compound having at least one hydroxyl group, both the organosilicon compounds having at least one hydroxyl group and their condensates can be present in the agent (a).

[0114] Condensate is understood to be the product produced by the reaction of at least two organosilicon compounds, each of which has at least one hydroxyl group or hydrolyzable group per molecule, with the removal of water and / or alkanol.Condensate can be, for example, not only dimer, but also trimer or oligomer, and condensate is in equilibrium with monomer.Depending on the amount of water used or consumed in hydrolysis, the equilibrium shifts from monomeric organosilicon compounds to condensate.

[0115] Particularly good results have been obtained when using organosilicon compounds of formula (I) and / or (II) in the method.As mentioned above, hydrolysis / condensation already starts with a small amount of moisture, so hydrolysis products and / or condensation products of organosilicon compounds of formula (I) and / or (II) are also included in this embodiment.

[0116] Color forming compound (a2) When agent (a) is applied to the keratinous material, in the presence of water, one or more organosilicon compounds (a1) containing one or more hydroxyl or hydrolyzable groups per molecule are first hydrolyzed and oligomerized or polymerized. The hydrolysis products or oligomers thus formed have a particularly high affinity for the surface of the keratinous material. The simultaneous presence of coloring compounds (a2) in agent (a) integrates them in the resulting oligomers or polymers, forming a colored film on the keratinous material. Following the application of agent (a), agent (b) is applied. The successive application of agents (a) and (b) thus results in a coloration that is particularly resistant to external influences. The coloring compounds trapped in these resistant films exhibit excellent wash resistance.

[0117] The agent (a) used in the dyeing process therefore contains, as essential component (a2) of the present invention, at least one colour-imparting compound. The at least one colouring compound (a2) contains at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a colouring compound (ii) from the group of metal oxides and / or metal oxide hydrates (i) and pigments.

[0118] The effect pigments are coloured by the presence in at least one layer of a coloured compound (ii) from the group of the pigments.

[0119] Thus, with the aid of "colored" effect pigments, keratin fibers can be dyed in particularly intense and diverse shades.

[0120] The effect pigment comprises a substrate platelet.

[0121] The substrate wafer preferably has an average thickness of at most 150 nm, preferably less than 50 nm, more preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred ranges of thickness of the substrate wafer are 2.5-50 nm, 5-50 nm, 10-50 nm, 2.5-30 nm, 5-30 nm, 10-30 nm, 2.5-25 nm, 5-25 nm, 10-25 nm, 2.5-20 nm, 5-20 nm, 10-20 nm. Preferably, each substrate plate has a thickness as uniform as possible.

[0122] The substrate plate is preferably monolithic. In this specification, "monolithic" means that it consists of a single self-contained unit without cracks, stratification or inclusions, although microstructural changes may occur within the substrate platelet. The substrate platelet is preferably homogeneous in structure, i.e., there is no concentration gradient within the platelet. In particular, the substrate platelet does not have a layered structure and does not have particles or dispersed particles therein.

[0123] The dimensions of the substrate platelets can be adjusted depending on the particular application, for example the desired effect on keratinous materials.Typically, the substrate platelets have an average maximum diameter of about 2 to 200 μm, especially about 5 to 100 μm.

[0124] In a preferred embodiment, the shape factor (aspect ratio), which is the ratio of the average dimension to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably more than 750. The average dimension of the uncoated substrate platelet is the d50 value of the uncoated substrate platelet. Unless otherwise stated, the d50 value is measured by quixel wet dispersion using a Sympatec Helos instrument. To prepare the sample, the sample to be analyzed is predispersed in isopropanol for 3 minutes.

[0125] The substrate platelet can be composed of any material that can be formed into a platelet shape.

[0126] The substrate platelet may be of natural origin, but may also be synthetically produced. Materials from which the substrate platelet can be made include metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds, and minerals, such as mica and (semi)precious stones, and plastics. Preferably, the substrate platelet is made of a metal or alloy.

[0127] Any metal suitable for effect pigments can be used. Such metals include iron and steel, and any (semi)metal that is resistant to air and water, such as platinum, tin, zinc, chromium, molybdenum and silicon, and their alloys, such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver and gold. Preferred substrate platelets include aluminum platelets and brass platelets, and aluminum substrate platelets are particularly preferred.

[0128] Aluminum substrate plates can be produced, inter alia, by stamping from aluminum foil or according to common milling and spraying techniques. For example, aluminum flakes are available from the Hall process, which is a wet milling process.

[0129] Other metal flakes, such as bronze flakes, can be obtained by dry milling processes such as the Hametag process.

[0130] The substrate platelets can have various shapes. For example, lamellar and lenticular metal platelets or so-called vacuum deposited pigments (VMP) can be used as substrate platelets. Lamellar substrate platelets are characterized by irregularly structured edges and are also called "cornflakes" due to their appearance. Lenticular substrate flakes have regular rounded edges and are also called "dollar coins" due to their appearance.

[0131] Metal or metal alloy substrate plates can be passivated, for example, by anodizing (oxide layer) or chromating.

[0132] The coating can change the surface and / or optical properties of the effect pigment and increase the mechanical and chemical load-bearing capacity of the effect pigment. For example, only the top and / or bottom surface of the substrate wafer may be coated, with the side surfaces being recessed. Preferably, the entire surface of the substrate platelet, which may be optionally passivated, including the side surfaces, is covered by the layer. The substrate platelet is preferably completely covered by the coating.

[0133] The coating may be composed of one or more layers. In a preferred embodiment, the coating only has layer A. In an equally preferred embodiment, the coating has a total of at least two layers, preferably two or three. It may be preferred that the coating has two layers A and B, layer B being different from layer A. Preferably, layer A is located between layer B and the surface of the substrate plate. In another preferred embodiment, the coating has three layers A, B and C. In this embodiment, layer A is located between layer B and the surface of the substrate wafer, and layer C is located above layer B, which is different from layer B below.

[0134] Suitable materials for layer A, and optionally layers B and C, are all substances that can be applied to the substrate platelet in the long term. Such materials should preferably be applied in the form of a film. Preferably, the entire surface of the substrate platelet, optionally passivated, including the side surfaces, is covered by layer A, or layers A and B, or layers A, B and C.

[0135] It is preferred that the metal oxide and / or metal oxide hydrate (i) is selected from the group consisting of silicon (di)oxide, silicon oxide hydrate, aluminium oxide, aluminium oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof.

[0136] Layer A preferably comprises at least one low refractive index metal oxide and / or metal oxide hydrate. Preferably, layer A comprises at least 95% by weight of low refractive index metal oxide (hydrate). The low refractive index material has a refractive index of 1.8 or less, preferably 1.6 or less.

[0137] Suitable low refractive index metal oxides for layer A include, for example, silicon (di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide and mixtures thereof, with silicon dioxide being preferred. Layer A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, and particularly preferably 5 to 20 nm.

[0138] If present, layer B may comprise at least one high refractive index metal oxide different from layer A. The high refractive index material has a refractive index of at least 1.9, preferably at least 2.0, more preferably at least 2.4. Preferably, layer B comprises at least 95% by weight, more preferably at least 99% by weight of the high refractive index metal oxide.

[0139] When layer B comprises a (high refractive index) metal oxide, it preferably has a thickness of at least 50 nm. Preferably, the thickness of layer B is equal to or less than 400 nm, more preferably equal to or less than 300 nm.

[0140] Suitable high refractive index metal oxides for layer B are, for example, selectively light absorbing (i.e. colored) metal oxides such as iron(III) oxide (α- and γ-Fe2O3, red), cobalt(II) oxide (blue), chromium(III) oxide (green), titanium(III) oxide (blue, usually present in a mixture with titanium oxynitride and titanium nitride) and vanadium(V) oxide (orange), as well as mixtures thereof. Colorless high refractive index oxides such as titanium dioxide and / or zirconium oxide are also suitable.

[0141] In addition to the high refractive index metal oxide, layer B can contain preferably 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, of a selectively absorbing dye, in each case based on the total amount of layer B. Suitable dyes are organic and inorganic dyes which can be stably incorporated into the metal oxide coating. Dyes within the meaning of the present invention have a solubility in water (760 mmHg) of more than 0.5 g / L at 25° C. and are therefore not considered pigments.

[0142] Alternatively, for metal oxides, layer B may comprise a metal particle-carrying layer, on the surface of which the metal particles are deposited. In a preferred embodiment, the metal particles directly cover part of the metal particle-carrying layer. In this embodiment, the effect pigment has areas where no metal particles are present, i.e. areas that are not covered by metal particles.

[0143] The metal particle supporting layer includes a metal layer and / or a metal oxide layer.

[0144] When the metal particle supporting layer includes a metal layer and a metal oxide layer, the arrangement of these layers is not limited.

[0145] The metal particle support layer preferably includes at least a metal layer, and more preferably the metal layer includes an element selected from tin (Sn), palladium (Pd), platinum (Pt) and gold (Au).

[0146] The metal layer can be formed, for example, by adding an alkali to a metal salt solution containing the metal.

[0147] When the metal particle support layer comprises a metal oxide layer, it preferably does not comprise silicon dioxide. The metal oxide layer preferably comprises an oxide of at least one element selected from the group consisting of Mg (magnesium), Sn (tin), Zn (zinc), Co (cobalt), Ni (nickel), Fe (iron), Zr (zirconium), Ti (titanium) and Ce (cerium). Particularly preferably, the metal particle support layer iii) in the form of a metal oxide layer comprises the metal oxides of Sn, Zn, Ti and Ce.

[0148] A metal particle support layer in the form of a metal oxide layer can be produced, for example, by hydrolysis of an alkoxide of the metal to form the metal of the metal oxide in a sol-gel process.

[0149] The thickness of the metal particle support layer is preferably 30 nm or less, and more preferably in the range of 0.1 to 10 nm.

[0150] The metal particles may comprise at least one element selected from the group consisting of aluminum (Al), titanium (Ti), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), gold (Au) and alloys thereof. It is particularly preferred that the metal particles comprise at least one element selected from copper (Cu), nickel (Ni) and silver (Ag).

[0151] The average particle size of the metal particles is preferably 50 nm or less, more preferably 30 nm or less. The distance between the metal particles is preferably 10 nm or less.

[0152] Suitable methods for forming the metal particles include vacuum deposition, sputtering, chemical vapor deposition (CVD), electroless plating, etc. Among these methods, electroless plating is particularly preferred.

[0153] In a preferred embodiment, the effect pigment has a further layer C which comprises a metal oxide (hydrate) different from the underlying layer B. Suitable metal oxides include 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. Silicon dioxide is preferred.

[0154] Layer C preferably has a thickness of 10 to 500 nm, more preferably 50 to 300 nm.

[0155] The coating of the effect pigments has at least one layer which, in addition to the metal oxide and / or metal oxide hydrate, further comprises a colour-imparting compound (ii) from the group of the pigments.

[0156] The at least one layer comprising a coloring compound (ii) selected from the group consisting of metal oxides and / or metal oxide hydrates (i) and pigments can be layers A, B and / or C. If the coating has exclusively one layer A, layer A also contains a coloring compound (ii) from the group of pigments.

[0157] If the coating of the effect pigment has two layers A and B, each containing a metal oxide (hydrate), then both layers A and B or only one of these two layers may contain a color-imparting compound (ii) from the group of pigments. Preferably, layer A contains a coloring compound (ii) from the group of pigments.

[0158] If the coating has layers A, B and C, each of which comprises a metal oxide (hydrate), each of layers A, B and C may comprise a coloring compound (ii) selected from the group consisting of pigments. Alternatively, in this embodiment, two of the three layers may comprise a coloring compound (ii) from the group consisting of pigments. Thus, the coloring compound (ii) may come from the group of pigments in layers A and B, layers A and C or layers B and C. Similarly, only one of the three layers may comprise a coloring compound (ii) from the group consisting of pigments. Thus, the coloring compound (ii) may come from the group of pigments in layers A, B or C. In a particularly preferred embodiment of the effect pigment comprising a coating with layers A, B and C, the coloring compound (ii) comes from the group of pigments in layers A and / or C.

[0159] When the coating comprises layers A, B and C, where layers A and C comprise metal oxides (hydrates) and layer B comprises a metal layer having metal particles deposited thereon, each of layers A and C may comprise a colouring compound (ii) selected from the group consisting of pigments. Alternatively, in this embodiment, only one of layers A and C may comprise a colouring compound (ii) from the group of pigments.

[0160] In a particularly preferred embodiment of the effect pigment comprising a coating with layers A, B and C, the colouring compound (ii) is derived from the group of the pigments in layers A and / or C.

[0161] It is particularly preferred that the effect pigment comprises an aluminum substrate platelet and a silica-containing layer A. If the substrate platelet-based effect pigment has layer A and layer C, it is preferred that the effect pigment has an aluminum substrate platelet and layers A and C which contain silica.

[0162] At least one layer of the effect pigment comprises a colour-imparting compound (ii) from the group of pigments.

[0163] A pigment in the sense of the present invention is a coloring compound that has a solubility in water at 25° C. of less than 0.5 g / L, preferably less than 0.1 g / L, more preferably less than 0.05 g / L. The solubility in water can be measured, for example, by the following method: 0.5 g of pigment is weighed into a beaker. A magnetic stir bar is added. Then 1 L of distilled water is added. The mixture is heated at 25° C. while stirring on a magnetic stirrer for 1 hour. If undissolved components of the pigment are visible in the mixture after this time, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be visually evaluated due to the high strength of the finely dispersed pigment, the mixture is filtered. If undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0164] Suitable pigments may be of inorganic and / or organic origin.

[0165] In a preferred embodiment, the effect pigment comprises at least one colour-imparting compound (ii) selected from the group consisting of inorganic pigments and / or organic pigments.

[0166] Preferred pigments are selected from synthetic or natural inorganic pigments. Inorganic pigments of natural origin can be prepared, for example, from chalk, ochre, umber, green earth, calcined sienna or graphite. Also black pigments, such as black iron oxide, colored pigments, such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments can be used as inorganic pigments.

[0167] Particularly suitable are colored metal oxides, metal hydroxides and metal oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and / or molybdates. 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), ultramarine (sodium aluminum sulfosilicate, CI 77007, pigment blue 29), chromium oxide hydrate (CI 77289), Prussian blue (ferric ferrocyanide, CI 77510) and / or carmine (cochineal).

[0168] Colored pearlescent pigments are also particularly preferred pigments. They are usually mica and / or mica-based and may be coated with one or more metal oxides. Micas belong to the group of layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce pearlescent pigments in combination with metal oxides, mica, mainly muscovite or phlogopite, is coated with the metal oxide.

[0169] As an alternative to natural mica, synthetic mica coated with one or more metal oxides can also be used as pearlescent pigments. Particularly preferred pearlescent pigments are based on natural or synthetic mica and coated with one or more of the abovementioned metal oxides. By varying the thickness of the metal oxide layer, the color of the respective pigment can be varied.

[0170] A preferred mica-based pigment is a synthetic mica platelet based on synthetic fluorphlogopite (INCI) and coated with metal oxide. The synthetic fluorphlogopite platelet is, for example, coated with tin oxide, iron oxide and / or titanium dioxide. The metal oxide layer may further comprise a pigment such as iron hexacyanoferrate (II / III) or carmine red. Such mica pigments are, for example, available from Eckart under the name SYNCRYSTAL.

[0171] Preferred effect pigments are therefore characterized in that they contain at least one colouring compound (ii) from the group of pigments selected from the group consisting of coloured metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, double metal cyanides, metal sulfates, bronze pigments and / or from coloured mica or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0172] In another preferred embodiment, the effect pigment is characterized in that it comprises at least one coloring compound (ii) from the group of pigments selected from mica or mica-based pigments reacted with one or more metal oxides selected from the group consisting 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), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or Prussian blue (ferric ferrocyanide, CI 77510).

[0173] Other suitable pigments are based on borosilicates in the form of platelets coated with metal oxides. These are, for example, coated with tin oxide, iron oxide, silicon dioxide and / or titanium dioxide. Such borosilicate-based pigments are available, for example, from Eckart under the name MIRAGE or from BASF SE under the name Reflecks.

[0174] Examples of particularly suitable pigments are sold under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® by Merck, Ariabel® and Unipure® by Sensient, Prestige® by Eckart Cosmetic Colors, Flamenco®, Cellini®, Cloisonne®, Duocrome®, Gemtone®, Timica®, MultiReflections, Chione by BASF SE and Sunshine® by Sunstar.

[0175] Particularly preferred pigments under the trade name Colorona® are, for example: Colorona Copper, Merck, Mica, CI 77491 (iron oxide) Colorona Passion Orange, Merck, Mica, CI 77491 (iron oxide), 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 oxide), mica Colorona Aborigine Amber, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Blackstar Blue, Merck, CI 77499 (iron oxide), mica Colorona Patagonian Purple, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) Colorona Red Brown, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Russet, Merck, CI 77491 (Titanium Dioxide), Mica, CI 77891 (Iron Oxides) Colorona Imperial Red, Merck, Mica, Titanium Dioxide (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (titanium dioxide), mica, CI 77288 (chromium oxide green) 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 Oxide (CI 77491) Colorona Carmine Red, Merck, Mica, Titanium Dioxide, Carmine Colorona Blackstar Green, Merck, Mica, CI 77499 (iron oxide) Colorona Bordeaux, Merck, Mica, CI 77491 (iron oxide) Colorona Bronze, Merck, Mica, CI 77491 (iron oxide) Colorona Bronze Fine, Merck, Mica, CI 77491 (iron oxide) Colorona Fine Gold MP 20, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Sienna Fine, Merck, CI 77491 (iron oxide), mica Colorona Sienna, Merck, Mica, CI 77491 (iron oxide) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, CI 77491 (Iron Oxide), Tin Oxide Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxide, Mica, CI 77891, CI 77491 (EU) Colorona Mica Black, Merck, CI 77499 (iron oxide), Mica, CI 77891 (titanium dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxide) Colorona Blackstar Gold, Merck, Mica, CI 77499 (Iron Oxide)

[0176] Other particularly preferred pigments under 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

[0177] Particularly preferred pigments under the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI 77491 (iron oxide), silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxide), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (iron oxide), silica

[0178] In another embodiment, the effect pigment may also comprise one or more color-imparting compounds (ii) selected from the group consisting of organic pigments.

[0179] The organic pigments are correspondingly insoluble organic dyes or colorants which may be selected, for example, from the group consisting of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine and / or triarylmethane compounds.

[0180] Examples of particularly suitable organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a color index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a color index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a color index of CI 61565, CI 61570, CI 74260, orange pigments with a color index of CI 11725, CI 15510, CI 45370, CI 71105, and orange pigments with a color index of 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 red pigments.

[0181] In another particularly preferred embodiment, the effect pigment is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a color index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a color index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a color index of CI 61565, CI 61570, CI 74260, orange pigments with a color index of CI 11725, CI 15510, CI 45370, CI 71105, red pigments with a color index of CI 12085, CI 130 ... 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, CI 75470 red pigments, and mixtures thereof.

[0182] The organic pigment may be a color paint. In the sense of the present invention, the term "color lacquer" means a particle comprising a layer of absorbed dye, the particle and the dye unit being insoluble under the above conditions. The particle may be, for example, an inorganic material, which may be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate or aluminum.

[0183] For example, alizarin color varnish can be used.

[0184] Suitable coloured compounds (ii) from the group of the pigments are also inorganic and / or organic pigments modified with a polymer, which makes it possible, for example, to increase the affinity of the pigment for the respective material of at least one layer.

[0185] The particle size of the coloring compound (ii) used depends on the layer in which the colorant layer is present. The color-imparting compound preferably has a particle size D smaller than the layer thickness of at least one layer. 90 More preferably, the coloring compound has a particle size D 95 is smaller than the layer thickness of at least one layer. Even more preferably, the particle size D of the coloring compound is 99 is smaller than the layer thickness of at least one layer. Very preferably, the particle size D of the coloring compound 100 is smaller than the layer thickness of at least one layer. The particle size of the colored compound can be measured, for example, using dynamic light scattering (DLS) or static light scattering (SLS). 90 D means that 90% of the particles of the coloring compound are smaller than the layer thickness of at least one layer. 95 means that 95% of the particles of the colouring compound are smaller than the layer thickness of at least one layer, and so on.

[0186] (i) metal oxides and / or metal oxide hydrates, and (ii) a coloring compound selected from the group consisting of pigments The amount of color-imparting compound (ii) from the group of pigments in at least one layer comprising is preferably up to 5% by weight, based on the total weight of the layer.

[0187] Layers A and C serve for corrosion protection and chemical and physical stabilization. Particularly preferably, layers A and C contain silicon dioxide or aluminum oxide applied by the sol-gel method.

[0188] Effect pigments based on coated substrate platelets preferably have a thickness of 70 to 500 nm, particularly preferably 100 to 400 nm, particularly preferably 150 to 320 nm, for example 180 to 290 nm. A small thickness of the coated substrate platelets is achieved by keeping the thickness of the uncoated substrate platelets small, but also by adjusting the thickness of coating A and, if present, coating C, to the smallest possible values.

[0189] The adhesion and abrasion resistance of effect pigments comprising a substrate platelet α) and a coating β) on keratinous materials, where the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, can be significantly increased by further modifying the layer A, B or C, which, depending on the structure, is the outermost layer, with organic compounds such as silanes, phosphates, titanates, borates or carboxylic acids. In this case, the organic compounds are bonded to the surface of the outermost, preferably metal oxide-containing, layer A, B or C. The outermost layer refers to the layer which is spatially furthest from the substrate platelet. The organic compounds are preferably functional silane compounds which can be bonded to the metal oxide-containing layer A, B or C. These can be either monofunctional or bifunctional compounds.

[0190] Examples of bifunctional organic compounds include methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyltris(methoxyethoxy)silane, 3-methacryloxypropyltris(butoxyethoxy)silane, 3-methacryloxypropyltris(butoxyethoxy)silane, 3-methacryloxypropyltris(butoxyethyl ... silane, 3-methacryloxypropyltris(butoxy)silane, 3-acryloxypropyltris(methoxyethoxy)silane, 3-acryloxypropyltris(butoxyethoxy)silane, 3-acryloxypropyltris(butoxy)silane, 3-acryloxypropyltris(butoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, phenylvinyldiethoxysilane, or phenylallyldichlorosilane.

[0191] Furthermore, modification with monofunctional silanes, alkylsilanes or arylsilanes can be carried out. This has only one functional group covalently bonded to the surface (i.e. the outermost, metal oxide (hydrate)-containing layer) of the effect pigment comprising the substrate platelet α) and the coating β) or to the metal surface if it is not completely coated. Here, the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments. The hydrocarbon group of the silane points away from the pigment. Depending on the type and nature of the hydrocarbon group of the silane, different degrees of hydrophobicity of the pigment are achieved. Examples of such silanes are hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Particularly preferred are effect pigments based on silica-coated aluminum substrate platelets surface-modified with monofunctional silanes. Octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane and hecadecyltriethoxysilane are particularly preferred. Due to the altered surface properties / hydrophobization, adhesion, abrasion resistance and tunability in application may be improved.

[0192] It has also been found that effect pigments with such surface modifications exhibit better compatibility with the organosilicon compounds and / or their condensates or polymerisates used.

[0193] Particularly satisfactory results have been obtained when agent (a) contains 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 0.2 to 6% by weight and very preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0194] The agent (a) may, in addition to the effect pigment, comprise further colouring compounds (a2) selected from the group consisting of pigments and / or direct dyes.

[0195] In the present invention, the use of pigments has been found to be particularly preferred.

[0196] In another very particularly preferred embodiment the method is characterized in that the agent (a) comprises at least one further colouring compound (a2) from the group of the pigments.

[0197] Pigments which can be used as further colouring compounds (a2) from the group of the pigments correspond to those already mentioned above as colouring compounds (ii).

[0198] In a preferred embodiment, the agent is characterized in that the agent (a) contains at least one further color-imparting compound (a2) from the group consisting of inorganic pigments and / or organic pigments.

[0199] In another preferred embodiment, the method is characterized in that the agent (a) comprises at least one further coloring compound (a2) from the group of inorganic pigments selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, double metal cyanides, metal sulfates, bronze pigments, and / or from colored mica or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0200] In another preferred embodiment, the method is characterized in that the agent (a) comprises at least one coloring compound (a2) from the group of pigments selected from mica or mica-based pigments reacted with one or more metal oxides selected from the group consisting 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), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (ferric ferrocyanide, CI 77510).

[0201] Other effect pigments, such as metallic luster pigments, may be used.

[0202] Effect pigments can include, for example, lamellar substrate platelet-based pigments, lenticular substrate platelet-based pigments, substrate platelet-based pigments including vacuum deposited pigments (VMPs).

[0203] Suitable effect pigments include, for example, the pigments Alegrace® Marvelous, Alegrace® Gorgeous or Alegrace® Aurous from Schlenk Metallic Pigments.

[0204] Also suitable effect pigments are the aluminum-based pigments of the SILVERDREAM series and the VISIONAIRE series of pigments from Eckart, which are based on aluminum or copper / zinc-containing metal alloys.

[0205] Other suitable effect pigments are the aluminium-based pigments of the Cosmicolor® series from Toyal Europe. A particularly suitable effect pigment is the coloured effect pigment Cosmicolor® Celeste.

[0206] Other suitable effect pigments are based on platelet-shaped borosilicates coated with metal oxides. These are, for example, coated with tin oxide, iron oxide, silicon dioxide and / or titanium dioxide. Such borosilicate-based pigments are available, for example, from Eckart under the name MIRAGE or from BASF SE under the name Reflecks.

[0207] In another embodiment of the method, agent (a) may contain one or more coloring compounds selected from the group consisting of organic pigments.

[0208] In another particularly preferred embodiment, the method further comprises the step of: the agent (a) being selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a Color Index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a Color Index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a Color Index of CI 61565, CI 61570, CI 74260, orange pigments with a Color Index of CI 11725, CI 15510, CI 45370, CI 71105, red pigments with a Color Index of CI 12085, CI 13060, CI 13062, CI 13064, CI 13066, CI 13068, CI 13068, CI 13069 ... 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 red pigments.

[0209] It is particularly preferred to use said pigments in agent (a) due to their excellent stability against light and temperature. It is also preferred that the pigments used have a specific particle size. This particle size, on the one hand, results in a uniform distribution of the pigment in the polymer film formed and, on the other hand, avoids rough hair or skin feel after application of the cosmetic product. Thus, according to the invention, at least one pigment has an average particle size D of 1 to 50 μm, preferably 5 to 45 μm, preferably 10 to 40 μm, 14 to 30 μm. 50 It is advantageous to have an average particle size D 50 can be measured, for example, using dynamic light scattering (DLS).

[0210] In addition to effect pigments, the agent (a) may contain, as one or more further coloured compounds (a2), other effect pigments, such as pigments based on layered substrate platelets and / or pigments based on VMP substrate platelets, VMP standing for vacuum metallised pigments.

[0211] In another preferred embodiment, the method is characterized in that agent (a) contains one or more further coloring compounds (a2) in the form of pigments in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight and very particularly preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0212] As further colouring compounds (a2), the agent (a) used in the method may contain one or more direct dyes. Direct action dyes are dyes that act directly on the hair and do not require an oxidation step to form colour. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols.

[0213] Direct dyes in the sense of the present invention have a solubility in water (760 mmHg) at 25° C. of greater than 0.5 g / L and are therefore not considered pigments. Preferably, direct dyes in the sense of the present invention have a solubility in water (760 mmHg) at 25° C. of greater than 1 g / L.

[0214] Direct dyes can be classified into anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

[0215] In another preferred embodiment, the method is characterized in that the agent (a) contains as further coloring compound (a2) at least one anionic direct dye, cationic direct dye and / or non-ionic direct dye.

[0216] In another preferred embodiment, the method is characterized in that the agent (a) comprises at least one further coloring compound (a2) selected from the group consisting of anionic direct dyes, nonionic direct dyes and / or cationic direct dyes.

[0217] Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, Basic Violet 2, 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.

[0218] As non-ionic direct dyes it is possible to use non-ionic nitro and quinone dyes as well as natural azo dyes. Suitable non-ionic direct dyes are those described under the following 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 as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)-aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2 -Nitrobenzene, 4-amino-3-nitrophenol, 1-(2'-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

[0219] In the course of the investigations leading to the present invention, it was found that dyeings of particularly high colour strength can be produced by using agent (a) which contains at least one anionic direct dye.

[0220] Thus, in a very particularly preferred embodiment, the method is characterized in that the agent (a) further comprises, as further colouring compound (a2), at least one anionic direct dye.

[0221] Anionic direct dyes are also called acid dyes. Acid dyes are direct dyes that have at least one carboxylic acid group (-COOH) and / or at least one sulfonic acid group (-SO3H). Depending on the pH value, the protonated forms of the carboxylic acid or sulfonic acid groups (-COOH, -SO3H) can be converted to their deprotonated forms (-COO - , -SO3 - The proportion of the protonated form increases with decreasing pH. When direct dyes are used as their salts, the carboxylic or sulfonic acid groups are present in deprotonated form and are neutralized with the corresponding stoichiometrically equivalent cation to maintain electrical neutrality. Acid dyes can also be used in the form of their sodium salts and / or their potassium salts.

[0222] Acid dyes in the sense 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 considered as pigments. Preferably, acid dyes in the sense of the present invention have a solubility in water (760 mmHg) at 25° C. of more than 1 g / L.

[0223] The alkaline earth (e.g. calcium and magnesium) or aluminium salts of acid dyes often have lower solubilities than the corresponding alkali salts. If the solubility of these salts is less than 0.5 g / L (25°C, 760 mmHg), they are not included in the definition of direct dyes.

[0224] An essential feature of acid dyes is their ability to form an anionic charge, the carboxylic or sulfonic acid groups which are usually attached to various chromophore systems. Suitable chromophore systems are found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthan dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.

[0225] In one embodiment, a method for dyeing keratinous materials is preferred, characterized in that the agent (a) further comprises, as further coloring compound (a2), at least one anionic direct dye selected from the group consisting of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes, each of which contains at least one carboxylic acid group (-COOH), sodium carboxylate group (-COONa), potassium carboxylate group (-COOK), sulfonic acid group (-SO3H), sodium sulfonate group (-SO3Na) and / or potassium sulfonate group (-SO3K).

[0226] For example, one or more compounds from the following groups may 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°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°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°015), Acid Orange 10(CI 16230;Orange G sodium salt), Acid Orange 11(CI 45370), Acid Orange 15(CI 50120), Acid Orange 20(CI 14600), Acid Orange 24(BROWN 1;CI 20170;KATSU201;Sodium free;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-Rot 46, Real red D, FD&C Red Nr.2、Food Red 9、Naphthol red S)、Acid Red 33(Red 33、Fuchsia Red、D&C Red 33、CI 17200)、Acid Red 35(CI C.I.18065)、Acid Red 51(CI 45430、Pyrosin B、Tetraiodfluorescein、Eosin J、Iodeosin)、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℃53、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、C.I. 60730、COLIPA n°063)、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、C.I. Food Blue 2)、Acid Blue 62(CI 62045)、Acid Blue 74(E 132、CI 73015)、Acid Blue 80(CI 61585)、Acid Green 3(CI 42085、Foodgreen1)、Acid Green 5(CI 42095)、Acid Green 9(C.I.42100)、Acid Green 22(C.I.42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brilliant Acid Green BS, CI 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n°401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n°B15), Acid Black 52(CI 15711), Food Yellow 8(CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1. .

[0227] For example, the water solubility of anionic direct dyes can be measured in the following way: 0.1 g of anionic direct dye is introduced into a beaker. A magnetic stir bar is added. Then 100 mL of water is added. The mixture is heated to 25°C while stirring on a magnetic stirrer. Stir for 60 minutes. The aqueous mixture is then visually evaluated. If undissolved residues are still present, increase the amount of water, for example in 10 mL increments. Add water until the amount of dye used is completely dissolved. If the dye-water mixture cannot be visually evaluated due to the high strength of the dye, filter the mixture. If undissolved dye remains on the filter paper, repeat the solubility test with more water. If 0.1 g of anionic direct dye dissolves in 100 mL of water at 25°C, the solubility of the dye is 1 g / L.

[0228] Acid Yellow 1 is referred to as 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, disodium salt, and has a solubility in water (25° C.) of at least 40 g / L. Acid Yellow 3 is a mixture of the mono- and disulfonic acid sodium salts of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a solubility in water (25° C.) of 20 g / L. Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, whose solubility in water is greater than 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 is highly soluble in water at 25°C. Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonate. Its solubility in water is greater than 7 g / L at 25 °C. Acid Red 18 is the trisodium salt of 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonate and has very high water solubility of greater than 20% by weight. Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate and has a solubility in water of 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, and its solubility in water is greater than 10 g / L (25° C.). Acid Blue 9 is the disodium salt of 2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonate and has a solubility in water greater than 20% by weight (25° C.).

[0229] Therefore, a particularly preferred method is such that the agent (a) is 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 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 D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1.

[0230] The direct dyes, in particular the anionic direct dyes, can be used in various amounts in the agent (a) depending on the desired color strength. Particularly good results are obtained when the agent (a) contains one or more direct dyes as further coloring compounds (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, very particularly preferably 0.5 to 4.5% by weight, based on the total weight of the agent (a).

[0231] In another preferred embodiment, the method is characterized in that agent (a) further contains one or more direct dyes as further coloring compounds (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight and very particularly preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0232] Silicone polymer (a3) In another very particularly preferred embodiment, the agent (a) used in the process further comprises at least one silicone polymer (a3).

[0233] Silicone polymers, sometimes simply called silicones, are understood to be poly(organo)siloxanes. Silicone polymers are a class of synthetic polymers in which silicon atoms are linked through oxygen atoms.

[0234] Silicone polymers are macromolecules that have a molecular weight of at least 500 g / mol, preferably at least 1000 g / mol, more preferably at least 2500 g / mol, particularly preferably at least 5000 g / mol, and comprise repeating organic units.

[0235] The maximum molecular weight of a silicone polymer depends on the degree of polymerization (the number of monomers being polymerized) and the batch size, and is determined in part by the polymerization method. For purposes of this invention, a maximum molecular weight of a silicone polymer is defined as 10 7 g / mol or less, preferably 10 6 g / mol or less, particularly preferably 10 5 It is preferably less than g / mol.

[0236] Silicone polymers contain many Si-O repeating units, where the Si atoms may carry organic groups, such as alkyl or substituted alkyl groups.

[0237] The silicone polymer, depending on its high molecular weight, is based on more than 10 Si-O repeat units, preferably more than 50 Si-O repeat units, more preferably more than 100 Si-O repeat units, most preferably more than 500 Si-O repeat units.

[0238] The silicone polymer (a3) ​​contained in agent (a) is therefore different from the silane (a1) also contained in agent (a).

[0239] Thus, in one embodiment, the method for dyeing keratinous materials comprises the step of: (a3) at least one silicone polymer It is preferred that the composition is characterized by comprising:

[0240] In the investigations leading to the present invention, it was found that the incorporation of a silicone polymer (a3) ​​into agent (a) leads to an improvement in the feel of the hair.

[0241] The film formed by oligomerization or polymerization of organosilicon compound (silane) (a1) may show some degree of tackiness or even flexibility, especially when using a large amount of silane (a1), which may have a negative effect on the feel of keratinous materials on the one hand and on the durability of the film on the other hand.Without being bound by this theory, it is believed that the simultaneous application of silane (a1) and silicone polymer (a3) ​​in agent (a) leads to a mutual reaction or interaction of these two components.When silane and silicone polymer are used together, as mentioned above, the silane forms a film, and the silicone polymer is incorporated into this film or aggregates in this film.The film formed in this way has higher flexibility, flexibility and durability, and is less brittle.

[0242] It has therefore been observed that the rheological properties of the film produced by agent (a) can be improved by the addition of at least one silicone polymer (a3). In the presence of silicone polymer (a3), the film becomes stronger or harder, resulting in a less sticky, smoother and better looking colored keratinous material. The higher film strength also has a positive effect on the fastness of the keratinous material, in particular on the rub fastness. The dyed film is more durable when in contact with combs, brushes and textile products, and therefore shows low abrasion when in contact with such items.

[0243] The above-mentioned advantages are particularly pronounced when certain silicone polymers (a3) ​​are used.It has therefore been found to be particularly preferred when the agent (a) used in the method comprises at least one alkoxy-modified silicone polymer and / or at least one amino-modified silicone polymer (a3).

[0244] Thus, in one embodiment, the method for dyeing keratinous materials comprises the step of: (a3) at least one alkoxy- and / or amino-modified silicone polymer It is preferred that the composition is characterized by comprising:

[0245] In another preferred embodiment, the method is characterized in that the agent (a) comprises at least one alkoxy-modified silicone polymer.

[0246] An alkoxy-modified silicone is a silicone whose structure comprises at least one alkoxy structural unit. This alkoxy structural unit can be, for example, an alkoxy group. The alkoxy group is a C2-C 10It is understood that the alkoxy group is an alkoxy group. The alkoxy group may be terminal with respect to the silicone (i.e., present, for example, as the group -O-CH3 or the group -O-CH2-CH3). However, it is equally according to the present invention if the alkoxy group itself still has a substituent, in which case the alkoxy modification is understood to be at least one group present on the silicone, such as (-CH2-CH2-O-), (-CH2-CH2-CH2-O-), (-CH(CH3)-CH2-O-), (-CH2-CH(CH3)-CH2-O-) or (-CH2-CH2-CH2-CH2-O-). Preferably, the alkoxy modified silicone (A) has at least one group (-CH2-CH2-O-) and / or (-CH2-CH2-CH2-O-).

[0247] The alkoxy group may be linked to the silicone through either a carbon atom or an oxygen atom, for example, the silicone may have structural units represented by the formula (Sa), (Sb), (Sc) and / or (Sd): TIFF0007657770000039.tif175168

[0248] It is particularly preferred that the alkoxy-modified silicone polymer (a3) ​​has more than one alkoxy group, i.e., the silicone polymer (a3) ​​is polyalkoxylated. Polyalkoxylated silicones contain, as structural units, polyoxyalkylene groups, polyoxyethylene groups (i.e., [-CH2-CH2-O-] m (i.e., groups of the type [-CH(CH3)-CH2-O-] m and / or [-CH2-CH2-CH2-O-] m Preferably, the number of polyoxyalkylene units in the silicone polymer is at least 2. Thus, m is an integer equal to or greater than 2.

[0249] Particularly preferably, the alkoxy-modified silicone (a3) ​​is a non-ionic silicone, which has neither a positive nor a negative charge.

[0250] Very particularly suitable polyalkoxylated silicones (a3) ​​have the formula (SI): TIFF0007657770000040.tif71168 [wherein n is an integer from 2 to 20, preferably an integer from 4 to 18, more preferably an integer from 6 to 16, even more preferably an integer from 8 to 14, and most preferably the number 12] The compound contains at least one structural unit represented by the formula:

[0251] The positions marked with an asterisk * in the above formula represent the free valence of the corresponding bond, which may then be to an additional Si atom, an additional O atom and / or an additional C atom.

[0252] Thus, in one embodiment, the method for dyeing keratinous materials comprises the step of: TIFF0007657770000041.tif71168 [wherein n is an integer from 2 to 20, preferably an integer from 4 to 18, more preferably an integer from 6 to 16, even more preferably an integer from 8 to 14, and most preferably the number 12] Preferably, said silicone polymer (a3) ​​comprises at least one structural unit represented by the formula:

[0253] Preferred alkoxy-modified silicone polymer (a3) ​​may contain one or more structural units of general formula (SI) and further structural units that are structurally different from the units of formula (SI). Particularly preferably, the alkoxy-modified silicone polymer further contains one or more dimethylsiloxane units. Depending on whether the silicone is linear or branched, it has two (in the case of linear silicone) or more (in the case of branched silicone) end groups. It has been found to be particularly advantageous when the silicone polymer (a3) ​​has in each case a trimethylsilyloxy group (i.e. the group -O-Si(CH3)3) as end group.

[0254] Thus, in another particularly preferred embodiment, the method comprises the steps of: (a) a compound represented by the formula (SI), (S-II), (S-III) and (S-IV): TIFF0007657770000042.tif150160 [wherein, independently in each structural unit (SI), n is in each occurrence an integer from 2 to 20, preferably an integer from 4 to 18, more preferably an integer from 6 to 16, even more preferably an integer from 8 to 14, and most preferably the number 12] The silicone polymer (a3) ​​is characterized in that it comprises at least one silicone polymer (a3) ​​composed of structural units represented by the following formula:

[0255] In the present specification, silicone polymer (a3) ​​composed of structural units of formula (SI), formula (S-II), formula (S-III) and formula (S-IV) is understood to mean silicones that exclusively have (in each case one or more) structural units of formula (SI), (S-II), (S-III) and (S-IV).Here, silicones may also contain various structural units of formula (SI), each of which is differentiated by its number n.

[0256] The positions marked with an asterisk in the structural units each represent a point of attachment to other structural units. For example, a very particularly preferred silicone polymer (a3) ​​composed of structural units of the formulae (SI), (S-II), (S-III) and (S-IV) has the following structure: TIFF0007657770000043.tif66169, in which x and y are selected depending on the desired molecular weight of the silicone and n represents one of the above-mentioned preferred or particularly preferred integers according to the invention. may have

[0257] Both low molecular weight alkoxy-modified silicones and high molecular weight alkoxy-modified silicones can be used as silicone polymer (a3). Particularly beneficial effects are observed for silicone polymers (a3) ​​having a molar mass of 800 to 10,000 g / mol, preferably 1,000 to 9,000 g / mol, more preferably 2,000 to 8,000 g / mol, particularly preferably 2,500 to 5,000 g / mol.

[0258] Particularly suitable silicone polymers are Abil B 8843, PEG-14 Dimethicone, from Evonik Dow Corning Xiameter OFX 0193 Fluid, PEG-12 Dimethicone Includes:

[0259] Particularly satisfactory results are also obtained when an agent (a) comprising an amino-modified silicone polymer (a3) ​​is used in the process. The amino-modified silicone polymer is also sometimes called amino-functionalized silicone polymer or aminosilicone.

[0260] In another preferred embodiment, the method is characterized in that agent (a) comprises at least one amino-modified silicone polymer.

[0261] The agent (a) may contain one or more different amino-modified silicone polymers (a3). Such silicones may, for example, be of the formula (SV): TIFF0007657770000044.tif990 [wherein R is a hydrocarbon or a hydrocarbon group having 1 to about 6 carbon atoms, and Q is a group represented by the general formula: -R 1 HZ (where R 1is a divalent linking group bonded to hydrogen, the group Z is composed of carbon and hydrogen atoms, or composed of carbon, hydrogen and oxygen atoms, or composed of carbon, hydrogen and nitrogen atoms, and Z is an organic amino functional group containing at least one amino functional group, a has a value ranging from about 0 to about 2, b has a value ranging from about 1 to about 3, a+b is 3 or less, c is a number ranging from about 1 to about 3, x is a number ranging from 1 to about 2000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, y is a number ranging from about 20 to about 10,000, preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M is a suitable silicone end group known in the prior art, preferably trimethylsiloxy. The group may be characterized by: R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 8 1 Examples include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH2CH(CH3)CH2-, phenylene, naphthylene, CH2CH2SCH2CH2-, -CH2CH2OCH2-, -OCH2CH2-, -OCH2CH2CH2-, CH2CH(CH3)C(O)OCH2-, -(CH2)3CC(O)OCH2CH2-, -C6H4C6H4-, -C6H4CH2C6H4-, and (CH2)3C(O)SCH2CH2-.

[0262] Z is an organic amino functional group containing at least one amino functional group. One formula for Z is NH(CH2) z NH2, where z is 1 or greater. Another formula for Z is -NH(CH2) z (CH2) zz NH, z and zz are each independently 1 or greater, and the structure includes a diamino ring structure such as piperazinyl. Z is most preferably a -NHCH2CH2NH2 group. Another formula for Z is -N(CH2) z (CH2) zz NX2 or -NX2, where each X in X2 is independently selected from the group consisting of hydrogen and an alkyl group having 1 to 12 carbon atoms, and zz is 0.

[0263] Q is most preferably a polar amine functional group represented by the formula -CH2CH2CH2NHCH2CH2NH2, where a ranges from about 0 to about 2, b ranges from about 2 to about 3, a+b is 3 or less, and c is a number ranging from about 1 to about 3. c SiO (4-c) / 2 R for units a Q b SiO (4-a-b) / 2 The molar ratio of units ranges from about 1:2 to 1:65, preferably from about 1:5 to about 1:65, and most preferably from about 1:15 to about 1:20. When more than one silicone of the above formula is used, the various variable substituents of the above formula may be different for the various silicone components present in the silicone mixture.

[0264] In a particularly preferred embodiment, the method comprises the step of reacting a compound represented by formula (S-VI): TIFF0007657770000045.tif8129[In the formula, -G is -H, phenyl group, -OH, -O-CH3, -CH3, -O-CH2CH3, -CH2CH3, -O-CH2CH2CH3, -CH2CH2CH3, -O-CH(CH3)2, -CH(CH3)2, -O-CH2CH2 CH2CH3, -CH2CH2CH2CH3, -O-CH2CH(CH3)2, -CH2CH(CH3)2, -O-CH(CH3)CH2CH3, -CH(CH3)CH2CH3, -OC(CH3)3, -C(CH3)3, -a represents a number from 0 to 3, especially 0; -b represents a number between 0 and 1, especially 1, - m and n are numbers whose sum (m+n) is between 1 and 2000, preferably between 50 and 150, n preferably assumes a value between 0 and 1999 and between 49 and 149, and m preferably assumes a value between 1 and 2000 and between 1 and 10, -R' is -QN(R")-CH2-CH2-N(R")2 -QN(R")2 -QN + (R")3A - -QN + H(R")2A - -QN + H2(R")A - -QN(R")-CH2-CH2-N + R"H2A - is a monovalent group selected from each Q is a chemical bond, -CH2-, -CH2-CH2-, -CH2CH2CH2-, C(CH3)2-, -CH2CH2CH2CH2-, -CH2C(CH3)2-, -CH(CH3)CH2CH2-; R" is -H, -phenyl, -benzyl, CH2-CH(CH3)Ph, C 1-20 alkyl groups, preferably the same or different groups selected from the group consisting of -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -CH2CH2CH2H3, -CH2CH(CH3)2, -CH(CH3)CH2CH3, -C(CH3)3, A represents an anion preferably selected from chloride, bromide, iodide or methosulfate. The method is characterized in that an agent (a), which is an amino-modified silicone polymer (a3) ​​represented by the following formula (1) is applied to a keratin material.

[0265] In another preferred embodiment, the method comprises the steps of: TIFF0007657770000046.tif25137 [wherein m and n are numbers whose sum (m+n) is between 1 and 2000, preferably between 50 and 150, n preferably assumes values ​​of 0 to 1999 and 49 to 149, and m preferably assumes values ​​of 1 to 2000 and 1 to 10] The method is characterized in that an agent (a) comprising at least one amino-modified silicone polymer (a3) ​​of the formula:

[0266] According to the INCI name, such a silicone is called trimethylsilylamodimethicone.

[0267] In another preferred embodiment, the method comprises the steps of: TIFF0007657770000047.tif23123 [wherein R represents -OH, -O-CH3 or -CH3 group, m, n1 and n2 are numbers whose sum (m+n1+n2) is between 1 and 2000, preferably between 50 and 150, the sum (n1+n2) preferably assuming a value of 0 to 1999 and 49 to 149, and m is preferably a number assuming a value of 1 to 2000 and 1 to 10] The method is characterized in that an agent (a) comprising at least one amino-modified silicone polymer (a3) ​​of the formula:

[0268] According to the INCI name, such amino-modified or amino-functionalized silicone polymers are known as amodimethicones.

[0269] Regardless of which amino-modified silicone is used, the agent (a) is preferably one that comprises an amino-modified silicone polymer with an amine value of more than 0.25 meq / g, preferably more than 0.3 meq / g, more preferably more than 0.4 meq / g. The amine value represents the milligram equivalent of amine per gram of amino-functional silicone. The amine value represents the milligram equivalent of amine per gram of amino-functional silicone.

[0270] In another preferred embodiment, the method comprises the steps of: TIFF0007657770000048.tif63163[in formula -m and n are numbers selected so that the sum (n+m) is in the range of 1 to 1000; - n is a number in the range of 0 to 999, and m is a number in the range of 1 to 1000, R1, R2 and R3 are the same or different and are each a hydroxy group or a C 1-4 represents an alkoxy group, -wherein at least one of R1 to R3 represents a hydroxy group. The method is characterized in that an agent (a) comprising at least one amino-modified silicone polymer (a3) ​​of the formula:

[0271] Another preferred method is to prepare a compound represented by the formula (SX) TIFF0007657770000049.tif59155[in formula -p and q are numbers selected so that the sum (p+q) is in the range of 1 to 1000; - p is a number in the range of 0 to 999, and q is a number in the range of 1 to 1000, R1 and R2 are different and are a hydroxy group or a C 1-4 represents an alkoxy group, and at least one of R1 and R2 represents a hydroxy group. The method is characterized in that an agent (a) comprising at least an amino-functional silicone polymer represented by the formula:

[0272] Silicones of formula (S-IX) and formula (SX) differ in the group at the Si atom that bears the nitrogen-containing group. In formula (S-IX), R2 is a hydroxy group or a C 1-4 represents an alkoxy group, whereas the group in formula (SX) is a methyl group. The individual Si groups marked with the subscripts m and n or p and q do not have to be present as blocks, rather the individual units may be present in a statistical distribution. That is, in formula (S-IX) and formula (SX), not all R1-Si(CH3)2 groups are bonded to -[O-Si(CH3)2] groups.

[0273] Also, the formula (S-XI): TIFF0007657770000050.tif53123[in the formula, A represents the group -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3, D represents the group -H, -Si(CH3)3, -Si(CH3)2OH, -Si(CH3)2OCH3; b, n, and c each represent an integer of 0 to 1000; For more information -n>0 and b+c>0 - at least one of the conditions A=-OH or D=-H is met. It has been found that the method of applying to the keratin fibres an agent (a) comprising at least one amino-modified silicone polymer (a3) ​​of the formula:

[0274] In the above formulas (S-XI), the individual siloxane units having the subscripts b, c and n are statistically distributed, ie, not necessarily block copolymers.

[0275] A particularly advantageous effect in terms of improving the rub fastness was observed when the agent (a) was applied to the keratinous material in a method comprising a specific 4-morpholinomethyl-substituted silicone polymer (a3). This very particularly preferred amino-functionalized silicone polymer has the formula (S-XIII): Contains at least one structural unit represented by TIFF0007657770000051.tif58130.

[0276] Thus, in one embodiment, the agent (a) has the formula (S-XIII): A method for dyeing keratinous materials is preferred, characterized in that the dye contains at least one silicone polymer (a3) ​​which contains at least one structural unit of the formula TIFF0007657770000052.tif58130.

[0277] Particularly advantageous effects in terms of improving the rub fastness have also been observed when the method involves applying to the keratinous material an agent (a) that comprises a specific 4-morpholinomethyl-substituted silicone polymer (a3). This very particularly preferred amino-functionalized silicone polymer is represented by the formula (S-XII) and the formula (S-XIII): Contains the structural unit indicated by TIFF0007657770000053.tif57170.

[0278] In an obviously very particularly preferred embodiment, the method comprises the steps of: (a) a compound represented by the formula (S-XII) and the formula (S-XIII): The composition is characterized in that it contains at least one amino-modified silicone polymer (a3) ​​containing a structural unit represented by TIFF0007657770000054.tif57170.

[0279] The corresponding 4-morpholinomethyl substituted silicone polymers are described below.

[0280] A very particularly preferred amino-functionalized silicone polymer is known as amodimethicone / morpholinomethylsilsesquioxane copolymer and is commercially available in the form of the raw material Belsil ADM 8301 E from Wacker.

[0281] As 4-morpholinomethyl substituted silicones, for example, those represented by the formulae (S-XII), (S-XIII') and (S-XIV'): TIFF0007657770000055.tif73168[In the formula, R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3 or -O-CH(CH3)2; R2 is -CH3, -OH or -OCH3. Silicones having the structural unit represented by the following formula can be used.

[0282] Particularly preferred agents (a) have the formula (S-XV): TIFF0007657770000056.tif66169[In the formula, R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3 or -O-CH(CH3)2; R2 is -CH3, -OH or -OCH3; B represents the group -OH, -O-Si(CH3)3, -O-Si(CH3)2OH, -O-Si(CH3)2OCH3, D represents the group -H, -Si(CH3)3, -Si(CH3)2OH, -Si(CH3)2OCH3; a, b, and c each independently represent an integer from 0 to 1000, provided that a+b+c>0; m and n each independently represent an integer of 1 to 1000; however, At least one of the conditions B=-OH or D=-H is satisfied, The units a, b, c, m and n are statistically distributed or block-shaped in the molecule. The silicone comprises at least one 4-morpholinomethyl substituted silicone represented by the formula:

[0283] In structural formula (Si-VI), it is intended to indicate that the siloxane groups n and m are not necessarily directly bonded to the end groups B or D, respectively. Rather, in preferred formula (Si-VI), a>0 or b>0, and in particularly preferred formula (Si-VI), a>0 and c>0, i.e., the end groups B or D are preferably bonded to dimethylsiloxy groups. Also, in formula (Si-VI), the siloxane units a, b, c, m and n are preferably statistically distributed.

[0284] The silicones used according to the invention and having the formula (Si-VI) may be trimethylsilyl-terminated (D or B=-Si(CH3)3), but may also be dimethylsilylhydroxy-terminated at both ends or dimethylsilylhydroxy-terminated and dimethylsilylmethoxy-terminated at one end. Particularly preferred silicones according to the invention are those in which, for each link, B=-O-Si(CH3)2OH and D=-Si(CH3)3 B=-O-Si(CH3)2OH and D=-Si(CH3)2OH B=-O-Si(CH3)2OH and D=-Si(CH3)2OCH3 B=-O-Si(CH3)3 and D=-Si(CH3)2OH B=-O-Si(CH3)2OCH3 and D=-Si(CH3)2OH The silicone is selected from those in which

[0285] In order to produce a particularly durable film, agent (a) comprises a silicone polymer, in particular an alkoxy-modified silicone polymer and / or an amino-modified silicone polymer, preferably in a specific amount range.

[0286] When an agent (a) containing one or more silicone polymers (a3) ​​in a total amount of 0.1 to 8% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight and very particularly preferably 0.1 to 0.5% by weight, based on the total weight of agent (a), is used in the process, particularly flexible films with low adhesion are obtained.

[0287] In another preferred embodiment, the method is characterized in that the agent (a) contains one or more silicone polymers (a3) ​​in a total amount of 0.1 to 15% by weight, preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight and very particularly preferably 2 to 8% by weight, relative to the total weight of agent (a).

[0288] In an obviously very particularly preferred embodiment, the method is characterized in that the agent (a) contains one or more alkoxy-modified silicone polymers (a3) ​​in a total amount of 0.1 to 15% by weight, preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight and very particularly preferably 2 to 8% by weight, relative to the total weight of agent (a).

[0289] In an obviously very particularly preferred embodiment, the method is characterized in that agent (a) contains one or more amino-modified silicone polymers in a total amount of 0.1 to 15% by weight, preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight and most preferably 2 to 8% by weight, relative to the total weight of agent (a).

[0290] pH value of agent (a) It has been found to be advantageous if the agent (a) is constituted in the form of a water-containing agent adjusted to an alkaline pH.

[0291] To adjust this pH value, agent (a) may contain at least one alkalizing agent.

[0292] Thus, in order to adjust the desired pH, agent (a) may contain at least one alkalizing agent. The pH values ​​for the purposes of the present invention are pH values ​​measured at a temperature of 22° C.

[0293] As an alkalizing agent, agent (a) may contain, for example, ammonia, alkanolamines and / or basic amino acids.

[0294] The alkanolamine that can be the agent in the composition is preferably selected from the primary amines having C2-C6 alkyl group with at least one hydroxyl group.Preferred alkanolamine is selected from the group consisting of 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-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol.

[0295] 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 the agent comprises an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol as alkalizing agent.

[0296] For the purposes of the present invention, amino acids are organic compounds that contain in their structure at least one protic amino group and at least one -COOH or at least one -SO3H group. Preferred amino acids are aminocarboxylic acids, in particular α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0297] A basic amino acid is an amino acid that has an isoelectric point pI greater than 7.

[0298] The basic α-aminocarboxylic acid contains at least one asymmetric carbon atom. In the present invention, both enantiomers can be equally used as specific compounds or mixtures thereof, in particular as racemates. However, it is particularly preferred to use the naturally preferred isomeric form, usually in the L configuration.

[0299] The basic amino acid is preferably selected from the group consisting of arginine, lysine, ornithine and histidine, particularly preferably arginine and lysine.Accordingly, in another particularly preferred embodiment, the agent is characterized in that the alkalizing agent is a basic amino acid selected from the group consisting of arginine, lysine, ornithine and / or histidine.

[0300] The product may also contain other alkalizing agents, in particular inorganic alkalizing agents. The inorganic alkalizing agents used according to the invention are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

[0301] 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-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

[0302] Agent (a) is preferably adjusted to a pH value in the alkaline range, although in principle it may be necessary to also use small amounts of an acidifier for fine adjustment to the desired pH value. Acidifiers suitable in the present invention are, for example, citric acid, lactic acid, acetic acid or also dilute mineral acids (e.g. hydrochloric acid, sulfuric acid, phosphoric acid).

[0303] However, in the course of research leading to the present invention, it was found that the presence of an alkalizing agent or adjustment to an alkaline pH is essential for the formation of a durable film on keratinous materials. The presence of an excessive amount of acid can have a detrimental effect on the strength of the film. It was therefore found to be preferable to keep the amount of acid used in agent (a) as low as possible. For this reason, it is advantageous when the total amount of organic and / or inorganic acid contained in agent (a) does not exceed a certain value.

[0304] In another preferred embodiment, the method is characterized in that the total amount of organic acids selected from the group consisting of citric acid, tartaric acid, malic acid and lactic acid contained in agent (a) is less than 1 wt.-%, preferably less than 0.7 wt.-%, more preferably less than 0.5 wt.-%, even more preferably less than 0.1 wt.-%, most preferably less than 0.01 wt.-%.

[0305] In another preferred embodiment, the method is characterized in that the total amount of inorganic acids selected from the group consisting of hydrochloric acid, sulfuric acid and phosphoric acid contained in agent (a) is less than 1% by weight, preferably less than 0.7% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.1% by weight and very particularly preferably less than 0.01% by weight.

[0306] The maximum total amount of acid contained in agent (a) is always relative to the total weight of agent (a).

[0307] Agent (b) The method for treating keratinous materials comprises, in addition to the application of agent (a), the application of agent (b). The agent (b) used in the method is characterized in that it comprises at least one sealant (b1).

[0308] Agent (b) is a post-treatment agent, the application of which to the keratinous material treated with agent (a) has the effect of making the coloration obtained in the process more durable. In particular, the use of agent (b) makes it possible to improve the wash fastness and rub fastness of the dyeings obtained in the process.

[0309] It is preferred that the sealing agent (b1) comprises a compound selected from the group consisting of film-forming polymers, alkalizing agents, acidifying agents and mixtures thereof.

[0310] It may be preferred that the sealant (b1) comprises a film-forming polymer.

[0311] Polymer is a macromolecule that has a molecular weight of at least 1000 g / mol, preferably at least 2500 g / mol, particularly preferably at least 5000 g / mol, and is composed of identical repeating organic units.The polymer of the present invention can be a synthetic polymer that is produced by polymerization of one type of monomer or by polymerization of several types of monomers that are structurally different from each other.When a polymer is produced by polymerization of one type of monomer, it is called a homopolymer.When several types of monomers that are structurally different are used in polymerization, the resulting polymer is called a copolymer.

[0312] The maximum molecular weight of the polymer depends on the degree of polymerization (the number of monomers being polymerized) and the batch size, which is determined by the polymerization method. In the present invention, the maximum molecular weight of the film-forming hydrophobic polymer is 10 7 g / mol or less, preferably 10 6 g / mol or less, particularly preferably 10 5 It is preferred that it is less than or equal to g / mol.

[0313] In the sense of the present invention, a film-forming polymer is a polymer capable of forming a film on a substrate, for example on a keratinous substance or on a keratinous fiber. The formation of a film can be demonstrated, for example, by observing a keratinous substance treated with the polymer under a microscope.

[0314] The film-forming polymer in agent (b) may be hydrophilic or hydrophobic.

[0315] In a first embodiment, it may be preferred to use at least one hydrophobic film-forming polymer as sealant (b1) in agent (b).

[0316] A hydrophobic polymer is a polymer that has a solubility in water of less than 1% by weight at 25° C. (760 mmHg).

[0317] The solubility of a film-forming hydrophobic polymer in water can be measured, for example, as follows: Place 1 g of polymer in a beaker. Make up to 100 g with water. Add a magnetic stir bar and heat to 25° C. on a magnetic stirrer while stirring the mixture. Allow it to stir for 60 minutes. Then visually evaluate this aqueous mixture. If the polymer-water mixture cannot be visually evaluated due to high turbidity of the mixture, filter the mixture. If undissolved polymer remains on the filter paper, the solubility of the polymer is less than 1% by weight.

[0318] These include acrylic acid type polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose polymers, nitrocellulose polymers, silicone polymers, acrylamide type polymers and polyisoprene.

[0319] Particularly suitable film-forming hydrophobic polymers are, for example, polymers 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 vinylpyrrolidone, 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.

[0320] In another preferred embodiment, the method is characterized in that the agent (b) comprises as sealant (b1) at least one film-forming hydrophobic polymer 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 vinylpyrrolidone, 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.

[0321] It has been found that film-forming hydrophobic polymers selected from the group of synthetic polymers, polymers obtained by radical polymerization or natural polymers are particularly suitable for solving the problems in the present invention.

[0322] Other particularly suitable film-forming hydrophobic polymers are olefins, such as cycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinyl amides, at least one C1-C 20 Alkyl, aryl or C2-C 10 It can be selected from homopolymers or copolymers of esters or amides of (meth)acrylic acid carrying hydroxyalkyl groups.

[0323] Other film-forming hydrophobic polymers may be selected from homopolymers 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 (meth)acrylate, 3-hydroxypropyl (meth)acrylate and / or mixtures thereof.

[0324] Another film-forming hydrophobic polymer is (meth)acrylamide, N-alkyl (meth)acrylamide, C2-C 18 It can be selected from those having an alkyl group, for example, homopolymers or copolymers of N-ethylacrylamide, N-tert-butylacrylamide, N-octylacrylamide, and N-di(C1-C4)alkyl(meth)acrylamide.

[0325] Other preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or their C1-C6 alkyl esters, which are sold under the INCI name Acrylates Copolymer. A suitable commercial product is, for example, Aculyn® 33 from Rohm & Haas. Also preferred are copolymers of acrylic acid, methacrylic acid or their C1-C6 alkyl esters and esters of ethylenically unsaturated acids with alkoxylated fatty alcohols. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid, and suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20.

[0326] Very particularly preferred commercially available polymers are, for example, Aculyn® 22 (acrylates / steareth-20 methacrylate copolymer), Aculyn® 28 (acrylates / beheneth-25 methacrylate copolymer), Structure 2001® (acrylates / steareth-20 itaconate copolymer), Structure 3001® (acrylates / ceteth-20 itaconate copolymer), Structure Plus® (acrylates / aminoacrylate C10-30 alkyl PEG-20 itaconate copolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (acrylates / C10-30 alkyl acrylate crosspolymer), Synthalen W 2000® (acrylates / palmethane-25 acrylate copolymer) or Rohme und The product is Soltex OPT (Acrylates / C12-22 Alkyl Methacrylate Copolymer), available from Haas.

[0327] Suitable polymers based on vinyl monomers include, for example, homo- and copolymers of N-vinylpyrrolidone, vinylcaprolactam, vinyl-(C1-C6)alkyl-pyrrole, vinyloxazole, vinylthiazole, vinylpyrimidine or vinylimidazole.

[0328] Also particularly suitable are the copolymers octylacrylamide / acrylates / butylaminoethyl methacrylate copolymers, such as those sold under the trade names AMPHOMER® or LOVOCRYL® 47 by NATIONAL STARCH, or the acrylates / octylacrylamide copolymers sold under the trade names DERMACRYL® LT and DERMACRYL® 79 by NATIONAL STARCH.

[0329] Suitable olefin-based polymers include homopolymers and copolymers of ethylene, propylene, butene, isoprene, and butadiene.

[0330] In another embodiment, the film-forming hydrophobic polymer may be a block copolymer comprising at least one block of styrene or a styrene derivative. Such block copolymers may be copolymers comprising one or more blocks in addition to the styrene block, such as styrene / ethylene, styrene / ethylene / butylene, styrene / butylene, styrene / isoprene, styrene / butadiene. Such polymers are marketed by BASF under the trade name "Luvitol HSB".

[0331] Surprisingly, it has been found that particularly strong, wash-fast colorations are obtained when the agent (b) comprises as sealant (b1) at least one film-forming polymer selected from the group consisting 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 vinylpyrrolidone, 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.

[0332] In another preferred embodiment, the method is characterized in that the agent (b) comprises as sealant (b1) at least one film-forming polymer selected from the group consisting 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 vinylpyrrolidone, 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.

[0333] In another embodiment, it may be preferred to use at least one hydrophilic film-forming polymer in agent (b) as sealant (b1).

[0334] A hydrophilic polymer is a polymer that has a solubility in water at 25° C. (760 mmHg) of greater than 1% by weight, preferably greater than 2% by weight.

[0335] The solubility of a film-forming hydrophilic polymer in water can be measured, for example, as follows: Place 1 g of polymer in a beaker. Make up to 100 g with water. Add a magnetic stir bar and heat to 25° C. on a magnetic stirrer while stirring the mixture. Allow it to stir for 60 minutes. This aqueous mixture is then visually assessed. A fully dissolved polymer will appear homogeneous to the naked eye. If the polymer-water mixture cannot be visually assessed due to high turbidity of the mixture, filter the mixture. If no undissolved polymer remains on the filter paper, the solubility of the polymer is greater than 1% by weight.

[0336] Nonionic, anionic and cationic polymers can be used as the film-forming hydrophilic polymer.

[0337] Suitable film-forming hydrophilic polymers may, for example, be selected from the group consisting 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.

[0338] Furthermore, it is particularly preferred to use polyvinylpyrrolidone (PVP) and / or vinylpyrrolidone-containing copolymers as film-forming hydrophilic polymers.

[0339] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises at least one film-forming hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone (PVP) and copolymers of polyvinylpyrrolidone as sealant (b1).

[0340] It is further preferred if the agent comprises polyvinylpyrrolidone (PVP) as the film-forming hydrophilic polymer. Surprisingly, the wash fastness of the dyeings obtained with the PVP-containing agent (b) was also very good.

[0341] Particularly suitable polyvinylpyrrolidones are available, for example, under the name Luviskol® K from BASF SE, in particular under the name Luviskol® K 90 or Luviskol® K 85 from BASF SE.

[0342] The polymer PVP K 30 sold by Ashland (ISP, POI Chemical) can also be used as another very suitable polyvinylpyrrolidone (PVP). PVP K 30 is a polyvinylpyrrolidone that is highly soluble in cold water and has the CAS number 9003-39-8. The molecular weight of PVP K 30 is about 40000 g / mol.

[0343] Other particularly suitable polyvinylpyrrolidones are the materials 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, available from BASF.

[0344] The use of film-forming hydrophilic polymers from the group of the polyvinylpyrrolidone copolymers as sealant (b1) also leads to particularly good and wash-fast colouring results.

[0345] Vinylpyrrolidone-vinyl ester copolymers, such as those sold under the trademark Luviskol® (BASF), are particularly suitable film-forming hydrophilic polymers. Luviskol® VA 64 and Luviskol® VA 73, both vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred non-ionic polymers.

[0346] Of the vinylpyrrolidone-containing copolymers, styrene / VP copolymer and / or vinylpyrrolidone-vinyl acetate copolymer and / or VP / DMAPA acrylate copolymer and / or VP / vinylcaprolactam / DMAPA acrylate copolymer are particularly preferred in cosmetic compositions.

[0347] Vinylpyrrolidone-vinyl acetate copolymers are sold by BASF SE under the name Luviskol® VA. For example, VP / vinylcaprolactam / DMAPA acrylate copolymers are sold by Ashland Inc under the trade name Aquaflex® SF-40. For example, VP / DMAPA acrylate copolymers are sold by Ashland under the name Styleze CC-10, which is a highly preferred vinylpyrrolidone-containing copolymer.

[0348] Other suitable copolymers of polyvinylpyrrolidone may also be obtained by reaction of N-vinylpyrrolidone with at least one further monomer from the group consisting of V-vinylformamide, vinyl acetate, ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactone and / or vinyl alcohol.

[0349] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises at least one film-forming hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / styrene copolymer, vinylpyrrolidone / ethylene copolymer, vinylpyrrolidone / propylene copolymer, vinylpyrrolidone / vinyl caprolactam copolymer, vinylpyrrolidone / vinyl formamide copolymer and / or vinylpyrrolidone / vinyl alcohol copolymer as sealant (b1).

[0350] Another fussy copolymer of vinylpyrrolidone is the polymer known by the INCI name Maltodextrin / VP Copolymer.

[0351] It has also been possible to obtain intensely coloured keratinous materials, especially hair, having particularly good wash fastness properties, when non-ionic film-forming hydrophilic polymers are used as the film-forming hydrophilic polymer.

[0352] In another embodiment, the agent (b) may comprise at least one non-ionic, film-forming hydrophilic polymer as sealant (b1).

[0353] According to the present invention, nonionic polymers are understood to be polymers that do not have structural units with permanent cationic or anionic groups that must be compensated by counterions under standard conditions in protic solvents, such as water, and remain electrically neutral. Cationic groups include quaternized ammonium groups, but do not include protonated amines. Anionic groups include carboxylic and sulfonic acid groups.

[0354] the below described: Polyvinylpyrrolidone, N-vinylpyrrolidone and copolymers of vinyl esters of N-vinylpyrrolidone and vinyl acetate of carboxylic acids containing 2 to 18 carbon atoms, Copolymers of N-vinylpyrrolidone, N-vinylimidazole and methacrylamide, Copolymers of N-vinylpyrrolidone, N-vinylimidazole and acrylamide, Copolymer of N-vinylpyrrolidone and N,N-di(C1-C4)alkylamino-(C2-C4)alkylacrylamide Preferred are formulations which comprise as non-ionic film-forming hydrophilic polymer at least one polymer selected from the group consisting of:

[0355] When using copolymers of N-vinylpyrrolidone and vinyl acetate, it is preferred if the molar ratio of structural units contained in the monomer N-vinylpyrrolidone to structural units contained in the polymer of the monomer vinyl acetate is in the range of 20:80 to 80:20, in particular 30:70 to 60:40. Suitable copolymers of vinylpyrrolidone 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.

[0356] Another particularly preferred polymer is selected from the INCI name VP / methacrylamide / vinylimidazole copolymer, which is available under the trade name Luviset Clear from BASF SE.

[0357] Another particularly preferred non-ionic film-forming hydrophilic polymer is the copolymer of N-vinylpyrrolidone and N,N-dimethylaminiopropylmethacrylamide, which is sold, for example, by ISP under the INCI name VP / DMAPA acrylates copolymer, e.g. under the trade name Styleze® CC 10.

[0358] The cationic polymer is a copolymer of N-vinylpyrrolidone, N-vinylcaprolactam, N-(3-dimethylaminopropyl) methacrylamide and 3-(methacryloylamino)propyl-lauryl-dimethylammonium chloride (INCI name: Polyquaternium-69), which is sold, for example, by ISP under the trade name AquaStyle® 300 (28-32% by weight of active substance in an ethanol-water mixture, molecular weight 350,000).

[0359] Other suitable film-forming hydrophilic polymers include: Vinylpyrrolidone-vinylimidazolium methchloride copolymers, offered under the names Luviquat® FC 370, FC 550 and the INCI names Polyquaternium-16 as well as FC 905 and HM 552; vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers (which are commercially available, for example under the name Aquaflex® SF 40, with acrylic esters and acrylic amides as third monomeric components); Examples include:

[0360] Polyquaternium-11 is a reaction product of diethyl sulfate with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. Suitable commercial products are available from BASF SE under the names Dehyquart® CC 11 and Luviquat® PQ 11 PN, or from Ashland Inc. under the names Gafquat 440, Gafquat 734, Gafquat 755 or Gafquat 755N.

[0361] Polyquaternium-46 is a reaction product of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulfate, and is available, for example, under the name Luviquat® Hold from BASF SE. Polyquaternium-46 is preferably used in an amount of 1-5% by weight, based on the total weight of the cosmetic composition. It is particularly preferred to use Polyquaternium-46 in combination with a cationic guar compound. It is even more highly preferred to use Polyquaternium-46 in combination with a cationic guar compound and Polyquaternium-11.

[0362] Suitable anionic film-forming hydrophilic polymers may be, for example, acrylic acid polymers, which may be in non-crosslinked or crosslinked form. Such products are sold under the trade names Carbopol 980, 981, 954, 2984 and 5984 by Lubrizol or under the names Synthalen M and Synthalen K by 3V Sigma (The Sun Chemicals, Inter Harz).

[0363] Examples of suitable film-forming hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum, carob gum.

[0364] Examples of suitable film-forming hydrophilic polymers from the group of the polysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.

[0365] Suitable film-forming hydrophilic polymers from the group of acrylamide are, for example, polymers prepared from monomers of (meth)acrylamido-C1-C4-alkylsulfonic acid or salts thereof. The corresponding polymers may be selected from the polymers of polyacrylamido-methanesulfonic acid, polyacrylamido-ethanesulfonic acid, polyacrylamido-propanesulfonic acid, poly-2-acrylamido-2-methylpropanesulfonic acid, poly-2-methylacrylamido-2-methylpropanesulfonic acid and / or poly-2-methylacrylamido-n-butanesulfonic acid.

[0366] Preferred polymers of poly(meth)acrylamide-C1-C4-alkyl-sulfonic acid are crosslinked and at least 90% neutralized. These polymers may be crosslinked or non-crosslinked.

[0367] Crosslinked fully or partially neutralized polymers of the poly-2-acrylamido-2-methylpropanesulfonic acid type are available under the INCI names "Ammonium polyacrylamido-2-methyl-propanesulfonate" or "Ammonium polyacryldimethyltauramide".

[0368] Another preferred polymer of this type is a crosslinked poly-2-acrylamido-2-methyl-propanesulfonic acid polymer, which is partially neutralized with ammonia, sold under the trade name Hostacerin AMPS by Clariant.

[0369] In another obviously very particularly preferred embodiment the method is characterized in that the agent (b) comprises at least one anionic film-forming polymer as sealant (b1).

[0370] In this context, the agent (b) comprises at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II): TIFF0007657770000057.tif29168[In the formula, M is a hydrogen atom, ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium. The best results were obtained when at least one film-forming polymer comprising as sealant (b1) was included.

[0371] In a further preferred embodiment, the method of the invention relates to a compound (b) comprising at least one structural unit of formula (PI) and at least one structural unit of formula (P-II): TIFF0007657770000058.tif29168[In the formula, M is a hydrogen atom, ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium. The composition is characterized in that it contains as a sealant (b1) at least one film-forming polymer comprising:

[0372] When M represents a hydrogen atom, the structural unit represented by formula (PI) is based on an acrylic acid unit.

[0373] When M represents an ammonium counterion, the structural unit of formula (PI) is based on the ammonium salt of acrylic acid.

[0374] When M represents a sodium counterion, the structural unit of formula (PI) is based on the sodium salt of acrylic acid.

[0375] When M represents a potassium counterion, the structural unit of formula (PI) is based on the potassium salt of acrylic acid.

[0376] When M represents one-half equivalent of a magnesium counter ion, the structural unit of formula (PI) is based on the magnesium salt of acrylic acid.

[0377] When M represents one-half equivalent of a calcium counterion, the structural unit of formula (PI) is based on the calcium salt of acrylic acid.

[0378] The one or more film-forming polymers are preferably used in the agent (b) in a specific quantitative range. In this connection, it has been found to be particularly preferred for solving the problem of the present invention when the agent (b) comprises one or more film-forming polymers as sealant (b1) in a total amount of 0.1 to 18% by weight, preferably 1 to 16% by weight, more preferably 5 to 14.5% by weight, very particularly preferably 8 to 12% by weight, relative to the total weight of the agent (b).

[0379] In a further preferred embodiment, the method is characterized in that agent (b) comprises one or more film-forming polymers as sealant (b1) in a total amount of 0.1 to 18% by weight, preferably 1 to 16% by weight, more preferably 5 to 14.5% by weight and very particularly preferably 8 to 12% by weight, relative to the total weight of agent (b).

[0380] The application of agent (b), which comprises a film-forming polymer as sealant (b1), is intended to seal and / or fix the colored film first formed by application of agent (a). By application of a second agent (b), which comprises a film-forming polymer as sealant (b1), the film-forming polymer (b1) is deposited as a further film on the colored film produced in the first layer. The multilayer film system thus produced shows improved resistance to external influences.

[0381] Here, the film produced by the agent (b) containing film-forming polymer as sealing agent (b1) is preferably not colored itself.This can also ensure that even if a certain degree of wear occurs on the second film formed by agent (b), it does not cause discoloration in the entire film system.Therefore, it is particularly preferred when agent (b) does not contain coloring compounds or contains only very small amounts of them.

[0382] In another embodiment, the sealing agent (b1) comprises an alkalizing agent.

[0383] Particularly preferably, the alkalizing agent is selected from the group consisting of ammonia, C2-C6 alkanolamines, basic amino acids, alkali metal hydroxides and alkaline earth metal hydroxides.

[0384] In another particularly preferred embodiment, the method is characterized in that the agent (b) comprises at least one alkalizing agent selected from the group consisting of ammonia, C2-C6 alkanolamines, basic amino acids, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal silicates, alkali metal metasilicates, alkaline earth metal silicates, alkaline earth metal metasilicates, alkali metal carbonates and alkaline earth metal carbonates as sealing agent (b1).

[0385] It has been found that aftertreatment with an ammonia-containing agent (b) has a particularly positive effect on improving the wash fastness and rub fastness properties of the dyeings obtained in the process.

[0386] In another very particularly preferred embodiment the method is characterized in that the agent (b) comprises ammonia as sealing agent (b1).

[0387] Satisfactory results were also obtained when the agent (b) contained at least one C2-C6 alkanolamine as sealing agent (b1).

[0388] The alkanolamine usable for agent (b) can be selected from the group of primary amines having C2-C6 alkyl groups with at least one hydroxyl group, for example.Preferred alkanolamines are selected from the group consisting of 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-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol.

[0389] In another preferred embodiment, the method of the invention is characterized in that the agent (b) comprises as sealing agent (b1) at least one alkalizing agent from the group of alkanolamines, preferably selected from the group consisting of 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-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol.

[0390] Likewise, satisfactory results are obtained when the composition (b) comprises at least one basic amino acid as sealing agent (b1).

[0391] For the purposes of the present invention, an amino acid is an organic compound that contains in its structure at least one protic amino group and at least one -COOH group or at least one -SO3H group. Preferred amino acids are aminocarboxylic acids, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0392] In the present invention, a basic amino acid is an amino acid with an isoelectric point pI greater than 7.0.

[0393] Basic α-aminocarboxylic acids contain at least one asymmetric carbon atom. In the present invention, both enantiomers can be used equally as specific compounds or mixtures thereof, especially as racemates. However, it is particularly advantageous to use the necessarily preferred isomer (usually the L-configuration).

[0394] The basic amino acid is preferably selected from the group consisting of arginine, lysine, ornithine and histidine, particularly preferably from the group consisting of arginine and lysine.Accordingly, in another particularly preferred embodiment, the method is characterized in that the sealing agent (b1) is an alkalizing agent comprising a basic amino acid selected from the group consisting of arginine, lysine, ornithine and / or histidine.

[0395] In a further preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one alkalizing agent selected from the group of basic amino acids, preferably selected from the group consisting of arginine, lysine, ornithine and histidine.

[0396] Satisfactory results have also been obtained when agent (b) contains at least one alkali metal hydroxide as sealing agent (b1). Examples of suitable alkali metal hydroxides are sodium hydroxide and potassium hydroxide.

[0397] Satisfactory results have also been obtained when agent (b) contains, as sealing agent (b1), an alkalizing agent which comprises at least one alkaline earth metal hydroxide. Suitable alkaline earth metal hydroxides include magnesium hydroxide, calcium hydroxide and barium hydroxide.

[0398] Satisfactory results have also been obtained when the agent (b) comprises at least one alkali metal silicate and / or alkali metal metasilicate as sealing agent (b1). Suitable alkali metal silicates include sodium silicate and potassium silicate. Suitable alkali metal metasilicates include sodium metasilicate and potassium metasilicate.

[0399] Satisfactory results have also been obtained when the agent (b) comprises at least one alkali metal carbonate and / or alkaline earth metal carbonate as sealing agent (b1). Suitable alkali metal carbonates include sodium carbonate and potassium carbonate. Suitable alkaline earth metal carbonates include magnesium carbonate and calcium carbonate.

[0400] In the group of sealing agents in the form of alkalizing agents (b1), ammonia, C2-C6 alkanolamines, basic amino acids and alkali metal hydroxides have been found to be particularly suitable.

[0401] In a further particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one alkalizing agent selected from the group consisting of ammonia, C2-C6 alkanolamines, basic amino acids and alkali metal hydroxides.

[0402] In another particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one alkalizing agent selected from the group consisting of ammonia, 2-aminoethan-1-ol, 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-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide and potassium hydroxide.

[0403] The agent (b) comprises an alkalizing agent as a sealing agent (b1) in a cosmetic carrier, preferably in an aqueous cosmetic carrier.

[0404] In the present invention, it has been found to be preferred if the agent (b) comprises 5.0 to 99.0% by weight, preferably 15.0 to 97.0% by weight, more preferably 25.0 to 97.0% by weight, even more preferably 35.0 to 97.0% by weight and very particularly preferably 45.0 to 97.0% by weight of water relative to the total weight of agent (b).

[0405] In another embodiment, the method is characterized in that the agent (b) comprises 5.0 to 99.0% by weight, preferably 15.0 to 97.0% by weight, more preferably 25.0 to 97.0% by weight, even more preferably 35.0 to 97.0% by weight and very particularly preferably 45.0 to 97.0% by weight of water relative to the total weight of agent (b).

[0406] The alkalizing agent contained in agent (b) influences the pH value of agent (b). It has been found that certain alkaline pH values ​​have a beneficial effect on the dyeing performance and fastness properties of the dyeings obtained in the process.

[0407] For this reason, the agent (b) containing an alkalizing agent as a sealing agent (b1) preferably has a pH of 7.0 to 12.0, preferably 7.5 to 11.5, more preferably 8.0 to 11.0, and most preferably 8.5 to 9.5.

[0408] The pH value can be measured by conventional methods known in the art, for example by pH measurement using a glass electrode via a combination electrode or using pH test paper.

[0409] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises an alkalizing agent as sealing agent (b1) and has a pH of 7.0 to 12.0, preferably 7.5 to 11.5, more preferably 8.0 to 11.0 and most preferably 8.5 to 9.5.

[0410] For the purposes of the present invention, pH values ​​are those measured at a temperature of 22°C.

[0411] In another embodiment, the sealing agent (b1) comprises an acidifying agent.

[0412] Particularly preferably, the acidifying agent is selected from the group consisting of inorganic acids, organic acids and mixtures thereof.

[0413] Satisfactory results have been obtained when agent (b) comprises at least one inorganic acid as sealing agent (b1). Suitable inorganic acids are, for example, phosphoric acid, sulfuric acid and / or hydrochloric acid, with sulfuric acid being particularly preferred.

[0414] In a further preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one acidifying agent selected from the group consisting of inorganic acids, which inorganic acids are preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid and mixtures thereof.

[0415] In another more preferred embodiment the method is characterized in that the agent (b) comprises sulfuric acid as sealing agent (b1).

[0416] Satisfactory results have also been obtained when the agent (b) comprises at least one organic acid as sealing agent (b1), preferably formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoylic acid, hydroatropic acid, atropic acid, cinnamic acid, methyl ethyl ketone, methyl ... acid, isonicotinic acid, nicotinic acid, bicarbamic acid, 4,4'-dicyano-6,6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalenepentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propanetricarboxylic acid, glycolic acid, gluconic acid, lactic acid, maleic acid, ascorbic acid, malic acid, tartaric acid, citric acid and mixtures thereof.

[0417] In another preferred embodiment, the method further comprises the step of: the agent (b) comprises as sealing agent (b1) at least one acidifying agent selected from the group consisting of organic acids, preferably formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o,m,p-phthalic acid, naphthoic acid, toluoic acid, hydoric ... Characterized in that the acid is selected from the group consisting of hydratropasic acid, atropasic acid, cinnamic acid, isonicotinic acid, nicotinic acid, bicarbamic acid, 4,4'-dicyano-6,6'-binicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalenepentaacetic acid, malonaldehyde acid, 4-hydroxyphthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propanetricarboxylic acid, glycolic acid, gluconic acid, lactic acid, maleic acid, ascorbic acid, malic acid, tartaric acid, citric acid and mixtures thereof.

[0418] In a further more preferred embodiment the method is characterized in that the agent (b) comprises acetic acid as sealing agent (b1).

[0419] Suitable acidifying agents also include methanesulfonic acid and / or 1-hydroxyethane-1,1-diphosphonic acid.

[0420] Within the group of the abovementioned sealing agents (b1) in the form of acidifying agents, sulfuric acid and / or acetic acid have been found to be particularly suitable.

[0421] In the context of a further particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one acidifying agent selected from the group consisting of sulfuric acid, acetic acid and mixtures thereof.

[0422] The agent (b) comprises an acidifying agent as a sealing agent (b1) in a cosmetic carrier, preferably in an aqueous cosmetic carrier.

[0423] The acidifying agent contained in agent (b) has an influence on the pH of agent (b). It has been found that an acidic pH value also has a beneficial effect on the dyeing performance and fastness properties of the dyeings obtained in the process.

[0424] For this reason, the agent (b) containing an acidifying agent as a sealing agent (b1) preferably has a pH of 2.0 to 6.5, preferably 3.0 to 6.0, more preferably 4.0 to 6.0, and most preferably 4.5 to 5.5.

[0425] The pH value can be measured by conventional methods known in the art, for example by pH measurement using a glass electrode via a combination electrode or using pH test paper.

[0426] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises an acidifying agent as sealing agent (b1) and has a pH of 2.0 to 6.5, preferably 3.0 to 6.0, more preferably 4.0 to 6.0 and most preferably 4.5 to 5.5.

[0427] For the purposes of the present invention, pH values ​​are those measured at a temperature of 22°C.

[0428] The application of agent (b) is intended to seal and fix the film initially produced by the application of agent (a).

[0429] Other ingredients in formulations (a) and (b) The agents (a) and (b) may contain one or more optional ingredients.

[0430] The formulation may contain one or more surfactants. The term "surfactant" refers to a surface-active substance. They are classified into anionic surfactants, which consist of a hydrophobic group and a negatively charged hydrophilic head group, amphoteric surfactants, which have both a negative charge and a countervailing positive charge, cationic surfactants, which have a positively charged hydrophilic group in addition to a hydrophobic residue, and nonionic surfactants, which have no charge but have a strong dipole moment and are strongly hydrated in aqueous solution.

[0431] Zwitterionic surfactants contain at least one quaternary ammonium group and at least one -COO (-) -or-SO3 (-) Groups of surface-active compounds. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethylammonium-glycinates, such as cocoalkyl-dimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, such as cocoacylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, each having 8 to 18 C atoms in the alkyl or acyl group, and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. One example of a preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name cocamidopropyl betaine.

[0432] Amphoteric surfactants are C8-C 24They are surface-active compounds which, in addition to an alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO3H group and can form an intramolecular salt. Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having about 8 to 24 C atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.

[0433] Particularly preferred amphoteric surfactants are N-cocos alkylaminopropionate, cocos acylaminoethylaminopropionate and C 12 -C 18 -Acylsarcosine.

[0434] The agent may also additionally contain at least one non-ionic surfactant. Suitable non-ionic surfactants are alkyl polyglycosides and alkylene oxide addition products to fatty alcohols and fatty acids of 2 to 30 mol of ethylene oxide per mol of fatty alcohol or fatty acid. Preparations with suitable properties are also obtained if the preparation contains as non-ionic surfactant fatty acid esters of ethoxylated glycerol reacted with at least 2 mol of ethylene oxide.

[0435] The formulation may also contain at least one cationic surfactant. Cationic surfactants are surfactants, i.e., surface-active compounds, each of which has one or more positive charges. Cationic surfactants contain only positive charges. Typically, such surfactants are composed of a hydrophobic portion and a hydrophilic head group, where the hydrophobic portion typically consists of a hydrocarbon backbone (e.g., consisting of one or two straight or branched alkyl chains) and the positive charge resides in the hydrophilic head group. Examples of cationic surfactants are: - quaternary ammonium compounds which may have one or two alkyl chains with a chain length of 8 to 28 carbon atoms as hydrophobic groups; - a quaternary phosphonium salt substituted with one or more alkyl chains having a chain length of 8 to 28 carbon atoms, or -Tertiary sulfonium salts It is.

[0436] Furthermore, the cationic charge may also be part of a heterocycle in the form of an onium structure (e.g., an imidazolium or pyridinium ring). In addition to the functional unit with a cationic charge, the cationic surfactant may also contain other uncharged functional groups, as in the case of esterquats for example. The cationic surfactant is used in a total amount of 0.1-45% by weight, preferably 1-30% by weight, most preferably 1-15% by weight, based on the total weight of each agent.

[0437] Furthermore, the agent may also contain at least one anionic surfactant. Anionic surfactants are surface active agents that exclusively have an anionic charge (neutralized by the corresponding counter cation). Examples of anionic surfactants are fatty acids, alkyl sulfates, alkyl ether sulfates and ether carboxylic acids, with 12-20 C atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

[0438] The anionic surfactant is used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight, and most preferably 1 to 15% by weight, based on the total weight of each agent.

[0439] Agent (a) and / or agent (b) may further comprise a matting agent. Suitable matting agents include, for example, (modified) starch, wax, talc and / or (modified) silica. The amount of matting agent is preferably 0.1-10% by weight based on the total amount of agent (a) or agent (b). Preferably, agent (a) comprises a matting agent.

[0440] The agent may also contain other active ingredients, auxiliaries and additives, such as solvents; fatty ingredients, such as C8-C 30 Fatty acid triglycerides, C8-C 30 Fatty acid monoglycerides, C8-C 30fatty acid diglycerides and / or hydrocarbons; structurants, such as glucose, maleic acid and lactic acid, hair conditioning compounds, such as phospholipids, for example lecithin and cephalin; perfume oils, dimethyl isosorbide and cyclodextrin; fibre structure improving active ingredients, in particular mono-, di- and oligosaccharides, for example glucose, galactose, fructose, fructose and lactose; dyes for colouring the product; anti-dandruff active ingredients, for example piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides; protein hydrolysates of animal and / or vegetable origin and fatty acid condensates or optionally in the form of anionic or cationically modified derivatives; vegetable oils; light stabilizers and UV blockers; active ingredients, for example panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acid and its salts, 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 kerosene; swelling and penetrating agents, such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidine, urea, primary, secondary and tertiary phosphates; opacifying agents, such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlizing agents, such as ethylene glycol mono- and distearate and PEG-3-distearate; and foaming agents, such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0441] The selection of these other substances is made by those skilled in the art according to the desired properties of the agent. Other optional ingredients and the amounts of such ingredients used are specified in the relevant manuals known to those skilled in the art. The additional active ingredients and auxiliary agents are preferably used in the preparations of the present invention in an amount of 0.0001-25% by weight, and 0.0005-15% by weight, based on the total weight of each agent.

[0442] Method for dyeing keratinous materials In the procedure of the present invention, agents (a) and (b) are applied to a keratinous material, for example human hair. For example, agents (a) and (b) are ready-to-use agents. Agents (a) and (b) are different.

[0443] In principle, agents (a) and (b) can be applied either simultaneously or successively, although successive application is preferred.

[0444] The best results were obtained when agent (a) was applied to the keratinous material in a first step and agent (b) was applied in a second step.

[0445] Therefore, the following steps: -As the first step, (a1) at least one organosilicon compound selected from the group consisting of silanes having 1, 2 or 3 silicon atoms, and (a2) at least one coloring compound containing at least one effect pigment comprising a substrate platelet α) and a coating β), where the coating (i) metal oxides and / or metal oxide hydrates, and (ii) Colored compounds from the group of pigments and having at least one layer which is applying to keratinous materials an agent (a) comprising As the second step, (b1) at least one encapsulant applying to the keratin material an agent (b) comprising Very particular preference is given to a method for treating keratinous materials, in particular human hair, and for colouring keratinous materials, in particular human hair, which comprises in that order:

[0446] Furthermore, in order to impart high washability to the dyed keratinous material for a long period of time, it is particularly preferred that agents (a) and (b) are applied within the same dyeing process, which means that there is at most a period of a few hours between the application of agents (a) and (c).

[0447] In another preferred embodiment, the method is characterized in that agent (a) is applied first and then agent (b), and the time between application of agents (a) and (b) is at most 24 hours, preferably at most 12 hours, particularly preferably at most 6 hours.

[0448] A distinctive feature of agent (a) is that it contains at least one reactive organosilicon compound (a1). The one or more reactive organosilicon compounds (a1) undergo an oligomerization or polymerization reaction and therefore functionalize the surface of the hair as soon as they meet. In this way, a first film is formed. The coloring compound (a2) is incorporated into the film so that it is colored. In a second step of the method, a second agent (b) is now applied to the hair. When agent (b) comprising at least one film-forming polymer is applied as sealant (b1), the latter interacts with the silane film and is thus bound to the keratin material. When agent (b) comprising at least one alkalizing or acidifying agent is applied as sealant (b1), the formation of the silane film is positively influenced.

[0449] In another embodiment, the method comprises the steps of: (1) applying agent (a) to keratinous materials; (2) allowing the agent (a) to act for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (3) optionally rinsing the keratinous material with water; (4) applying agent (b) to the keratin material; (5) allowing agent (b) to act for 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (6) Rinse the keratinous material with water. In particular, a procedure comprising the steps of:

[0450] Rinsing the keratinous material with water in steps (3) and (6) of the method means in the present invention that in this rinsing step, no other agents than agents (a) and (b) are used, but only water.

[0451] In step (1), agent (a) is first applied to keratinous materials, in particular human hair.

[0452] After application, the agent (a) is left to act on the keratinous substances. In this context, application times on the hair of from 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes, particularly preferably from 30 seconds to 2 minutes, have been found to be particularly advantageous.

[0453] In a preferred embodiment of the method, agent (a) can be washed off from the keratinous material before applying agent (b) to the hair in a subsequent step.

[0454] When agent (b) was applied to keratinous materials still exposed to agent (a), dyeings with similarly good washfastness were obtained.

[0455] In step (4), agent (b) is applied to the keratinous material. After application, agent (b) is left on the hair to act.

[0456] Even if the contact time of agent (b) is short, the process allows the production of dyeings having particularly good strength and washing fastness. It has been found to be particularly advantageous for application times on the hair to be between 10 seconds and 10 minutes, preferably between 20 seconds and 5 minutes, most preferably between 30 seconds and 3 minutes.

[0457] In step (6), agent (b) (and agent (a) if still present) is rinsed from the keratinous material with water.

[0458] In this embodiment, the sequence of steps (1) to (6) is preferably carried out within 24 hours.

[0459] Agent (a) contains highly reactive compounds which, together with one or more organosilicon compounds, can undergo hydrolysis or oligomerization and / or polymerization during use. These organosilicon compounds are highly reactive and therefore form a film on the keratinous materials.

[0460] It is of considerable advantage to the user to prepare the ready-to-use agent (a) exclusively immediately prior to application in order to avoid premature oligomerization or polymerization.

[0461] In another embodiment, the method comprises the steps of: (1) preparing agent (a) by mixing a first agent (a') and a second agent (a"), the first agent (a') comprises at least one organosilicon compound (a1) selected from the group consisting of silanes containing one, two or three silicon atoms, - the second agent (a") comprises at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, (2) applying agent (a) to keratinous materials; (3) allowing the agent (a) to act for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) optionally rinsing the keratinous material with water; (5) applying agent (b) to the keratin material; (6) allowing agent (b) to act for 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratinous material with water. in that order is preferred.

[0462] In order to provide a composition that is as stable as possible during storage, it is preferred that the agent (a') itself be prepared with low or no moisture.

[0463] In a preferred embodiment, the multicomponent packaging unit (kit) is characterized in that agent (a') comprises water in a content of 0.001 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight, very preferably 1.5 to 7% by weight, based on the total weight of agent (a').

[0464] The agent (a") comprises water. In a preferred embodiment, the multicomponent packaging unit (kit) is characterized in that the agent (a") has a water content of 15 to 100% by weight, preferably 35 to 100% by weight, more preferably 55 to 100% by weight, even more preferably 65 to 100% by weight and very particularly preferably 75 to 100% by weight, based on the total weight of the agent (a2).

[0465] In this embodiment, the ready-to-use agent (a) is prepared by mixing agent (a') and agent (a").

[0466] For example, the user can first mix or shake agent (a') containing one or more organosilicon compounds (a1) with the aqueous effect pigment-containing agent (a"). The user can then apply this mixture of (a') and (a") to the keratin material either immediately after its preparation or after a short reaction time of 10 seconds to 20 minutes. The user can then apply agent (b) as described above.

[0467] The silicone polymer (a3), which may be optionally included, may be included in agent (a') or in agent (a"). Preferably, the silicone polymer (a3) ​​is included in agent (a").

[0468] In another embodiment, the method comprises the steps of: (1) preparing agent (a) by mixing a first agent (a') and a second agent (a"), the first agent (a') comprises at least one organosilicon compound (a1) selected from the group consisting of silanes containing one, two or three silicon atoms, and at least one silicone polymer (a3), - the second agent (a") comprises at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, (2) applying agent (a) to keratinous materials; (3) allowing the agent (a) to act for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) optionally rinsing the keratinous material with water; (5) applying agent (b) to the keratin material; (6) allowing agent (b) to act for 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratinous material with water. in that order is preferred.

[0469] In another embodiment, the method comprises the steps of: (1) preparing agent (a) by mixing a first agent (a') and a second agent (a"), the first agent (a') comprises at least one organosilicon compound (a1) selected from the group consisting of silanes containing one, two or three silicon atoms, the second agent (a") comprises at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), further comprising at least one silicone polymer (a3), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, (2) applying agent (a) to keratinous materials; (3) allowing the agent (a) to act for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) optionally rinsing the keratinous material with water; (5) applying agent (b) to the keratin material; (6) allowing agent (b) to act for 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratinous material with water. In particular, a method comprising the steps of:

[0470] In another preferred embodiment, the method is also characterized in that the one or more silicone polymers (a3) ​​are provided in a third, separately prepared agent (a''').

[0471] With respect to this alternative embodiment, a method is preferred which comprises the following steps in the order listed: (1) preparing agent (a) by mixing a first agent (a'), a second agent (a"), and a third agent (a"') [wherein the first agent (a') comprises at least one organosilicon compound (a1) selected from the group consisting of silanes containing one, two or three silicon atoms, - the second agent (a") comprises at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, the third agent (a"') comprises at least one silicone polymer (a3); (2) applying agent (a) to keratinous materials; (3) allowing the agent (a) to act for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) optionally rinsing the keratinous material with water; (5) applying agent (b) to the keratin material; (6) allowing agent (b) to act for 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinsing the keratinous material with water.

[0472] Multi-component packaging unit (kit) To enhance the user's comfort, it is preferable to provide the user with all the necessary resources in the form of a multi-component packaged unit (kit).

[0473] A second object of the present invention is therefore to provide a method for manufacturing a pharmaceutical product which is packaged separately from one another, a first container containing the agent (a'), a second container containing agent (a"), and a third container containing agent (b); A multi-component packaging unit (kit) for coloring keratinous materials, comprising: the agent (a') comprises at least one organosilicon compound (a1) selected from the group consisting of silanes containing one, two or three silicon atoms, the agent (a") comprises at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, agent (b) contains at least one sealing agent (b1), Components (a1), (a2) and (b1) are multi-component packaging units as described in detail above.

[0474] The organosilicon compound (a1) from the group consisting of silanes having one, two or three silicon atoms contained in agent (a') of the kit corresponds to the organosilicon compound (a1) used in agent (a) of the above-described method.

[0475] The coloring compound (a2) contained in agent (a") of the kit and comprising at least one effect pigment comprising a substrate platelet α) and a coating β), wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, corresponds to the coloring compound (a2) used in agent (a) of the above method and comprising an effect pigment comprising a substrate platelet α) and a coating β), wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments.

[0476] The sealant (b1) contained in the agent (b) of the kit corresponds to the sealant used in the agent (b) of the above method.

[0477] In this regard, it is also possible to use the silicone polymer (a3) ​​which may optionally be included and which is prepared in agent (a'), agent (a") or agent (a").

[0478] In another embodiment, a multi-component packaging unit (kit) for coloring keratinous materials comprises a first container, a second container and a third container, preferably packaged separately from each other, the first container contains an agent (a'), which comprises at least one organosilicon compound (a1) from the group consisting of silanes containing 1, 2 or 3 silicon atoms and at least one silicone polymer (a3); - a second container comprises an agent (a"), which comprises at least one coloring compound (a2) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, the third container comprises an agent (b), the agent (b) comprising at least one sealing agent (b1); Components (a1), (a2), (a3) ​​and (b1) are as described in detail above.

[0479] In another embodiment, a multi-component packaging unit (kit) for coloring keratinous materials comprises a first container, a second container, a third container and a fourth container, preferably packaged separately from one another, the first container contains an agent (a'), which comprises at least one organosilicon compound (a1) from the group consisting of silanes containing 1, 2 or 3 silicon atoms, a second container comprises an agent (a"), which comprises at least one coloring compound (a2) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, and further comprises at least one silicone polymer (a3), the third container contains an agent (a"'), which is a water-containing cosmetic carrier; the fourth container comprises an agent (b), the agent (b) comprising at least one sealing agent (b1); Components (a1), (a2), (a3) ​​and (b1) are as described in detail above.

[0480] In this embodiment, agents (a') and (a") have a low water content. To prepare the ready-to-use agent (a), agents (a'), (a") and (a"') are mixed. In this case, agent (a") represents the water-containing cosmetic carrier.

[0481] In another embodiment, a multi-component packaging unit (kit) for coloring keratinous materials comprises a first container, a second container and a third container, preferably packaged separately from each other, the first container contains an agent (a'), which comprises at least one organosilicon compound (a1) from the group consisting of silanes containing 1, 2 or 3 silicon atoms, a second container comprises an agent (a"), which comprises at least one coloring compound (a2) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, and further comprises at least one silicone polymer (a3), the third container comprises an agent (b), the agent (b) comprising at least one sealing agent (b1); Components (a1), (a2), (a3) ​​and (b1) are as described in detail above.

[0482] In another embodiment, a multi-component packaging unit (kit) for coloring keratinous materials comprises a first container, a second container, a third container and a fourth container, preferably packaged separately from one another, the first container contains an agent (a'), which comprises at least one organosilicon compound (a1) from the group consisting of silanes containing 1, 2 or 3 silicon atoms, - a second container comprises an agent (a"), which comprises at least one coloring compound (a2) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, a third container comprises an agent (a"'), the agent (a"') comprising at least one silicone polymer (a3); the fourth container comprises an agent (b), the agent (b) comprising at least one sealing agent (b1); Components (a1), (a2), (a3) ​​and (b1) are as described in detail above.

[0483] In this embodiment of the multi-component packaging unit, it may be preferred that the agent (a"') further comprises at least one further colouring compound (a2).

[0484] With regard to further preferred embodiments of the multi-component packaging unit, what has already been said with regard to the method applies. Preferred aspects of the present invention include the following. [1] The following process: - applying to the keratin material an agent (a) comprising at least one organosilicon compound (a1) selected from the group consisting of silanes having 1, 2 or 3 silicon atoms and at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, and - applying an agent (b) comprising at least one sealant (b1) to the keratinous material; 1. A method for dyeing keratinous materials, particularly human hair, comprising: [2] The agent (a) is represented by the formula (I) and / or (II): Formula (I): R 1 R 2 NL-Si(OR 3 ) a (R 4 )b (I) [In the formula, -R 1 、R 2 are independently a hydrogen atom or C 1 -C 6 represents an alkyl group, -L is a linear or branched divalent C 1 -C 20 is an alkylene group, -R 3 、R 4 are C 1 -C 6 represents an alkyl group, -a represents an integer from 1 to 3; -b represents the integer 3-a] Formula (II): TIFF0007657770000059.tif6134 [In the formula, -R 5 、R 5' 、R 5" 、R 6 、R 6' and R 6" is independent, C 1 -C 6 represents an alkyl group, -A, A', A", A"' and A"" are independently linear or branched divalent C 1 -C 20 represents an alkylene group, -R 7 and R 8 are independently a hydrogen atom, C 1 -C 6 Alkyl group, hydroxy C 1 -C 6 Alkyl group, C 2 -C 6 Alkenyl group, Amino C 1 -C 6 An alkyl group or a group of formula (III): -(A"")-Si(R 6 ") d" (OR 5 ") c" (III) represents a group represented by -c represents an integer from 1 to 3, -d represents the integer 3-c, -c' represents an integer from 1 to 3, -d' represents the integer 3-c', -c" represents an integer from 1 to 3, -d" represents the integer 3-c", -e represents 0 or 1, -f stands for 0 or 1, -g stands for 0 or 1, -h represents 0 or 1, - at least one of e, f, g and h is different from 0] The method according to [1], characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula: [3] The agent (a) is represented by the formula (I): R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b (I) [In the formula, -R 1 、R 2 Both represent a hydrogen atom, -L is a linear divalent C 1 -C 6 An alkylene group, preferably a propylene group (-CH 2 -CH 2 -CH 2 -) or ethylene group (-CH 2 -CH 2 -) and -R 3 、R 4 each independently represents a methyl group or an ethyl group; -a represents the number 3, -b represents the number 0] The method according to [1] or [2], characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula: [4] Agent (a) is -(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, and / or -1-(2-dimethylaminoethyl)silanetriol The method according to any one of [1] to [3], comprising at least one organosilicon compound (a1) represented by formula (I) selected from the group consisting of: [5] The agent (a) is represented by the formula (II): TIFF0007657770000060.tif6134 [In the formula, - e and f together represent the number 1, - g and h together represent the number 0, -A and A' are independently a linear divalent C 1 -C 6 represents an alkylene group, -R 7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group, or a group represented by formula (III). The method according to any one of [1] to [4], comprising at least one organosilicon compound (a1) represented by the following formula: [6] Agent (a) is -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, and / or -N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The method according to any one of [1] to [5], comprising at least one organosilicon compound (a1) represented by formula (II) selected from the group consisting of: [7] The agent (a) is represented by the formula (IV): R 9 Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R 9 is C 1 -C18 represents an alkyl group, -R 10 is a hydrogen atom or C 1 -C 6 represents an alkyl group, -R 11 is C 1 -C 6 represents an alkyl group, -k is an integer from 1 to 3; -m represents the integer 3-k] The method according to any one of [1] to [6], comprising at least one organosilicon compound (a1) represented by the following formula: [8] Agent (a) is -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Propyltrimethoxysilane -Propyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -Dodecyltrimethoxysilane -Dodecyltriethoxysilane -Octadecyltrimethoxysilane -Octadecyltriethoxysilane and -Mixtures of these The method according to any one of [1] to [7], comprising at least one organosilicon compound (a1) represented by formula (IV) selected from the group consisting of: [9] The method according to any one of [1] to [8], wherein the agent (a) contains at least two structurally different organosilicon compounds (a1).

[10] The method according to any one of [1] to [9], wherein the base plate comprises aluminum.

[11] The method according to any one of [1] to

[10] , wherein the metal oxide and / or metal oxide hydrate (i) is selected from the group consisting of silicon dioxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide, zinc oxide, and mixtures thereof.

[12] The method according to any one of [1] to

[11] , wherein the metal oxide and / or metal oxide hydrate (i) is silicon dioxide.

[13] Particle size D of coloring compound (ii) 90 , preferably with particle size D 95 , more preferably particle size D 99 , most preferably particle size D 100 The method according to any one of [1] to

[12] , characterized in that is smaller than the layer thickness of at least one layer.

[14] The method according to any of [1] to

[13] , characterized in that the agent (a) comprises at least one further coloring compound (a2), preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or from colored mica or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[15] Separately packaged, a first container containing an agent (a') comprising at least one organosilicon compound (a1) selected from the group consisting of silanes containing 1, 2 or 3 silicon atoms, - a second container containing an agent (a") comprising at least one coloring compound (a2) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, and a third container containing an agent (b) containing at least one sealing agent (b1); A kit for dyeing keratinous materials comprising: EXAMPLES

[0485] Example 1 The following compositions were prepared (all numbers are in weight percent unless otherwise stated): TIFF0007657770000061.tif2795

[0486] TIFF0007657770000062.tif3392

[0487] A ready-to-use preparation (a) was prepared by mixing 5 g of preparation (a') and 20 g of preparation (a"). The pH value of preparation (a) was adjusted to a value of 10.5 by adding ammonia or lactic acid. Preparation (a) was then left to stand for about 5 minutes.

[0488] TIFF0007657770000063.tif21120

[0489] Agent (a) was massaged into a lock of hair (Kerling, Euronatural hair white) at once and left to act for 1 minute. Agent (a) was then rinsed off with water. Subsequently, agent (b) was applied to the hair tresses, left to act for 1 minute and then rinsed off with water.

Claims

1. The following steps: - applying to the keratin material an agent (a) comprising at least one organosilicon compound (a1) selected from the group consisting of silanes having 1, 2 or 3 silicon atoms and at least one coloring compound (a2) containing at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, and - applying an agent (b) comprising at least one sealing agent (b1) to the keratinous material A method for dyeing keratinous materials, comprising the steps of: R 9 Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R 9 is C 1 -C 18 represents an alkyl group, -R 10 is a hydrogen atom or C 1 -C 6 represents an alkyl group, -R 11 is C 1 -C 6 represents an alkyl group, -k is an integer from 1 to 3, -m represents an integer 3-k. and the keratinous material is one or more selected from the group consisting of hair, nails, wool, fur and feathers.

2. The agent (a) is represented by the formula (I) and / or (II): Formula (I): R 1 R 2 N-L-Si(OR 3 ) a (R 4 ) b (I) [In the formula, -R 1 , R 2 are independently a hydrogen atom or C 1 -C 6 represents an alkyl group, -L is a linear or branched divalent C 1 -C 20 is an alkylene group, -R 3 , R 4 are C 1 -C 6 represents an alkyl group, -a represents an integer from 1 to 3, -b represents the integer 3-a. Formula (II): [In the formula, -R 5 , R 5' , R 5" , R 6 , R 6' and R 6" is independent, C 1 -C 6 represents an alkyl group, - A, A', A", A"' and A"" are independently linear or branched bivalent C 1 -C 20 represents an alkylene group, -R 7 and R 8 are independently a hydrogen atom, C 1 -C 6 Alkyl group, hydroxy C 1 -C 6 Alkyl group, C 2 -C 6 Alkenyl group, Amino C 1 -C 6 An alkyl group or a group of formula (III): -(A"")-Si(R 6 ") d" (OR 5 ") c" (III) represents a group represented by -c represents an integer from 1 to 3, -d represents the integer 3-c; -c' represents an integer from 1 to 3, -d' represents the integer 3-c', -c" represents an integer from 1 to 3, -d" represents the integer 3-c", -e represents 0 or 1; -f represents 0 or 1; -g represents 0 or 1; -h represents 0 or 1; - at least one of e, f, g and h is different from 0.

2. The process according to claim 1, characterized in that it comprises at least one organosilicon compound (a1) of the formula

3. The agent (a) has the formula (I): R 1 R 2 N-L-Si(OR 3 ) a (R 4 ) b (I) [In the formula, -R 1 , R 2 Both represent a hydrogen atom, -L is a linear divalent C 1 -C 6 represents an alkylene group, -R 3 , R 4 each independently represents a methyl group or an ethyl group; -a represents the number 3, -b represents the number 0.

3. The process according to claim 1 or 2, characterized in that it comprises at least one organosilicon compound (a1) of the formula

4. The agent (a) is -(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, and / or - 1-(2-dimethylaminoethyl)silanetriol 4. The process according to claim 1, comprising at least one organosilicon compound (a1) of formula (I) selected from the group consisting of:

5. The agent (a) has the formula (II): [In the formula, - e and f together represent the number 1, - g and h together represent the number 0, - R5, R5', R5", R6, R6' and R6" independently represent a C1-C6 alkyl group; -A and A' are independently linear divalent C 1 -C 6 represents an alkylene group, - A", A"', and A"" independently represent a linear or branched divalent C1-C20 alkylene radical; -R 7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group, or a group of formula (III): -(A"")-Si(R 6 ") d" (OR 5 ") c" (III) represents a group represented by -R 8 represents a hydrogen atom, a C 1 -C 6 alkyl group, a hydroxy C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, an amino C 1 -C 6 alkyl group or a group represented by formula (III); -c represents an integer from 1 to 3, -d represents the integer 3-c; -c' represents an integer from 1 to 3, -d' represents the integer 3-c', -c" represents an integer from 1 to 3, -d" represents the integer 3-c" 5. The process according to claim 1, further comprising at least one organosilicon compound (a1) having the formula

6. The agent (a) is -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, and / or -N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine 6. The process according to claim 1, comprising at least one organosilicon compound (a1) of formula (II) selected from the group consisting of:

7. The agent (a) is -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Propyltrimethoxysilane -Propyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -Dodecyltrimethoxysilane -Dodecyltriethoxysilane -Octadecyltrimethoxysilane -Octadecyltriethoxysilane and - their mixtures 7. The process according to claim 1, comprising at least one organosilicon compound (a1) of formula (IV) selected from the group consisting of:

8. 8. The method according to claim 1, wherein the agent (a) contains at least two structurally different organosilicon compounds (a1).

9. The method according to any one of claims 1 to 8, characterized in that the substrate plate comprises aluminium.

10. 10. The method according to any one of claims 1 to 9, characterized in that the metal oxide and / or metal oxide hydrate (i) is selected from the group consisting of silicon (di)oxide, silicon oxide hydrate, aluminium oxide, aluminium oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof.

11. 11. The method according to claim 1, wherein the metal oxide and / or metal oxide hydrate (i) is silicon dioxide.

12. Particle size D of coloring compound (ii) 90 The method according to any of the preceding claims, characterized in that is smaller than the layer thickness of at least one layer.

13. The method according to any of the preceding claims, characterized in that the agent (a) comprises at least one further colouring compound (a2).

14. Separately packaged, a first container containing an agent (a′) comprising at least one organosilicon compound (a1) selected from the group consisting of silanes containing 1, 2 or 3 silicon atoms; a second container containing an agent (a″) comprising at least one coloring compound (a2) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments, and a third container containing an agent (b) which contains at least one sealing agent (b1); A kit for dyeing keratinous materials comprising the agent (a') of formula (IV): R 9 Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R 9 is C 1 -C 18 represents an alkyl group, -R 10 is a hydrogen atom or C 1 -C 6 represents an alkyl group, -R 11 is C 1 -C 6 represents an alkyl group, -k is an integer from 1 to 3, -m represents an integer 3-k. wherein the keratinous material is one or more selected from the group consisting of hair, nails, wool, fur and feathers.

Images