Method for coloring keratinous materials involving the use of organosilicon compounds, effect pigments and sealing agents VI

Abstract

The present invention relates to a method for producing a method for manufacturing a semiconductor device comprising the steps of: - applying an agent (a) to keratinous materials, said agent (a) comprising: (a1) at least one organosilicon compound selected from the group consisting of silanes having one, two, or three silicon atoms; and (a2) at least one substrate comprising a vacuum metallized pigment; and at least one colorant compound comprising a flake-based pigment. and - applying an agent (b) to the keratinous material, said agent (b) comprising: (b1) at least one sealing reagent Processes including The present invention relates to a method for dyeing keratinous materials, in particular human hair, comprising:

Description

[Technical field]

[0001] The subject of the present application is a method for treating keratinous materials, in particular human hair, which comprises applying 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 sealing agent.

[0002] A further subject of the present application is a multi-component packaged unit (kit-of-parts) for dyeing keratinous materials, in particular human hair, comprising at least four separately prepared means (a'), (a'') and (b). The agents (a') and (a'') can be used to prepare the agent (a) used in the above-mentioned method. [Background technology]

[0003] The change of shape and color of keratin fibers, especially hair, is an important area of ​​modern cosmetics. To change the color of hair, experts know various coloring systems depending on the coloring requirements. Oxidation dyes are usually used for permanent and solid dyeing, have good fastness properties and provide good gray coverage. Such dyes usually contain oxidation dye precursors, so-called developer and coupler components, which form each other and the dye itself under the influence of an oxidizing agent such as hydrogen peroxide. Oxidation dyes are characterized by a very long-lasting dyeing result.

[0004] When using direct dyes, the ready-made dye diffuses from the coloring agent into the hair fiber. Compared to oxidative hair dyes, the stain obtained with direct dyes is short-lived and washes out quickly. The stain with direct dyes usually remains on the hair for 5 to 20 washes.

[0005] The use of color pigments is known to produce short-term color changes on hair and / or skin. Color pigments are generally understood to be insoluble coloring substances. They exist in the dye formulation in an undissolved state in the form of small particles and are only deposited on the outer surface of hair fibers and / or skin surfaces. Therefore, they can be removed without residue by rinsing several times with a detergent that usually contains a surfactant. Various products of this type are available on the market under the name of hair mascara.

[0006] If users want particularly long-lasting dyeing, the use of oxidative dyes has been the only option up to now. However, despite numerous optimization attempts, the unpleasant ammonia and amine odors in oxidative hair dyes cannot be completely avoided. In addition, the damage to hair that still accompanies the use of oxidative dyes has a negative effect on the user's hair.

[0007] EP 2168633 B1 addresses the problem of producing long-lasting pigmented hair coloring. This document teaches that when a combination of pigment, organosilicon compound, film-forming polymer and solvent is used on hair, it is possible to produce a coloration that is particularly durable to washing.

[0008] Metallic luster pigments or metallic effect pigments are widely used in many technical fields. They are used, for example, to color coatings, printing inks, inks, plastics, glass, ceramic products, and preparations for decorative cosmetics, such as nail varnish. They are characterized, among other things, by an attractive angle-dependent color sensation (goniochromism) and a luster that appears metallic.

[0009] Hair with a metallic finish or metallic highlights is in fashion. Metallic tones make hair appear fuller and shinier.

[0010] There is a need to provide hair dyes with effect pigments which, on the one hand, have high wash-off and rub-off fastness and, on the other hand, do not negatively affect hair properties such as manageability and feel. For this purpose, it would be desirable for the effect pigments used to have high dye build-up and be able to be applied to the hair in a thin layer. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] European Patent Application Publication No. 2168633B1 Summary of the Invention [Problem to be solved by the invention]

[0012] The object of the present invention was therefore to provide a coloring system with effect pigments which have fastness properties comparable to those of oxidative coloring. The wash-off fastness should be excellent, but the use of oxidative dye precursors which are usually used for this purpose should be avoided. [Means for solving the problem]

[0013] Surprisingly, it has now been found that this problem can be solved by coloring keratinous materials, in particular human hair, by a method in which at least two agents (a) and (b) are applied to the keratinous materials (hair). Here, the first agent (a) comprises at least one organosilicon compound from the group of silanes having one, two or three silicon atoms and at least one selected additional coloring compound. In the medium (a), the organosilicon compound and the coloring compound are thus prepared together. The second agent (b) comprises at least one sealing agent.

[0014] When the two agents (a) and (b) were used in a dyeing process, it was possible to dye keratinous materials with particularly high colour strength. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] A first object of the present invention is to provide a method for producing ... liquid crystal display comprising the steps of: - applying an agent (a) to a keratinous material, said agent (a) comprising: (a1) at least one organosilicon compound selected from the group consisting of silanes having one, two or three silicon atoms, and (a2) at least one substrate comprising a vacuum metallization pigment, at least one colorant compound comprising a flake-based pigment; A process comprising: - applying an agent (b) to the keratinous material, said agent (b) comprising: (b1) at least one sealing agent A process including The present invention relates to a method for coloring keratinous materials, particularly human hair, comprising:

[0016] In the research leading to the present invention, it has been found that the preferential successive application of agents (a) and (b) makes it possible to produce very stable and wash-fast colorings on keratinous materials.Without being limited to this theory, it is believed that in this situation, the joint application of the organosilicon compound (a1) and the coloring compound (a2) leads to the formation of a particularly durable first film on the keratinous materials.This first layer is sealed by the application of the second agent (b).For example, a film-forming polymer is then deposited in the form of a further film on this first layer as sealing agent (b1).

[0017] Due to this special type of package, i.e. the combined application of the silane (a1) and the coloring compound (a2) and the separate application of the sealing agent (b1), the film system thus produced exhibited improved resistance to external influences. In this way, the coloring compound (a2) was permanently fixed to the keratinous materials, so that very wash-fast colorations with good resistance to washing could be obtained.

[0018] Keratinous substances Keratinous materials include hair, skin, nails (e.g., fingernails and / or toenails). Also included within the definition of keratinous materials are wool, fur and feathers.

[0019] Preferably, keratinous material is understood to be human hair, human skin and human nails, in particular fingernails and toenails. Keratinous material is understood to be human hair.

[0020] Agents (a) and (b) In the procedure according to the invention, the agents (a) and (b) are applied to keratinous material, in particular human hair. The two means (a) and (b) are different from each other.

[0021] In other words, the first object of the present invention is to provide a method for producing a cellular membrane comprising the steps of: Applying an agent (a) to a keratinous material, the agent (a) comprising: (a1) at least one organosilicon compound selected from the group consisting of silanes having one, two or three silicon atoms, and (a2) at least one substrate comprising a vacuum metallization pigment, at least one colorant compound comprising a platelet-based pigment; A process comprising: applying an agent (b) to the keratinous material, the agent (b) comprising: (b1) at least one sealing agent A process including The present invention relates to a method for treating keratinous material, particularly human hair, comprising:

[0022] Agent (a) Preferably, the composition (a) comprises the essential components (a1) and (a2) of the invention in a cosmetic carrier, particularly preferably in an aqueous or aqueous-alcoholic cosmetic carrier. This cosmetic carrier may be in the form of a liquid, gel or cream. Also, pasty, solid or powdery cosmetic carriers can be used for the preparation of the agent (a). For hair treatment, in particular for hair coloring, such carriers are, for example, creams, emulsions, gels or also surfactant-containing foaming solutions, such as shampoos, aerosol foams, foam formulations or other preparations suitable for application to the hair.

[0023] Preferably, the cosmetic carrier contains at least 2% by weight of water relative to its weight. More preferably, the water content is above 10% by weight, even more preferably above 20% by weight, particularly preferably above 40% by weight. The cosmetic carrier may also be hydroalcoholic. Aqueous / alcoholic solutions in the context of the present invention are aqueous solutions containing 2-70% by weight of C1-C4 alcohols, more particularly 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. Preference is given to all water-soluble organic solvents.

[0024] Organosilicon compounds from the group of silanes (a1) As essential component (a1) of the invention, composition (a) comprises at least one organosilicon compound from the group of the silanes containing one, two or three silicon atoms.

[0025] Particularly preferably, the agent (a) comprises at least one organosilicon compound (a1) selected from silanes having one, two or three silicon atoms, which organosilicon compound contains one or more hydroxyl and / or hydrolyzable groups per molecule.

[0026] Such organosilicon compounds (a1) or organosilanes contained in the agent (a) are reactive compounds.

[0027] Organosilicon compounds, alternatively referred to as organosilicon compounds, are compounds that either have a silicon-carbon direct bond (Si-C) or carbon is bonded to a silicon atom via an oxygen, nitrogen or sulfur atom.The organosilicon compounds of the present invention are compounds that contain 1-3 silicon atoms.The organosilicon compounds preferably contain 1 or 2 silicon atoms.

[0028] According to IUPAC rules, the term silane is a chemical 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. Also in organosilanes, some hydrogen atoms may be replaced by hydroxy groups.

[0029] In one particularly preferred embodiment, the method according to the invention comprises applying an agent (a) to keratinous materials, said agent (a) being characterized in that it 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.

[0030] In one very particularly preferred embodiment, the method according to the invention comprises applying an agent (a) to keratinous materials, said agent (a) 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.

[0031] The basic group or basic chemical functionality may be, for example, an amino group, an alkylamino group, or a dialkylamino group, which is preferably linked 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.

[0032] The hydrolyzable group(s) are preferably C1-C6 alkoxy groups, in particular ethoxy or methoxy groups. It is preferred if the hydrolyzable group is directly bonded to the silicon atom. For example, if the hydrolyzable group is an ethoxy group, the organosilicon compound preferably comprises the structural unit R'R''R'''Si-O-CH2-CH3. The residues R', R'' and R'''' represent the free valences of the remaining three bonds of the silicon atom.

[0033] One example of a particularly preferred method according to the invention is characterized in that the composition comprises (a) at least one organosilicon compound selected from silanes having one, two or three silicon atoms and preferably containing one or more basic chemical functions and one or more hydroxyl or hydrolyzable groups per molecule.

[0034] Particularly good results have been obtained when the agent (a) comprises at least one organosilicon (a1) compound of the formulae (I) and / or (II).

[0035] The compounds of formulas (I) and (II) are organosilicon compounds selected from silanes having one, two or three silicon atoms, which contain one or more hydroxyl and / or hydrolyzable groups per molecule.

[0036] In another very particularly preferred embodiment, the method comprises applying an agent to keratinous materials (or human hair), the agent (a) comprising at least one organosilicon compound (a) of formula (I) and / or (II), R1R2N-L-Si(OR3) a (R4) b (I), During the ceremony -R1 and R2 each independently represent a hydrogen atom or a C1-C6 alkyl group; -L is a straight 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 to C6 alkyl group; -a represents an integer from 1 to 3; -b represents an integer equal to 3-a, (R5O) c (R6) d Si-(A) e -[NR7-(A')] f -[O-(A'')] g -[NR8-(A''')] h -Si(R6') d’ (OR5') c’ (II), During the ceremony -R5, R5', and R5'' each independently represent a hydrogen atom or a C1-C6 alkyl group; -R6, R6' and R6'' each independently represent a C1 to C6 alkyl group; -A, A', and A'' are each independently a straight or branched divalent C1-C 20 represents an alkylene group, - R7 and R8 independently represent 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), -c represents an integer from 1 to 3, -d represents an integer equal to 3-c, -c' represents an integer from 1 to 3, -d' represents an integer equal to 3-c', -c'' represents an integer from 1 to 3, -d'' represents an integer equal to 3-c'', -e represents 0 or 1, -f stands for 0 or 1, -g stands for 0 or 1, -h represents 0 or 1. -However, at least one of e, f, g and h is different from 0. It is characterized by:

[0037] The substituents R1, R2, R3, R4, R5, R5', R5'', R6, R6', R6'', R7, R8, L, A', A'''' and A'''' in the compounds of formula (I) and (II) are illustrated by way of example below:

[0038] Examples of C1-C6 alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and 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. The 2-aminoethyl group is particularly preferred. Straight-chain divalent C1-C 20 Examples of alkylene groups include methylene (-CH2), ethylene (-CH2-CH2-), propylene (-CH2-CH2-CH2-) and butylene (-CH2-CH2-CH2-). Propylene (-CH2-CH2-CH2-) is particularly preferred. In addition, due to the chain length of three C atoms, the divalent alkylene group may be branched. The branched divalent C3-C 20 Examples of alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0039] In the organosilicon compound of formula (I) R1R2N-L-Si(OR3) a (R4) b (I), The R1 and R2 groups each independently represent a hydrogen atom or a C1-C6 alkyl group. In particular, the R1 and R2 groups both represent a hydrogen atom.

[0040] The central part of the organosilicon compound is a linear or branched divalent C1-C 20 There is a structural unit or linker -L- which represents an alkylene group.

[0041] Divalent C1-C 20 The alkylene group is alternatively a divalent or divalent C1-C 20 Sometimes referred to as an alkylene group, it is intended that each L group may form two bonds: the first bond is from the amino group R1R2N to the linker L, and the second bond is between the linker L and the silicon atom.

[0042] Preferably, -L- is a linear divalent (i.e., bivalent) C1-C 20 It represents an alkylene group. More preferably, -L- represents a linear divalent C1 to C6 alkylene group. Particularly preferably, -L represents a methylene group (CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-) or a butylene (-CH2-CH2-CH2-CH2-). L represents a propylene group (-CH2-CH2-CH2-).

[0043] The straight-chain propylene group (-CH2-CH2-CH2-) is sometimes alternatively referred to as a propane-1,3-diyl group.

[0044] Organosilicon compounds of formula (I) R1R2N-L-Si(OR3) a (R4) b (I), One end of each is a silicon-containing group -Si(OR3) a (R4) b It carries the following:

[0045] 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. Particularly preferably, R3 and R4 each independently represent a methyl group or an ethyl group.

[0046] Here, a represents an integer between 1 and 3, and b represents an integer 3-a. If a represents the number 3, then b is 0. If a represents the number 2, then b is 1. If a represents the number 1, then b is 2.

[0047] Particularly durable coatings could be produced when the agent (a) contained at least one organosilicon compound (a1) of formula (I) in which the R3, R4 groups, independently of one another, represent methyl or ethyl groups.

[0048] When the method according to the invention is used for dyeing keratinous materials, dyeings with the best wash-off fastness can be obtained, as well as when agent (a) comprises at least one organosilicon compound of formula (I) in which the radicals R3, R4, independently of one another, represent a methyl or ethyl radical.

[0049] Moreover, dyeings with the best wash-off fastness could be obtained when agent (a) comprises at least one organosilicon compound of formula (I) in which the residue a has the value 3. In this case, the remaining b has the value 0.

[0050] In a further preferred embodiment, the agent (a) used in the method has the formula - R3 and R4 each independently represent a methyl group or an ethyl group; -a represents the number 3, -b represents the number 0, It is characterized in that it contains at least one organosilicon compound (a1) of formula (I).

[0051] In a further preferred embodiment, the method according to the invention 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, It is characterized in that it contains at least one organosilicon compound (a1) of formula (I).

[0052] Organosilicon compounds of formula (I) which are particularly suitable for solving the problems according to the invention are -(3-aminopropyl)triethoxysilane TIFF0007621267000001.tif3473-(3-aminopropyl)trimethoxysilane TIFF0007621267000002.tif3465-1-(3-aminopropyl)silanetriol TIFF0007621267000003.tif2160-(2-aminoethyl)triethoxysilane TIFF0007621267000004.tif3465-(2-aminoethyl)trimethoxysilane TIFF0007621267000005.tif3456-1-(2-aminoethyl)silanetriol TIFF0007621267000006.tif2151-(3-Dimethylaminopropyl)triethoxysilane TIFF0007621267000007.tif3475-(3-Dimethylaminopropyl)trimethoxysilane TIFF0007621267000008.tif3466-1-(3-Dimethylaminopropyl)silanetriol TIFF0007621267000009.tif2362-(2-Dimethylaminoethyl)triethoxysilane TIFF0007621267000010.tif3566-(2-Dimethylaminoethyl)trimethoxysilane, and TIFF0007621267000011.tif3457-1-(2-Dimethylaminoethyl)silanetriol The file is TIFF0007621267000012.tif2753.

[0053] In a further preferred embodiment, the method according to the invention 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 contains at least one organosilicon compound (a1) selected from the group consisting of:

[0054] Organosilicon compounds of formula (I) are commercially available.

[0055] For example, (3-aminopropyl)trimethoxysilane can be purchased from Sigma-Aldrich, and (3-aminopropyl)triethoxysilane is commercially available from Sigma-Aldrich.

[0056] In a further embodiment, the composition according to the invention comprises at least one organosilicon compound (a1) of formula (II) (R5O) c (R6) dSi-(A) e -[NR7-(A')] f -[O-(A'')] g -[NR8-(A''')] h -Si(R6') d’ (OR5') c’ (II) Includes.

[0057] The organosilicon compounds of formula (II) according to the present invention each contain a silicon-containing group (RO) c (R6) d Si- and -Si(R6') d’ (OR5') c are supported on both ends.

[0058] The central portion of the molecule of formula (II) contains -(A) e -group and -[NR7-(A')] f -group and -[O-(A'')] g - and -[NR8-(A''')] groups h - group is present, where each of the residues e, f, g and h can independently of one another represent the numerical value 0 or 1, provided that at least one of the residues e, f, g and h is different from 0. In other words, the organosilicon compound of formula (II) according to the invention comprises at least one group 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, R5, R5', and R5'' are each independently a hydrogen atom or a C1 to C6 alkyl group. R6, R6', and R6'' are each independently a C1 to C6 alkyl group.

[0060] Here, a is an integer between 1 and 3, and d is an integer between 3 and c. If c is the number 3, then d is 0. If c is the number 2, then d is 1. If c is the number 1, then d is 2.

[0061] Similarly, c' represents the natural numbers 1 to 3, and d' represents the natural number 3-c'. If c' represents the number 3, then d' is 0. If c' represents the number 2, then d' is 1. If c' represents the number 1, then d' is 2.

[0062] The most stable film or the dyestuff with the best wash-off fastness could be obtained if the residues c and c' both have the value 3. In this case, d and d' both have the value 0.

[0063] In another preferred embodiment, the method further comprises the step of: (R5O) c (R6) d Si-(A) e -[NR7-(A')] f -[O-(A'')] g -[NR8-(A''')] h -Si(R6') d’ (OR5') c’ (II), In the formula -R5 and R5' are independently a methyl group or an ethyl group; -c and c' together represent the number 3, -d and d' both represent the number 0, It is characterized in that it contains at least one organosilicon compound (a1) of formula (II).

[0064] If c and c' are both the number 3 and d and d' are both the number 0, then 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] Residues e, f, g and h can independently represent the numerical values ​​0 or 1, where at least one of e, f, g and h is different from zero. Thus, the abbreviations e, f, g and h refer to -(A) e - and -[NR7-(A')] f - and - [O-(A'')] g - and -[NR8-(A'')] h - is present in the central portion of the organosilicon compound of formula (II).

[0066] In this connection, the presence of certain groups has been found to be particularly beneficial in terms of increasing the water-washability. Particularly good results have been obtained when at least two of the residues e, f, g and h have the value 1. Particularly preferred are e and f, both of which have the value 1. Furthermore, g and h, both of which have the value 0.

[0067] When e and f are both equal to the number 1 and g and h are both equal to the number 0, the organosilicon compound according to 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 chain divalent C1-C 20 Preferably, the groups A, A', A'', A''' and A'''' are each independently a linear divalent C1-C 20It represents an alkylene group. More preferably, the groups A, A', A'', A''', and A'''' independently represent a straight-chain divalent C1-C6 alkylene group. In particular, the groups A, A', A'', A''', and A'''' independently represent a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-) or a butylene group (-CH2-CH2-CH2-CH2-). In particular, the groups A, A', A'', A''', and A'''' represent a propylene group (-CH2-CH2-CH2-).

[0069] Divalent C1-C 20 The alkylene group may alternatively be a divalent or divalent C1-C 20 Sometimes referred to as alkylene groups, it is intended that each of the A, A', A'', A''' and A'''' groups may form two bonds.

[0070] The straight-chain propylene group (-CH2-CH2-CH2-) is sometimes alternatively referred to as a propane-1,3-diyl group.

[0071] If the residue f represents the number 1, the organosilicon compound of formula (II) according to the invention comprises a group of structure -[NR7-(A')]-.

[0072] If the residue f represents the number 1, the organosilicon compound of formula (II) according to the invention comprises a group of structure -[NR8-(A''')]-.

[0073] In the formula, R7 and R7 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.

[0074] Very preferably, the groups R7 and R8 independently of each other represent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III).

[0075] When the residue f represents the value 1 and the residue h represents the value 0, the organosilicon compound according to the invention comprises a [NR7-(A')] group but not a -[NR8-(A''')] group. Also, when the R7 group represents a group of formula (III), the agent (a) comprises an organosilicon compound having three reactive silane groups.

[0076] In another preferred embodiment, the method further comprises the step of: the agent (a) comprises at least one organosilicon compound (a1) of formula (II), (R5O) c (R6) d Si-(A) e -[NR7-(A')] f -[O-(A'')] g -[NR8-(A''')] h -Si(R6') d’ (OR5') c’ (II), During the ceremony -e and f both represent the number 1, -g and h both 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 of formula (III) It is characterized by:

[0077] In a further preferred embodiment, the method further comprises the step of: -e and f both represent the number 1, -g and h both represent the number 0, -A and A' are each independently 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 of formula (III), It is characterized in that it contains at least one organosilicon compound of formula (II).

[0078] Organosilicon compounds of formula (II) which are well suited to solving the problems according to the invention are: -3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007621267000013.tif39113-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007621267000014.tif45130-N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007621267000015.tif39113-N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007621267000016.tif45130-2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol TIFF0007621267000017.tif48113-2-[Bis[3-(triethoxysilyl)propyl]amino]ethanol TIFF0007621267000018.tif53130-3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007621267000019.tif60113-3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007621267000020.tif63125-N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine TIFF0007621267000021.tif48113-N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine TIFF0007621267000022.tif54130-N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine TIFF0007621267000023.tif45113-N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The file is TIFF0007621267000024.tif51130.

[0079] Organosilicon compounds of formula (II) are commercially available.

[0080] Bis(trimethoxysilylpropyl)amine, having the CAS number 82985-35-1, can be purchased from Sigma-Aldrich.

[0081] Bis[3-(triethoxysilyl)propyl]amine, having the CAS number 13497-18-2, can be purchased, for example, from Sigma-Aldrich.

[0082] N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine, alternatively referred to as bis(3-trimethoxysilylpropyl)-N-methylamine, can be purchased commercially from Sigma-Aldrich or Fluorochem.

[0083] 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.

[0084] In a further 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 contains at least one organosilicon compound (a1) selected from the group consisting of:

[0085] In further tests, in particular dye tests, it has also been found that the agent (a) applied to the keratinous material in the method has the formula (IV) R9Si(OR 10 ) k (R 11 ) m (IV) It has proven particularly advantageous when the composition comprises at least one organosilicon compound of the formula:

[0086] The compound of formula (IV) is an organosilicon compound selected from silanes having one, two or three silicon atoms, which organosilicon compound contains one or more hydroxyl and / or hydrolyzable groups per molecule.

[0087] The organosilicon compound(s) of formula (IV) may also be referred to as silanes of the alkyl-alkoxy-silane or alkyl-hydroxy-silane type, R9Si(OR 10 ) k (R 11 ) m (IV), During the ceremony -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 an integer of 3-k.

[0088] In a further preferred embodiment, the method further comprises the step of: the agent (a) comprises at least one organosilicon compound (a1) of formula (IV), R9Si(OR 10 ) k (R 11 ) m (IV), During the ceremony -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 an integer of 3-k It is characterized by:

[0089] In a further preferred embodiment, the method comprises the steps of: (a) comprising, in addition to the organosilicon compound(s) of formula (I), at least one further organosilicon compound of formula (IV), R9Si(OR 10 ) k (R 11 ) m (IV), During the ceremony -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 an integer of 3-k It is characterized by:

[0090] In a further preferred embodiment, the method comprises the steps of: (a) comprising, in addition to the organosilicon compound(s) of formula (II), at least one further organosilicon compound of formula (IV), R9Si(OR 10 ) k (R 11 ) m (IV), During the ceremony -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 an integer of 3-k It is characterized by:

[0091] In a further preferred embodiment, the method comprises the steps of: (a) comprising, in addition to the organosilicon compound(s) of formula (I) and / or (II), at least one further organosilicon compound of formula (IV), R9Si(OR 10 ) k (R11 ) m (IV), During the ceremony -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 an integer of 3-k It is characterized by:

[0092] In the organosilicon compound of formula (IV), the R group is a C1-C 18 Represents an alkyl group. 18 The alkyl group is saturated and may be linear or branched. Preferably, R is a linear C1-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-hexyl group or an n-octyl group.

[0093] In the organosilicon compound of the form (IV), R 10 The group represents a hydrogen atom or a C1 to C6 alkyl group. 10 represents a methyl group or an ethyl group.

[0094] In the organosilicon compound of the form (IV), R 11 The group represents a C1 to C6 alkyl group. Particularly preferably, R 11 represents a methyl group or an ethyl group.

[0095] Furthermore, k represents a natural number between 1 and 3, and m represents a natural number between 3 and k. If k represents the number 3, then m is 0. If k represents the number 2, then m is 1. If k represents the number 1, then m is 2.

[0096] Particularly stable films, i.e. dyeings having particularly good wash-off fastness properties, can be obtained when an agent (a) is used in the process, which comprises at least one organosilicon compound (a1) corresponding to formula (IV): in which the residue k has the value 3. In this case, the remaining m represents the value 0.

[0097] Organosilicon compounds of the formula (IV) which are particularly suitable for solving the problems according to the invention are -Methyltrimethoxysilane TIFF0007621267000025.tif3430-Methyltriethoxysilane TIFF0007621267000026.tif4138-Ethyltrimethoxysilane TIFF0007621267000027.tif3439-Ethyltriethoxysilane TIFF0007621267000028.tif4148-n-Hexyltrimethoxysilane TIFF0007621267000029.tif3474-n-Hexyltriethoxysilane TIFF0007621267000030.tif4185-n-Octyltrimethoxysilane TIFF0007621267000031.tif3493-n-Octyltriethoxysilane TIFF0007621267000032.tif41102-n-dodecyltrimethoxysilane, and / or TIFF0007621267000033.tif34130-n-Dodecyltriethoxysilane TIFF0007621267000034.tif43140 n-Octadecyltrimethoxysilane and / or n-Octadecyltriethoxysilane.

[0098] In a further preferred embodiment, the method according to the invention comprises the step of: -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -Dodecyltrimethoxysilane -Dodecyltriethoxysilane octadecyltrimethoxysilane, and / or -Octadecyltriethoxysilane The present invention is characterized in that it contains at least one organosilicon compound (a1) of formula (IV) selected from the group consisting of:

[0099] The above-mentioned organosilicon compounds are reactive compounds. In this connection, 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).

[0100] In a further preferred embodiment, the process according to the invention is characterized in that the agent (a) comprises 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).

[0101] In order to obtain particularly good dyeing results, it is particularly advantageous to use the organosilicon compounds of formula (I) and / or (II) in a specific range of amounts, which is on average (a).Particularly preferably, the 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 the agent (a).

[0102] In a further preferred embodiment, the process according to the invention is characterized in that the agent (a) comprises 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).

[0103] Furthermore, it has been found to be particularly preferred when the organosilicon compound(s) of formula (IV) are also present in a specific range of amounts, which average to (a). Particularly preferably, agent (a) comprises 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).

[0104] In a further preferred embodiment, the process according to the invention is characterized in that the agent (a) comprises one or more organosilicon compounds of the 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).

[0105] In the course of the research leading to the present invention, it was found that even when agent (a) contains two organosilicon compounds which are structurally different from one another, it is possible to obtain a particularly stable and uniform film on keratinous materials.

[0106] In another preferred embodiment, the process according to the invention is characterized in that the agent (a) comprises at least two structurally different organosilicon compounds.

[0107] In one 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.

[0108] In one obviously quite particularly preferred embodiment, the method according to the invention is characterized in that the agent (a) is applied to the keratinous material, which comprises at least one organosilicon compound of formula (I) selected from the group consisting of (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and further comprises at least one organosilicon compound of formula (IV) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.

[0109] In a further 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 wt. % of at least one second organosilicon compound (a1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane The present invention is characterized by comprising:

[0110] In this embodiment, the agent (a) contains one or more organosilicon compounds of the first group in a total amount of 0.5 to 3% by weight, the organosilicon compounds of the first group being 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.

[0111] In this embodiment, the agent (a) contains one or more organosilicon compounds of the second group in a total amount of 3.2 to 10% by weight, the organosilicon compounds of the second group being selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane and / or octadecyltriethoxysilane.

[0112] Even the addition of a small amount of water leads to the hydrolysis of the organosilicon compound having at least one hydrolyzable group.The hydrolysis product and / or the organosilicon compound having at least one hydroxyl group may react with each other in condensation reaction.For this reason, both the organosilicon compound having at least one hydrolyzable group and its hydrolysis product and / or condensation product may be present in agent (a).When using an organosilicon compound having at least one hydroxyl group, both the organosilicon compound having at least one hydroxyl group and its condensation product may be present in agent (a).

[0113] Condensation product is understood to be the product formed 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 elimination of water and / or the elimination of alkanol.Condensation product may be, for example, a dimer, but also a trimer or oligomer, and the condensation product is in equilibrium with the monomer.Depending on the amount of water used or consumed in hydrolysis, the equilibrium shifts from the monomeric organosilicon compound to the condensation product.

[0114] Particularly good results have been obtained when using organosilicon compounds of formula (I) and / or (II) in the method.As described above, hydrolysis / condensation is already initiated at traces of moisture, so the condensation products of organosilicon compounds (I) and / or (II) are also included in this embodiment.

[0115] Color forming compound (a2) When agent (a) is applied to keratinous materials, the organosilicon compound(s) (a1) containing one or more hydroxyl or hydrolyzable groups per molecule are first hydrolyzed and oligomerized or polymerized in the presence of water. The hydrolysis products or oligomers thus formed have a particularly high affinity for the surface of the keratinous materials. The simultaneous presence of coloring compound (a2) in agent (a) results in the incorporation of said compound in the resulting oligomer or polymer, forming a colored film on the keratinous materials. After application of agent (a), agent (b) is then applied. The successive application of agents (a) and (b) thus results in a coloration that is particularly durable to external influences. The coloring compound encapsulated in such a durable film exhibits good wash-off fastness.

[0116] Thus, as essential component (a2) of the present invention, the agent (a) used in the dyeing process comprises at least one colorant compound, including at least one substrate flake-based pigment, including vacuum metal deposition pigments.

[0117] The substrate flakes have an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, particularly preferably at most 20 nm. The average thickness of the substrate flakes 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 substrate flake thickness 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 and 10-20 nm. Preferably, each substrate flake has a thickness as uniform as possible.

[0118] Due to the small thickness of the substrate flakes, the pigments exhibit particularly high hiding power.

[0119] The substrate flakes have a monolithic structure. Monolithic in this context means that they consist of a single closed unit without cracks, stratification or inclusions, although structural variations may occur within the substrate flakes. The substrate flakes are preferably of uniform structure, i.e., there are no concentration gradients within the flakes. In particular, the substrate flakes do not have a layered structure and do not have any particles or particles distributed within them.

[0120] The size of the substrate flakes can be adjusted for each application purpose, in particular for the desired effect on keratinous materials.Typically, the substrate flakes have an average maximum diameter of about 2 to 200 μm, in particular about 5 to 100 μm.

[0121] In one preferred design, the aspect ratio, which is the ratio of the average size to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, more preferably more than 750. The average size of the uncoated substrate flakes is the d50 value of the uncoated substrate flakes. Unless otherwise stated, the d50 value was measured by quixel wet dispersion using a Sympatec Helos instrument. To prepare the samples, the samples to be analyzed were pre-dispersed in isopropanol for 3 minutes.

[0122] The substrate flakes can be composed of any material that can be formed into a flake shape.

[0123] The substrate flakes can be of natural origin, but can also be synthetically produced. Materials from which the substrate flakes can be constructed 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 flakes are constructed of metals (alloys).

[0124] Any metal suitable for metallic luster pigments can be used. Such metals include iron and steel, and any (semi)metal that is durable in air and water, such as platinum, zinc, chromium, molybdenum and silicon, and its alloys, such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver and gold. Preferred substrate flakes include aluminum flakes and brass flakes, with aluminum substrate flakes being particularly preferred.

[0125] Vacuum metal deposition pigments (VMP) are obtained, for example, by stripping off metals, metal alloys or metal oxides in the form of a suitable coating. They are characterized by a particularly low substrate flake thickness in the range of 5-50 nm and a particularly smooth surface with high reflectivity. The substrate flakes constituting the vacuum metal deposition pigments are also referred to as VMP substrate flakes in the context of the present application. VMP substrate flakes of aluminum are obtained, for example, by stripping off aluminum in the form of a metal deposition coating.

[0126] Substrate flakes of metal or metal alloy may be passivated, for example, by anodization (oxide layer) or chromate treatment.

[0127] Uncoated VMP substrate flakes, especially those made of metals or metal alloys, are highly reflective of incident light, resulting in light / dark flop but not color.

[0128] The color may be produced, for example, by optical interference effects. Such pigments may be based on substrate flakes having at least one coating. Such show interference effects due to the overlap of light rays that are refracted and reflected differently.

[0129] Thus, preferred pigments are pigments based on coated VMP substrate flakes. The substrate flakes preferably have at least one coating B of a highly refractive metal oxide with a coating thickness of at least 50 nm. Preferably, there is another coating A between coating B and the substrate flake surface. If necessary, there is a further coating C on layer B, which is different from the underlying layer B.

[0130] Suitable materials for coatings A, B and C are any substances that can be applied in a film-like, permanent manner to the substrate flakes and that, in the case of coatings A and B, have the required optical properties. In general, the coating on the substrate flake surface is sufficient to obtain a pigment with a gloss effect. For example, only the top and / or bottom surface of the substrate flakes may be coated, but not the side(s). Preferably, the entire surface, including the optionally passivated side surfaces of the substrate flakes, is covered by coating B. Thus, the substrate flakes are completely covered by coating B. This improves the optical properties of the pigment and increases its mechanical and chemical durability. The above also applies to layer A and, if present, preferably to layer C.

[0131] Although several coatings A, B and / or C may be present in each case, the coated substrate flake preferably has only one coating A, B and, if present, C in each case.

[0132] Coating B is composed of at least one highly refractive metal oxide. Highly refractive materials have a refractive index of at least 1.9, preferably at least 2.0, more preferably at least 2.4. Preferably, Coating B comprises at least 95% by weight, more preferably at least 99% by weight of the high refractive index metal oxide(s).

[0133] Coating B has a thickness of at least 50 nm. Preferably, the thickness of Coating B is no greater than 400 nm, more preferably no greater than 300 nm.

[0134] Highly refractive metal oxides suitable for coating B are preferably 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), and mixtures thereof. Colorless high refractive index oxides such as titanium dioxide and / or zirconium oxide are also suitable.

[0135] Coating B may also contain selectively light-absorbing dyes, preferably in an amount of 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, in each case based on the total amount of coating B. Suitable dyes are organic and inorganic dyes which are stably incorporated into the metal oxide coating.

[0136] Coating A preferably comprises at least one low refractive index metal oxide and / or metal oxide hydrate. Preferably, Coating A comprises at least 95% by weight, more preferably at least 99% by weight, of a 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 coating A include, for example, silicon dioxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, and mixtures thereof, with silicon dioxide being preferred. Coating A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, and particularly preferably 5 to 20 nm.

[0138] Preferably, the distance between the substrate flake surface and the inner surface of coating B is at most 100 nm, particularly preferably at most 50 nm, particularly preferably at most 20 nm. By ensuring that the thickness of coating A and thus the distance between the substrate flake surface and coating B is within the ranges specified above, it is possible to ensure that the pigment has high hiding power.

[0139] If the VMP substrate flake based pigment only has layer A, it is preferred that the pigment has a VMP substrate flake of aluminum and a layer A of silica. If the VMP substrate flake based pigment has layers A and B, it is preferred that the pigment has a VMP substrate flake of aluminum, a layer A of silica and a layer B of iron oxide.

[0140] According to a preferred embodiment, the pigment has a further coating C of a metal oxide (hydrate) different from the base coating 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.

[0141] Coating C preferably has a thickness of 10 to 500 nm, more preferably 50 to 300 nm. For example, by providing coating C on TiO2, better interference can be obtained while maintaining high hiding power.

[0142] Layers A and C perform the functions of preservation and chemical and physical stabilization. Particularly preferred layers A and C are silica or alumina applied by a sol-gel process. This method comprises dispersing VMP substrate flakes, either uncoated or already coated with layers A and / or B, in a solution of a metal alkoxide, e.g. tetraethyl orthosilicate or aluminum triisopropanolate (usually in an organic solvent or a mixture of an organic solvent and water, where the organic solvent is at least 50% by weight an organic solvent, e.g. a C1-C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, thereby forming a film of metal oxide on the surface of the (coated) substrate flakes.

[0143] Layer B can be produced, for example, by hydrolytic decomposition of one or more organometallic compounds and / or by deposition of one or more dissolved metal salts, followed by an optional post-treatment, for example, conversion of the formed hydroxide-containing layer to an oxide layer by annealing.

[0144] Each of coatings A, B and / or C may be composed of a mixture of two or more metal oxides (hydrates), however each coating is preferably composed of one metal oxide (hydrate).

[0145] The pigments based on coated VMP substrate flakes 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. Due to the low thickness of the substrate flakes, the pigments exhibit a particularly high hiding power. The low thickness of the coated substrate flakes is obtained by keeping the thickness of the uncoated substrate flakes low, but also by adjusting the thickness of coating A and, if present, coating C, to the smallest possible values. The thickness of coating B determines the color appearance of the pigment.

[0146] The adhesion and abrasion resistance of the coated VMP substrate flake-based pigments on keratinous materials can be significantly increased by further modifying the outermost layer, layer A, B or C, with an organic compound, such as silane, phosphate ester, titanate, borate or carboxylic acid, depending on the structure. In this case, the organic compound is bonded to the surface of the outermost, preferably metal oxide-containing layer A, B or C. The outermost layer refers to the layer spatially furthest from the VMP substrate flake. The organic compound is preferably a functional silane compound capable of bonding to the metal oxide-containing layer A, B or C. It can be either a monofunctional or bifunctional compound. Examples of bifunctional organic compounds are methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyl-triethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyltris(meth-ethoxy)silane, 3-methacryloxypropyltris(butoxyethoxy)silane, 3-methacryloxypropyltris(propoxy)silane. , 3-methacryloxypropyltris(butoxy)silane, 3-acryloxypropyltris(methoxyethoxy)silane, 3-acryloxypropyltris(butotrimethoxy)silane, vinyl,propoxyethoxy)silane, vinyl,butoxyethoxy,tris(butoxyethoxy), vinyl,butoxyethoxy)silane, vinyl,vinyltriethoxysilane, vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, phenylvinyldiethoxysilane or phenylallyldichlorosilane. Furthermore, modification with monofunctional silanes, alkylsilanes or arylsilanes may be carried out.It has only one functional group, which can be covalently bonded to the surface of the coated VMP substrate flake-based pigment (i.e., to the outermost metal oxide-containing layer) or to the metal surface if not completely covered. The hydrocarbon residue of the silane points away from the pigment. Depending on the type and nature of the hydrocarbon residue of the silane, pigments with different degrees of hydrophobicity are obtained. Examples of such silanes include hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Particularly preferred are silica-coated aluminum substrate flake-based pigments surface-modified with monofunctional silanes. Octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane and hecadecyltriethoxysilane are particularly preferred. The modification / hydrophobization of the surface properties results in improvements in adhesion, abrasion resistance and orientation in the application.

[0147] It has also been shown that VMP substrate flake-based pigments having such surface modifications exhibit better compatibility with the organosilicon compounds and / or their condensation or polymerization products used.

[0148] Particularly good results have been obtained when agent (a) contains one or more VMP substrate flake base 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, very preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0149] Substrate flake-based pigments which constitute vacuum metal deposition pigments are available, for example, under the name Alegrace® Marvelous from Schlenk Metallic Pigments GmbH.

[0150] VMP substrate flake based pigments have a defined particle size in terms of thickness and particle area, which allows complete coverage of keratinous materials when used in appropriate amounts, and dyeings with VMP substrate flake based pigments show extremely high rub and wash-off fastness due to their smooth surface structure.

[0151] In addition to the VMP substrate flake base pigment, agent (a) may contain further colorant compounds selected from the group consisting of pigments and / or direct dyes.

[0152] In this connection, the use of pigments has proven to be particularly advantageous.

[0153] In another very particularly preferred embodiment the process is characterized in that the agent (a) comprises at least one further colorant compound (a2) from the group of the pigments.

[0154] Pigments within the meaning of the present invention are colored compounds that have a solubility in water at 25°C of less than 0.5 g / L, preferably less than 0.1 g / L, and even 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 stir bar is added. Then 1 liter of distilled water is added. The mixture is heated to 25°C for 1 hour while stirring with a magnetic stirrer. If after this period undissolved components of the pigment are still visible in the mixture, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be visually evaluated, possibly due to a high loading of finely dispersed pigment, the mixture is filtered. If a certain percentage of undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0155] Suitable colour pigments can be of inorganic and / or organic origin.

[0156] In one preferred embodiment, the composition according to the invention is characterized in that the composition (a) comprises at least one further colorant compound (a2) from the group consisting of pigments) inorganic and / or organic pigments.

[0157] Preferred color pigments are selected from synthetic or natural inorganic pigments.Natural inorganic color pigments can be made, for example, from chalk, yellow ocher, amber, green earth, red earth (burnt Terra di Siena) or graphite.Furthermore, black pigments, such as black iron oxide, colored pigments, such as ultramarine or red iron oxide, as well as fluorescent or phosphorescent pigments can be used as inorganic color pigments.

[0158] Particularly suitable are colored metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, metal cyanide complexes, metal sulfates, chromates and / or molybdates.Preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red-brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510) and / or carmine (cochineal).

[0159] According to the present invention, colored pearlescent pigments are also particularly preferred color pigments. They are usually based on mica and / or glimmer and can be coated with one or more metal oxides. Micas belong to the group of layered silicates. The most important representatives of such silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and nacre. To prepare pearlescent pigments in combination with metal oxides, mica, mainly muscovite or phlogopite, is coated with metal oxide.

[0160] 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 (Mica) (Glimmer) and are coated with one or more of the above metal oxides. The color of each pigment can be modified by changing the thickness of the layer of the metal oxide(s).

[0161] Also preferred mica-based pigments are synthetically produced mica flakes based on synthetic fluorophlogopite (INCI: synthetic fluorophlogopite) coated with metal oxide. The synthetic fluorophlogopite flakes are coated with, for example, tin oxide, iron oxide(s) and / or titanium dioxide. The metal oxide layer may further comprise a pigment, for example, ferricyanide ferrate (II / III) or carmine red. Such mica pigments are available, for example, from Eckart under the name SYNCRYSTAL.

[0162] In a further preferred embodiment, the method is characterized in that the agent (a) comprises at least one further colorant compound (a2) from the group of inorganic pigments selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, metal cyanide complexes, metal sulfates, bronze pigments and / or the group of colored Mica or Glimmer-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0163] In a further preferred embodiment, the method is characterized in that the agent (a) comprises at least one further colorant compound (a2) from the group of pigments selected from mica or glimmer-based pigments reacted with one or more metal oxides 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).

[0164] Other suitable pigments are based on metal oxide-coated platelet-shaped borosilicates. These are coated with, for example, tin oxide, iron oxide(s), silicon dioxide and / or titanium dioxide. Such borosilicate-based pigments are available, for example, under the name MIRAGE from Eckart or under the name Reflecks from BASF SE.

[0165] Examples of particularly suitable colored pigments are those commercially available under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors, Flamenco®, Cellini®, Cloisonne®, Duocrome®, Gemtone®, Timica®, MultiReflections, Chione from BASF SE, and Sunshine® from Sunstar.

[0166] Particularly preferred color pigments having 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 Oxides) Colorona Bordeaux, Merck, Mica, CI 77491 (Iron Oxide) Colorona Bronze, Merck, Mica, CI 77491 (Iron Oxide) Colorona Bronze Fine, Merck, Mica, CI 77491 (Iron Oxides) Colorona Fine Gold MP 20, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Sienna Fine, Merck, CI 77491 (iron oxide), mica Colorona Sienna, Merck, Mica, CI 77491 (Iron Oxide) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, CI 77491 (Iron Oxides), Tin Oxide Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxide, Mica, CI 77891, CI 77491(EU) Colorona Mica Black, Merck, CI 77499 (iron oxides), mica, CI 77891 (titanium dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Blackstar Gold, Merck, Mica, CI 77499 (Iron Oxides) Colorona SynCopper, Merck, synthetic fluorphlogopite (and) iron oxide Colorona SynBronze, Merck, synthetic fluorphlogopite (and) iron oxide It is.

[0167] Other particularly preferred colour pigments having the trade name Xirona® are, for example: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Le Rouge, Merck, iron oxide (and) silica It is.

[0168] Particularly preferred colour pigments also have the trade name Unipure®, for example: Unipure Red LC 381 EM, Sensient CI 77491 (iron oxide), silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (iron oxide), silica It is.

[0169] Particularly preferred pigments also have the trade name Flamenco®, for example: Flamenco® Summit Turquoise T30D, BASF, titanium dioxide (and) mica Flamenco® Super Violet 530Z, BASF, mica (and) titanium dioxide It is.

[0170] In a further embodiment of the process, the agent (a) may also contain one or more colorant compounds from the group of the organic pigments as further colorant compounds (a2).

[0171] The organic pigments are correspondingly insoluble organic dyes or colorants and may be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketo-pyrrolopyorrole, indigo, thioindido, dioxazine and / or triarylmethane compounds.

[0172] Particularly suitable examples of organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments having the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments having the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments having the color index numbers CI 61565, CI 61570, CI 74260, orange pigments having the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, and the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0173] In another particularly preferred embodiment, the method according to the invention is characterized in that the composition (a) is composed of carmine, quinacridone, phthalocyanine, sorghum, blue pigments having the Color Index Numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments having the Color Index Numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments having the Color Index Numbers CI 61565, CI 61570, CI 74260, orange pigments having the Color Index Numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments having the Color Index Numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0174] The organic pigment may also be a pigmented coating. In the sense of the present invention, the term pigmented varnish is understood to mean a particle comprising an adsorbed dye layer, the particle and the dye unit being insoluble under the above conditions. The particle may be, for example, an inorganic substrate, which may be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate or may be aluminum.

[0175] For example, alizarin colored varnish can be used.

[0176] Due to their excellent light and temperature stability, it is particularly preferred to use the above mentioned pigments in agent (a). It is also preferred if the pigment used has a certain particle size, which on the one hand results in a uniform distribution of the pigment in the polymer film formed and on the other hand avoids a feeling of roughness on the hair or skin after application of the cosmetic product. Thus, according to the invention, the 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 if the average particle size D 50 can be measured, for example, using dynamic light scattering (DLS).

[0177] In addition to the VMP substrate flake-based pigments, the agent (a) may contain, as further colorant compound(s) (a2), other effect pigments, for example lamellar-structured substrate flake-based pigments and / or biconvex substrate flake-based pigments.

[0178] In a further preferred embodiment, the method is characterized in that agent (a) comprises one or more further 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, relative to the total weight of agent (a).

[0179] As further colorant compound(s) (a2), the agent (a) used in the method may also contain one or more direct dyes. Direct action dyes are dyes that are applied directly to the hair and do not require an oxidative process for color formation. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols.

[0180] Direct dyes within the meaning of the present invention are those that have a solubility in water greater than 0.5 g / L at 25° C. (760 mmHg) and are therefore not considered pigments.

[0181] Preferably, direct dyes within the meaning of the present invention have a solubility in water of more than 1 g / L at 25° C. (760 mmHg).

[0182] Direct dyes can be divided into anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

[0183] In a further preferred embodiment, the method is characterized in that the agent (a) comprises at least one anionic direct dye, cationic direct dye and / or non-ionic direct dye as further coloring compound (a2).

[0184] In a further preferred embodiment, the method is characterized in that the agent (a) comprises at least one further colorant compound (a2) from the group consisting of anionic direct dyes, nonionic direct dyes and / or cationic direct dyes.

[0185] Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51, Basic Red 76.

[0186] As nonionic direct dyes, nonionic nitro and quinone dyes as well as neutral azo dyes can be used. Suitable nonionic direct dyes are known compounds designated by the international designation or trade name 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, 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)-amino-2-nitrobenzene, 4-nitro-2-nitrophenol, 5-nitro-2-nitrophenol, 6-nitro-2-nitrophenol, 7-nitro-2-nitrophenol, 8-nitro-2-nitrophenol, 9-nitro-2-nitrophenol, 10-nitro-2-nitrophenol, 11-nitro-2-nitrophenol, 12-nitro-2-nitrophenol, 13-nitro-2-nitrophenol, 14-nitro-2-nitrophenol, 15-nitro-2-nitrophenol, 16-nitro-2-nitrophenol, 17-nitro-2-nitrophenol, 18-nitro-2-nitrophenol, 19-nitro-2-nitrophenol, 20-nitro-2-nitrophenol, 21-nitro-2-nitrophenol, 22-nitro-2-nitrophenol, 23-nitro-2-nitrophenol, 24-nitro-2-nitrophenol, 25-nitro-2-nitrophenol, 26-nitro-2-nitrophenol, 27-nitro- 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.

[0187] In the course of the research which led to the present invention, it was found that dyeings of particularly high colour strength can be produced with an agent (a) which contains at least one anionic direct dye.

[0188] Thus, in one obviously quite particularly preferred embodiment, the method is characterized in that the agent (a) further comprises at least one anionic direct dye.

[0189] Anionic direct dyes are also called acid dyes. Acid dyes are direct dyes that have at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H). Depending on the pH value, the protonated form of the carboxylic acid or sulfonic acid group (-COOH, -SO3H) can be converted into its deprotonated form (-OO - , -SO3 - The proportion of the protonated form increases with decreasing pH. When the direct dye is used in the form of its salt, the carboxylic acid or sulfonic acid group is present in the deprotonated form and is neutralized with the corresponding stoichiometric equivalent of cation to maintain electrical neutrality. The acid dye in the present invention can also be used in the form of its sodium and / or potassium salt.

[0190] Acid dyes within the meaning of the present invention are those that have a solubility of more than 0.5 g / L in water at 25° C. (760 mmHg) and are therefore not considered pigments. Preferably, acid dyes within the meaning of the present invention have a solubility of more than 1 g / L in water at 25° C. (760 mmHg).

[0191] The alkaline earth (e.g. calcium and magnesium) or aluminum 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.

[0192] An essential feature of acid dyes is the ability to form an anionic charge, the carboxylic or sulfonic acid group which carries this is usually linked to different chromophore systems. Suitable chromophore systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.

[0193] In one embodiment, the method for dyeing keratinous materials is therefore preferably characterized in that the composition (a) further comprises 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, xanthene dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes, each of the dyes derived from the above groups having 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).

[0194] 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, Japanese Yellow No. 403, CI 10316, COLIPA No. B001), Acid Yellow 3 (COLIPA No.: C 54, D&C Yellow No. 10, Quinoline Yellow, E104, Food Yellow No. 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA No. C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow No. 4, Japanese Yellow No. 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 No. C015), Acid Orange 10 (CI 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (Brown 1; CI 20170; KATSU201; not sodium salt; Brown No. 201; Resorcinol Brown; Acid Orange 24; Japanese Brown No. 201; D&C Brown No. 1), Acid Red 14 (CI 14720), Acid Red 18 (E124, Red No. 18; CI 16255), Acid Red 27 (E 123, CI 16185, C-Rot 46, Real Red D, FD&C Red No. 2, Food Red No. 9, Naphthol Red S), Acid Red 33 (Red No. 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CI18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodofluorescein, Eosin J, Iodoeosin), Acid Red 52 (CI 45100, Food Red No. 106, Solar Rhodamine B, Acid Rhodamine B, Red No. 106 Pontacil Brilliant Pink), Acid Red 73 (CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA No. C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine, Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet No. 2, CI 60730, COLIPA No. C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), Acid Blue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blue V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133, Patent Blue AE, Amido Blue AE, Erioglaucine A, CI 42090, CI Food Blue No. 2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585), Acid Green 3 (CI 42085, Food Green No. 1), Acid Green 5 (CI 42095), Acid Green 9 (CI 42100), Acid Green 22 (CI 42170), Acid Green 25 (CI 61570, Japanese Green No. 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 No.401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA No. B15), Acid Black 52 (CI 15711), Food Yellow No. 8 (CI 14270), Food Blue No. 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.

[0195] For example, the solubility of an anionic direct dye in water can be measured as follows: 0.1 g of anionic direct dye is placed in a beaker. A stir bar is added. Then 100 ml of water is added. The mixture is heated to 25° C. while stirring with a magnetic stirrer. It is stirred for 60 minutes. The aqueous mixture is then visually evaluated. If there is still undissolved residue, the amount of water is increased, for example by 10 ml increments. Water is added until the amount of dye used is completely dissolved. If the dye-water mixture cannot be visually evaluated due to high dye loading, the mixture is filtered. If a percentage of undissolved dye remains on the filter paper, the solubility test is repeated with a larger amount of 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.

[0196] Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40 g / L (25°C).

[0197] Acid Yellow 3 is a mixture of the sodium salts of monosulfonic acid and disulfonic acid of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione, and has a solubility in water of 20 g / L (25° C.).

[0198] Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, and its solubility in water is greater than 40 g / L (25°C).

[0199] 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 very soluble in water at 25°C.

[0200] Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonic acid. Its solubility in water is greater than 7 g / L (25 °C).

[0201] Acid Red 18 is 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonic acid trisodium salt, and has a very high solubility in water of more than 20% by weight.

[0202] Acid Red 33 is 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonic acid disodium salt, and its solubility in water is 2.5 g / L (25° C.).

[0203] 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, whose solubility in water has been shown to be greater than 10 g / L (25° C.).

[0204] Acid Blue 9 is 2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonic acid disodium salt, and its solubility in water is greater than 20% by weight (25°C).

[0205] Thus, a highly preferred method is one in which the agent (a) is selected from the group consisting of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 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 Violet 51, Acid Violet 52, Acid Violet 53, Acid Violet 54, Acid Violet 55, Acid Violet 56, Acid Violet 57, Acid Violet 58, Acid Violet 59, Acid Violet 60, Acid Violet 61, Acid Violet 62, Acid Violet 63, Acid Violet 64, Acid Violet 65, Acid Violet 66, Acid Violet 67, Acid Violet 68, Acid Violet 69, Acid Violet 70, Acid Violet 71, Acid Violet 72, Acid Violet 73, Acid Violet 74, Acid Violet 75, Acid Violet 76, Acid Violet 77, Acid Violet 78, Acid Violet 79, Acid Violet 80, Acid Violet 81, Acid Violet 82, Acid Violet 83, Acid Violet 84, Acid Violet 85, Acid Violet 86, Acid Violet 87, Acid Violet 88, Acid Violet 89 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow No. 8, Food Blue No. 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.

[0206] The direct dye(s), in particular the anionic direct dye(s), can be used in various amounts in the medium (a) depending on the desired color strength. Particularly good results have been obtained when the agent (a) contains one or more direct dyes (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, relative to its total weight.

[0207] In a further preferred embodiment the method is characterised in that the agent (a) further comprises one or more direct dyes as further colorant 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 preferably 0.5 to 4.5% by weight, relative to the total weight of agent (a).

[0208] Silicone polymer (a3) In another very particularly preferred embodiment, the agent (a) used in the process further comprises at least one silicone polymer (a3).

[0209] Silicone polymers, alternatively sometimes abbreviated as 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.

[0210] Silicone polymers generally have a molecular weight of at least 500 g / mol, preferably at least 1000 g / mol, more preferably at least 2500 g / mol, and particularly preferably at least 5000 g / mol, and are macromolecules that contain repeating organic units.

[0211] The maximum molecular weight of the 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 the purposes of the present invention, it is preferred if the maximum molecular weight of the silicone polymer is 107 g / mol or less, preferably 106 g / mol or less, and particularly preferably 105 g / mol or less.

[0212] Silicone polymers contain many Si-O repeating units, where the Si atoms may carry organic residues, such as alkyl or substituted alkyl groups.

[0213] The silicone polymer 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, and most preferably more than 500 Si-O repeat units, corresponding to a high molecular weight.

[0214] The silicone polymer (a3) ​​contained in agent (a) is therefore different from the silane (a1) also contained in agent (a).

[0215] In the context of one embodiment, the method for dyeing keratinous materials is therefore characterized in that the agent (a) is: (a3) at least one silicone polymer It is preferred that the composition is characterized by comprising:

[0216] In the research 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.

[0217] The film produced by oligomerization or polymerization of organosilicon compounds (silanes) (a1) may show some degree of stickiness or even flexibility, especially when using large amounts of silanes (a1), which may have a detrimental effect on the feel of keratinous materials on the one hand and on the other hand on the durability of the film.Without being bound by this theory, it is believed that the joint application of silanes (a1) and silicone polymers (a3) ​​in medium (a) leads to the reaction or interaction of these two components with each other.When silanes and silicone polymers are used together, it has been found that the silanes, as previously described, form a film, in which the silicone polymers are either incorporated or aggregated.The film thus formed is much more pliable, flexible, durable and less brittle.

[0218] It was therefore observed that the rheological properties of the film provided by agent (a) could be significantly improved by the addition of at least one silicone polymer (a3). In the presence of silicone polymer (a3), the film became stronger or harder, resulting in colored keratinous materials with a less sticky, smoother and more pleasant appearance. Furthermore, the higher film strength also had a positive effect on the fastness properties of the keratinous material, in particular on the friction fastness properties. The dyed film showed less abrasion when in contact with combs, brushes and textile products, as it became more durable when in contact with such items.

[0219] The above advantages are particularly evident 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).

[0220] In the context of one embodiment, the method for dyeing keratinous materials is therefore characterized in that the agent (a) is: (a3) at least one alkoxy- and / or amino-modified silicone polymer It is preferred that the composition is characterized by comprising:

[0221] In a further preferred embodiment, the method according to the invention is characterized in that the agent (a) comprises at least one alkoxy-modified silicone polymer.

[0222] 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 can be any of C2 to C6. 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 a group -O-CH3 or -O-CH2-CH3). However, it is equally according to the invention if the alkoxy group itself carries further substituents; in this 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) carries at least one group (-CH2-CH2-O-) and / or (-CH2-CH2-CH2-O-).

[0223] The alkoxy group may be linked to the silicone by either a carbon atom or an oxygen atom, for example the silicone may bear structural units of formula (Sa), (Sb), (Sc) and / or (Sd): TIFF0007621267000035.tif156147

[0224] It is particularly preferred when the alkoxy-modified silicone polymer(s) (a3) ​​carry more than one alkoxy group, i.e. when the silicone polymer (a3) ​​is of polyalkoxylated type. 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.

[0225] Particularly preferably, the alkoxy-modified silicone (a3) ​​is a non-ionic silicone, which carries no positive or negative charge.

[0226] Very particularly suitable polyalkoxylated silicones (a3) ​​are those which have at least one formula (SI) TIFF0007621267000036.tif contains 66119 structural units, During the ceremony n is an integer of 2 to 20, preferably an integer of 4 to 18, more preferably an integer of 6 to 16, even more preferably an integer of 8 to 14, and most preferably the value 12.

[0227] In the above formula, the asterisk * The positions marked with represent the free valence of the corresponding bond, where said bond may be to an additional Si atom, an additional O atom and / or an additional C atom.

[0228] In the context of one embodiment, the method for dyeing keratinous materials is therefore characterized in that the agent (a) is: At least one formula (SI) At least one silicone polymer (a3) ​​containing structural units of TIFF0007621267000037.tif66119, During the ceremony 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. It is preferable that the present invention is characterized by the above.

[0229] A preferred example of alkoxy-modified silicone polymer (a3) ​​may contain, in addition to one or more structural units of general formula (SI), further structural units that are structurally different from the units of formula (SI).Particularly preferably, alkoxy-modified silicone polymer further comprises one or more dimethylsiloxane units.Depending on whether the silicone of the present invention 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) ​​according to the present invention has in each case a trimethylsilyloxy group (i.e. the group -O-Si(CH3)3) as end group.

[0230] In a further particularly preferred embodiment, the method therefore comprises the steps of: (a) a compound represented by the formula (SI), (S-II), (S-III) and (S-IV) TIFF0007621267000038.tif102161 At least one silicone polymer (a3) ​​composed of structural units of TIFF0007621267000039.tif3166, In the formula, n represents, independently in each structural unit (SI), in each case 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 value 12. It is characterized by:

[0231] Silicone polymer (a3) ​​consisting of structural units of formula (SI), formula (S-II), formula (S-III) and formula (S-IV) is understood in this context 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, said silicones can also contain different structural units of formula (SI), each of which is differentiated by its numerical value n.

[0232] Each position marked with an asterisk in a structural unit represents a point of attachment to other structural units. For example, one example of a very particularly preferred silicone polymer (a3) ​​composed of structural units of formula (SI), formula (S-II), formula (S-III) and formula (S-IV) may have the following structure: TIFF0007621267000040.tif60131 where x and y are selected depending on the desired molecular weight of the silicone and n represents one of the abovementioned preferred or particularly preferred integers according to the invention.

[0233] Both low molecular weight alkoxy-modified silicones and high molecular weight alkoxy-modified silicones can be used as silicone polymer (a3). Particularly beneficial effects have been observed with 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.

[0234] Particularly suitable silicone polymers are: Abil B 8843, PEG-14 Dimethicone, from Evonik Dow Corning Xiameter OFX 0193 Fluid, PEG-12 Dimethicone Examples include:

[0235] Furthermore, particularly good results were also obtained when an agent (a) comprising an amino-modified silicone polymer (a3) ​​was used in the process, which may alternatively be called amino-functionalized silicone polymer or aminosilicone.

[0236] In another preferred embodiment, the method is characterized in that agent (a) comprises at least one amino-modified silicone polymer.

[0237] The agent (a) may contain one or more different amino-modified silicone polymers (a3). Such silicones may, for example, be of the formula (SV) M(R a Q b SiO (4-a-b) / 2)x (R c SiO (4-c) / 2)y M (SV) wherein R is a hydrocarbon or hydrocarbon residue having from 1 to about 6 carbon atoms and Q is of the general formula -R 1 HZ, where R 1 is bonded to hydrogen and to the Z residue and is a divalent linking group composed of a carbon atom and a hydrogen atom, a carbon atom, a hydrogen atom and an oxygen atom, or a carbon atom, a hydrogen atom and a nitrogen atom; Z is an organic amino functional residue 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 2,000, 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. Non-limiting examples of groups represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl, and the like; alkenyl groups such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, and the like; phenyl groups, benzyl groups, halohydrocarbon residues such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl, and the like; and sulfur-containing groups such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl, and the like; preferably, R is an alkyl group containing from 1 to about 6 carbon atoms, and most preferably R is methyl. 1Examples include methylene, ethylene, propylene, hexamethylene, decamethylene, -CH2CH(CH3)CH2-, phenylene, naphthylene, -CH2CH2SCH2CH2-, -CH2CH2OCH2-, -OCH2CH2-, -OCH2CH2CH2-, -CH2CH(CH3)C(O)OCH2-, -(CH2)3CC(O)OCH2CH2-, -CH4C6H4-, -C6H4CH2C6H4-; and -(CH2)3C(O)SCH2CH2-.

[0238] Z is an organic amino functional residue containing at least one amino functional group. One possible formula for Z is NH(CH2) z NH2, where z is 1 or greater. One possible formula for Z is -NH(CH2) z (CH2) zz NH, where z and zz are both independently 1 or greater, and the structure includes a diamino ring structure, such as piperazinyl. Z is most preferably a -NHCH2CH2NH2 residue. Another possible 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.

[0239] Q is most preferably a polar amine functional residue of the formula -CH2CH2CH2NHCH2CH2NH2, where "a" has a value ranging from about 0 to about 2, "b" has a value ranging 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. If more than one silicone of the above formula is used, the various variable substituents in the above formula may be different for the various silicone components present in the silicone blend.

[0240] In one particularly preferred embodiment, the method according to the invention comprises applying an agent (a) to keratinous materials, which agent (a) is an amino-modified silicone polymer (a3) ​​of formula (S-VI), R' a G 3-a -Si(OSiG2) n -(OSiG b R' 2-b ) m -O-SiG 3-a -R' a (S-VI), 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-CH2CH2C H2CH3, -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 between 0 and 3, especially 0, -b represents a number between 0 and 1, especially 1, -m and n are numbers whose sum (m+n) is 1 to 2000, preferably 50 to 150, where n is preferably a value of 0 to 1999 and 49 to 149, and m is preferably a value of 1 to 2000 and 1 to 10; -R' is 〇-QN(R'')-CH2-CH2-N(R'')2 〇-QN(R'')2 〇-QN + (R'')3A - 〇-QN + H(R'')2A - 〇-QN + H2(R'')A - 〇-QN(R'')-CH2-CH2-N + R''H2A - , is a monovalent residue selected from where 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 represents an alkyl group, 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, and A represents an anion preferably selected from chloride, bromide, iodide or methosulfate. It is characterized by meaning that.

[0241] In another preferred embodiment, the method comprises applying an agent (a) to a keratinous material, the agent (a) comprising at least one amino-modified silicone polymer (a3) ​​of formula (S-VII), In the TIFF0007621267000041.tif23111 formula, m and n are numbers whose sum (m+n) is 1 to 2000, preferably 50 to 150, and n preferably assumes a value of 0 to 1999 and 49 to 149, and m preferably assumes a value of 1 to 2000 and 1 to 10. According to the INCI declaration, such silicones are called trimethylsilylamodimethicones.

[0242] In another preferred embodiment, the method comprises applying an agent (a) to keratinous materials, the agent (a) comprising at least one amino-modified silicone polymer (a3) ​​of formula (S-VIII), In the formula TIFF0007621267000042.tif2596, R represents an -OH, -O-CH3 or -CH3 group, m, n1 and n2 are numbers such that the sum (m+n1+n2) is 1 to 2000, preferably 50 to 150, and the sum (n1+n2) is preferably assumed to be a value of 0 to 1999 and 49 to 149, and m is preferably assumed to be a value of 1 to 2000, 1 to 10.

[0243] According to the INCI declaration, such amino-modified or amino-functionalized silicone polymers are known as amodimethicones.

[0244] 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 and 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.

[0245] In another preferred embodiment, the method comprises applying an agent (a) to keratinous materials, the agent (a) comprising at least one amino-modified silicone polymer (a3) ​​of formula (S-IX), TIFF0007621267000043.tif52111 expression -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 represent a hydroxy group or a C1-4 alkoxy group; wherein at least one of R1 to R3 represents a hydroxy group.

[0246] Another preferred method comprises applying an agent (a) to a keratinous material, said agent (a) comprising at least an amino-functional silicone polymer of formula (SX), TIFF0007621267000044.tif51115 expression -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 represent a hydroxy group or a C1-4 alkoxy group, and at least one of R1 and R2 represents a hydroxy group.

[0247] Silicones of formula (S-IX) and (SX) differ in the group at the Si atom carrying the nitrogen-containing group: in formula (S-IX), R2 represents a hydroxyl group or a C1-4 alkoxy group, while in formula (SX) the residue is a methyl group. The individual Si groups indicated by 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 statistically distributed manner, i.e., in formulas (S-IX) and (SX), not every R1-Si(CH3)2 group is bonded to a -[O-Si(CH3)2] group.

[0248] It has also been found that the method of applying to keratin fibers an agent (a) comprising at least one amino-modified silicone polymer (a3) ​​of formula (S-XI) is particularly effective in terms of the desired effect, TIFF0007621267000045.tif45101, where 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 fulfilled.

[0249] 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.

[0250] Particularly good effects in terms of improving the rub fastness were observed when the agent (a) containing a special 4-morpholinomethyl-substituted silicone polymer (a3) ​​was applied to the keratinous material in the procedure. This very particularly preferred amino-functionalized silicone polymer comprises at least one compound of the formula (S-XIII) TIFF0007621267000046.tif contains 5477 structural units.

[0251] In the context of one embodiment, the method for dyeing keratinous materials is therefore characterized in that the agent (a) is: At least one of the formula (S-XIII) Preferably, the silicone polymer (a3) ​​comprises at least one silicone polymer containing structural units of TIFF0007621267000047.tif5477.

[0252] Particularly good effects in terms of improving the rub fastness were also observed when the agent (a) containing the special 4-morpholinomethyl-substituted silicone polymer (a3) ​​was applied to the keratinous material in the procedure. This very particularly preferred amino-functionalized silicone polymer has the formula (S-XII) and the formula (S-XIII) TIFF0007621267000048.tif contains 53141 structural units.

[0253] In one obviously quite particularly preferred embodiment, the method according to the invention is characterized in that the agent (a) is a compound of 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 of TIFF0007621267000049.tif53141.

[0254] The corresponding 4-morpholinomethyl substituted silicone polymers are shown below.

[0255] One example of 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.

[0256] Examples of 4-morpholinomethyl-substituted silicones include those represented by the formulae (S-XII), (S-XIII') and (S-XIV') Silicone having a structural unit of TIFF0007621267000050.tif64150 can be used, During the ceremony R1 is -CH3, -OH, -OCH3, -O-CH2CH3, -O-CH2CH2CH3 or -O-CH(CH3)2; R2 is -CH3, -OH or -OCH3.

[0257] Particularly preferred compositions (a) according to the invention comprise at least one 4-morpholinomethyl-substituted silicone of formula (S-XV), TIFF0007621267000051.tif67165, where 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 fulfilled, The units a, b, c, m and n shall be statistically distributed in the molecule or in blocks.

[0258] Structural formula (Si-VI) is intended to show that the siloxane groups n and m are not necessarily directly bonded to the end groups B or D, respectively. Instead, in preferred formulae (Si-VI)a>0 or b>0, and in particularly preferred formulae (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.

[0259] The silicones of formula (Si-VI) used according to the invention 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 in the context of the invention are, for each context: 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

[0260] To produce a particularly durable coating, agent (a) comprises silicone polymer(s), in particular an alkoxy-modified silicone polymer and / or an amino-modified silicone polymer, preferably in amounts within certain ranges.

[0261] In particular, low-tack flexible coatings have been obtained when an agent (a) is used in the process which comprises 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, very particularly preferably 0.1 to 0.5% by weight, based on the total weight of agent (a).

[0262] In the context of a further preferred embodiment, the method is characterized in that agent (a) comprises one or more 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, most preferably 2 to 8% by weight, relative to the total weight of agent (a).

[0263] In one obviously quite particularly preferred embodiment, the method is characterized in that the agent (a) comprises one or more alkoxy-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, most preferably 2 to 8% by weight, relative to the total weight of agent (a).

[0264] In the context of an obviously quite particularly preferred embodiment, the method is characterized in that the agent (a) comprises 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, very particularly preferably 2 to 8% by weight, relative to the total weight of the agent (a).

[0265] pH value of agent (a) It has proven to be preferable if the agent (a) is constituted in the form of a moisture-containing agent adjusted to an alkaline pH.

[0266] To adjust this pH value, agent (a) may contain at least one alkalizing agent.

[0267] Thus, in order to adjust the desired pH, agent (a) may also contain at least one alkalizing agent. The pH values ​​for the purposes of the present invention are those measured at a temperature of 22° C.

[0268] As an alkalizing agent, agent (a) may contain, for example, ammonia, alkanolamines and / or basic amino acids.

[0269] The alkanolamines that can be used in the composition are preferably selected from primary amines with parent C2-C6 alkyl bearing at least one hydroxyl group.Preferred alkanolamines are selected from the group formed by 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.

[0270] 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 according to the invention comprises an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol as alkalizing agent.

[0271] For the purposes of the present invention, amino acids are organic compounds that contain at least one protonatable amino group and at least one -COOH or one -SO3H group in their structure. Preferred amino acids are aminocarboxylic acids, in particular α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0272] A basic amino acid is an amino acid that has an isoelectric point pI greater than 7.

[0273] Basic α-aminocarboxylic acids contain at least one asymmetric carbon atom. In the context of the present invention, both possible enantiomers can be equally used as specific compounds or as mixtures thereof, especially racemates. However, it is particularly advantageous to use the isomeric form that is preferred in the natural state, usually the L form.

[0274] The basic amino acid is preferably selected from the group formed by arginine, lysine, ornithine and histidine, particularly preferably arginine and lysine. In a further particularly preferred embodiment, the method is therefore characterized in that the alkalizing agent is a basic amino acid selected from the group consisting of arginine, lysine, ornithine and / or histidine.

[0275] The product may also contain other alkalizing agents, in particular inorganic alkalizing agents.The inorganic alkalizing agents usable according to the invention are preferably selected from the group formed by sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

[0276] 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.

[0277] 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 to fine-tune the desired pH value. Suitable acidifiers according to the invention are, for example, citric acid, lactic acid, acetic acid or also dilute mineral acids (e.g. hydrochloric acid, sulfuric acid, phosphoric acid).

[0278] 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 negative effect on the strength of the film. For this reason, it was found to be preferable to keep the amount of acid used in the medium (a) as low as possible. For this reason, it is advantageous if the total amount of organic and / or inorganic acid contained in the agent (a) does not exceed a certain value.

[0279] In a further preferred embodiment, the method is characterized in that the total amount of organic acids 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.-% and most preferably less than 0.01 wt.-%.

[0280] In a further preferred embodiment, the method is characterized in that the total amount of inorganic acids 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, very particularly preferably less than 0.01% by weight.

[0281] The above-mentioned maximum total amounts of acids contained in agent (a) are always based on the total weight of agent (a).

[0282] Agent (b) The method for treating keratinous materials comprises, in addition to the application of agent (a), the application of agent (b), characterized in that agent (b) used in said method comprises at least one sealing agent (b1).

[0283] 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 by the process more durable. In particular, the use of agent (b) improves the fastness to washing out and the fastness to rubbing of the dyeing obtained by the process.

[0284] The sealing agent (b1) preferably comprises a compound selected from the group consisting of a film-forming polymer, an alkalizing agent, an acidifying agent and mixtures thereof.

[0285] It may be preferred that the sealing agent (b1) comprises a film-forming polymer.

[0286] Polymer is a macromolecule that has a molecular weight of at least 1000g / mol, preferably at least 2500g / mol, particularly preferably at least 5000g / mol, and is composed of identical repeating organic units.The polymer of the present invention can be a synthetically produced polymer, which is produced by polymerization of one type of monomer, or by polymerization of different types of monomers that are structurally different from each other.When a polymer is produced by polymerizing one type of monomer, it is called a homopolymer.When structurally different monomer types are used in polymerization, the resulting polymer is called a copolymer.

[0287] 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. For 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.

[0288] 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 material or keratinous fibers. The formation of a film can be demonstrated, for example, by viewing under a microscope keratinous substances treated with the polymer.

[0289] The film-forming polymer in agent (b) may be hydrophilic or hydrophobic.

[0290] In the first embodiment, it may be preferred to use at least one hydrophobic film-forming polymer as sealing agent (b1) in agent (b).

[0291] A hydrophobic polymer is a polymer that has a solubility in water of less than 1% by weight at 25° C. (760 mmHg).

[0292] 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 stir bar and heat the mixture to 25° C. while stirring with a magnetic stirrer. Allow it to stir for 60 minutes. Then visually evaluate the aqueous mixture. If the polymer-water mixture cannot be visually evaluated due to high turbidity of the mixture, filter the mixture. If a percentage of undissolved polymer remains on the filter paper, the solubility of the polymer is less than 1% by weight.

[0293] These include acrylic acid type polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose polymers, nitrocellulose polymers, silicone polymers, acrylamide type polymers and polyisoprene.

[0294] Particularly suitable film-forming hydrophobic polymers are, for example, polymers from the group of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of 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.

[0295] In a further preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (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.

[0296] It has been found that film-forming hydrophobic polymers selected from the group of synthetic polymers, polymers obtainable by radical polymerization or natural polymers are particularly suitable for solving the problem according to the invention.

[0297] 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 group, aryl group or C2-C 10 They can be selected from homopolymers or copolymers of esters or amides of (meth)acrylic acid carrying hydroxyalkyl groups.

[0298] 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.

[0299] Further film-forming hydrophobic polymers can be selected from homopolymers or copolymers of (meth)acrylamide, N-alkyl(meth)acrylamides, those with C2-C18 alkyl groups, such as N-ethylacrylamide, N-tert-butylacrylamide, N-octylacrylamide, N-di(C1-C4)alkyl(meth)acrylamides.

[0300] Other preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid or C1-C6 alkyl esters thereof, which are sold under the INCI Declaration acrylate copolymers. A suitable commercial product is, for example, Aculyn® 33 from Rohm & Haas. Also preferred are copolymers of acrylic acid, methacrylic acid or C1-C6 alkyl esters thereof and esters of ethylenically unsaturated acids and alkoxylated fatty alcohols. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20.

[0301] 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.

[0302] 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.

[0303] 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.

[0304] Suitable olefin-based polymers include homopolymers and copolymers of ethylene, propylene, butene, isoprene, and butadiene.

[0305] In another embodiment, the film-forming hydrophobic polymer may be a block copolymer comprising at least one block of styrene or a derivative of styrene. Such a block copolymer may be a copolymer 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".

[0306] Surprisingly, it has been found that particularly intense and wash-off fast colorations are obtained when agent (b) comprises as sealing agent (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.

[0307] In a further 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.

[0308] In a further embodiment, it may be preferred to use at least one hydrophilic film-forming polymer as sealing agent (b1) in agent (b).

[0309] 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.

[0310] 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 stir bar and heat the mixture to 25° C. while stirring with a magnetic stirrer. Allow it to stir for 60 minutes. Then visually evaluate the aqueous mixture. A completely dissolved polymer will appear homogeneous to the naked eye. If the polymer-water mixture cannot be visually evaluated 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.

[0311] Nonionic, anionic and cationic polymers can be used as film-forming hydrophilic polymers.

[0312] 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.

[0313] Furthermore, it is particularly preferred to use polyvinylpyrrolidone (PVP) and / or vinylpyrrolidone-containing copolymers as film-forming hydrophilic polymers.

[0314] 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 sealing agent (b1).

[0315] It is further preferred when the agent comprises polyvinylpyrrolidone (PVP) as the film-forming hydrophilic polymer. Surprisingly, the wash-off fastness of the dyeings obtained with the PVP-containing agent (b) was also particularly good.

[0316] Particularly suitable polyvinylpyrrolidones are available, for example, under the name Luviskol® K from BASF SE, in particular Luviskol® K 90 or Luviskol® K 85 from BASF SE.

[0317] The polymer PVP K 30, sold by Ashland (ISP, POI Chemical), can also be used as another obviously 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.

[0318] 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.

[0319] The use as sealing agent (b1) of film-forming hydrophilic polymers from the group of the copolymers of polyvinylpyrrolidone also resulted in particularly good wash-off fastness coloring results.

[0320] 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.

[0321] 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.

[0322] 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.

[0323] Other suitable copolymers of polyvinylpyrrolidone may also be obtained by reacting N-vinylpyrrolidone with at least one further monomer from the group consisting of V-vinylformamide, vinyl acetate, ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactone and / or vinyl alcohol.

[0324] 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 / vinylcaprolactam copolymer, vinylpyrrolidone / vinylformamide copolymer and / or vinylpyrrolidone / vinyl alcohol copolymer as sealing agent (b1).

[0325] Another fussy copolymer of vinylpyrrolidone is the polymer known by the INCI designation Maltodextrin / VP Copolymer.

[0326] Furthermore, when non-ionic film-forming hydrophilic polymers are used as film-forming hydrophilic polymers, it has been possible to obtain intensively colored keratinous materials, especially hair, having particularly good wash-off fastness properties.

[0327] In another embodiment, agent (b) may comprise at least one non-ionic film-forming hydrophilic polymer as sealing agent (b1).

[0328] According to the present invention, nonionic polymers are understood to be polymers that do not carry 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 electronically neutral.Cationic groups include quaternized ammonium groups, but do not include protonated amines.Anionic groups include carboxylic and sulfonic acid groups.

[0329] As a non-ionic film-forming hydrophilic polymer, Polyvinylpyrrolidone, - N-vinylpyrrolidone and copolymers of vinyl esters of N-vinylpyrrolidone and vinyl acetate of carboxylic acids containing 2 to 18 carbon atoms, -copolymer of N-vinylpyrrolidone, N-vinylimidazole and methacrylamide, -copolymer of N-vinylpyrrolidone, N-vinylimidazole and acrylamide, -Copolymer of N-vinylpyrrolidone and N,N-di(C1-C4)alkylamino-(C2-C4)alkylacrylamide Preferred is a product comprising at least one polymer selected from the group consisting of:

[0330] If copolymers of N-vinylpyrrolidone and vinyl acetate are used, it is again preferred if the molar ratio of structural units of the monomer N-vinylpyrrolidone to structural units of 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.

[0331] Another particularly preferred polymer is selected from the INCI designation VP / methacrylamide / vinylimidazole copolymers, which are available from BASF SE under the trade name Luviset Clear.

[0332] 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 designation VP / DMAPA Acrylates Copolymer, e.g. under the trade name Styleze® CC 10.

[0333] The cationic polymer is a copolymer of N-vinylpyrrolidone, N-vinylcaprolactam, N-(3-dimethylaminopropyl) methacrylamide and 3-(methacryloylamino)propyl-lauryl-dimethylammonium chloride (INCI designation: 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).

[0334] Other suitable film-forming hydrophilic polymers include: vinylpyrrolidone-vinylimidazolium methchloride copolymers offered under the designations Luviquat® FC 370, FC 550 and INCI designations Polyquaternium-16 as well as FC 905 and HM 552, - vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, which have as their third monomer component an acrylic acid ester and an acrylic acid amide, for example as sold under the name Aquaflex® SF 40; Examples include:

[0335] 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.

[0336] Polyquaternium-46 is a reaction product of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulfate, and is available, for example, from BASF SE under the name Luviquat® Hold. 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.

[0337] 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 by Lubrizol under the trade names Carbopol 980, 981, 954, 2984 and 5984 or by 3V Sigma (The Sun Chemicals, Inter Harz) under the names Synthalen M and Synthalen K.

[0338] Examples of suitable film-forming hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum, carob gum.

[0339] Examples of suitable film-forming hydrophilic polymers from the group of the polysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.

[0340] Suitable film-forming hydrophilic polymers from the group of acrylamides are, for example, polymers prepared from monomers of (meth)acrylamido-C1-C4-alkylsulfonic acids or their salts. 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.

[0341] Preferred polymers of poly(meth)acrylamide-C1-C4-alkyl-sulfonic acid are crosslinked and at least 90% neutralized. Such polymers may be crosslinked or non-crosslinked.

[0342] 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".

[0343] Another preferred polymer of this type is a crosslinked poly-2-acrylamido-2 methyl-propanesulfonic acid polymer, partially neutralized with ammonia, sold under the tradename Hostacerin AMPS by Clariant.

[0344] 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 sealing agent (b1).

[0345] In this connection, the best results are obtained when the agent (b) comprises, as sealing agent (b1), at least one film-forming polymer comprising at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II), TIFF0007621267000052.tif32148 expression M is a hydrogen atom or ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium.

[0346] In a further preferred embodiment, the method according to the invention is characterized in that the agent (b) comprises as sealing agent (b1) at least one film-forming polymer comprising at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II), TIFF0007621267000053.tif32148 expression M is characterized in that it is a hydrogen atom or ammonium (NH4), sodium, potassium, 1 / 2 magnesium or 1 / 2 calcium.

[0347] When M represents a hydrogen atom, the structural units of formula (PI) are based on acrylic acid units.

[0348] When M represents an ammonium counterion, the structural unit of formula (PI) is based on the ammonium salt of acrylic acid.

[0349] When M represents a sodium counterion, the structural unit of formula (PI) is based on the sodium salt of acrylic acid.

[0350] When M represents a potassium counterion, the structural unit of formula (PI) is based on the potassium salt of acrylic acid.

[0351] When M represents one-half equivalent of a magnesium counterion, the structural unit of formula (PI) is based on the magnesium salt of acrylic acid.

[0352] 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.

[0353] The film-forming polymer(s) are preferably used in agent (b) in amounts within certain ranges. In this context, it has been found to be particularly preferred for solving the problem according to the invention when agent (b) comprises one or more film-forming polymers as sealing agent (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, based on the total weight of agent (b).

[0354] In a further preferred embodiment the method is characterized in that the agent (b) comprises one or more film-forming polymers as sealing agent (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, based on the total weight of agent (b).

[0355] The application of agent (b), which comprises a film-forming polymer as sealing agent (b1), is intended to seal and / or fix the colored film initially produced by the application of agent (a). The application of a second agent (b), which has a film-forming polymer as sealing agent (b1), deposits the film-forming polymer in the form of a further film on the colored film produced in the first layer. The multilayer film system thus produced shows improved resistance to external influences.

[0356] Here, the film made by the agent (b) containing a film-forming polymer as sealing agent (b1) is preferably not colored itself.In this way, it can be ensured that a certain degree of wear on the second film made by the agent (b) does not cause any color change in the entire film system.Therefore, it is particularly preferred when the agent (b) does not contain colorant compounds or contains only small amounts of them.

[0357] In an alternative embodiment, the sealing reagent (b1) comprises an alkalizing agent.

[0358] 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.

[0359] 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 reagent (b1).

[0360] It has been found that aftertreatment with an agent (b) containing ammonia has a particularly positive effect on improving the wash-off fastness and rub fastness properties of the dyeings obtained by the process.

[0361] In the context of a further very particularly preferred embodiment, the method is characterized in that the composition (b) comprises ammonia as sealing agent (b1).

[0362] Good results were also obtained when the composition (b) contained at least one C2-C6 alkanolamine as sealing agent (b1).

[0363] The alkanolamines usable in composition (b) can be selected, for example, from the group of primary amines having a parent C2-C6 alkyl carrying at least one hydroxyl group. Preferred alkanolamines are selected from the group formed by 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.

[0364] In a further preferred embodiment, the method according to the invention is characterized in that the composition (b) comprises as sealing agent (b1) at least one alkalizing agent from the group of alkanolamines, which alkanolamine is 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 and 2-amino-2-methylpropane-1,3-diol.

[0365] Likewise, good results were obtained when the composition (b) contained at least one basic amino acid as sealing agent (b1).

[0366] For the purposes of the present invention, an amino acid is an organic compound that contains at least one protonatable amino group and at least one -COOH or one -SO3H group in its structure. Preferred amino acids are aminocarboxylic acids, in particular α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0367] According to the present invention, a basic amino acid is an amino acid having an isoelectric point pI greater than 7.0.

[0368] Basic α-aminocarboxylic acids contain at least one asymmetric carbon atom. In the context of the present invention, both possible enantiomers can be equally used as specific compounds or as mixtures thereof, especially racemates. However, it is particularly advantageous to use the isomeric form that is preferred in the natural state, usually the L form.

[0369] The basic amino acid is preferably selected from the group formed by arginine, lysine, ornithine and histidine, particularly preferably arginine and lysine. In a further particularly preferred embodiment, the method is therefore characterized in that the sealing reagent (b1) is an alkalizing agent comprising a basic amino acid selected from the group consisting of arginine, lysine, ornithine and / or histidine.

[0370] In a further preferred embodiment, the method is characterized in that the agent (b) comprises as sealing reagent (b1) at least one alkalizing agent selected from the group of basic amino acids, the basic amino acids being preferably selected from the group of arginine, lysine, ornithine and histidine.

[0371] Good results have also been obtained when agent (b) comprises at least one alkali metal hydroxide as sealing agent (b1). Examples of suitable alkali metal hydroxides are sodium hydroxide and potassium hydroxide.

[0372] Good results were also obtained when the composition (b) contained as sealing agent (b1) an alkalizing agent comprising at least one alkaline earth metal hydroxide. Suitable alkaline earth metal hydroxides include magnesium hydroxide, calcium hydroxide and barium hydroxide.

[0373] Good 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.

[0374] Good results have also been obtained when the agent (b) contains 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.

[0375] In the group of sealing reagents in the form of alkalizing agents (b1), ammonia, C2-C6 alkanolamines, basic amino acids and alkali metal hydroxides have proven to be particularly suitable.

[0376] In the context of a further particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing reagent (b1) at least one alkalizing agent selected from the group consisting of ammonia, C2-C6 alkanolamines, basic amino acids and alkali metal hydroxides.

[0377] In another particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing reagent (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.

[0378] Composition (b) comprises an alkalizing agent as a sealing agent (b1) in a cosmetic carrier, preferably in an aqueous cosmetic carrier.

[0379] In this connection, it has proven to be preferred when 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).

[0380] In the context of a further 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).

[0381] The alkalizing agent contained in agent (b) has an influence on 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.

[0382] For this reason, the agent (b) containing an alkalizing agent as sealing reagent (b1) preferably has a pH of 7.0 to 12.0, preferably 7.5 to 11.5, more preferably 8.0 to 11.0, most preferably 8.5 to 9.5.

[0383] The pH value can be measured using conventional methods known in the state of the art, for example pH measurement by combination electrodes using a glass electrode or by using pH test papers.

[0384] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises an alkalizing agent as sealing reagent (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.

[0385] For the purposes of the present invention, pH values ​​are those measured at a temperature of 22°C.

[0386] In yet a further alternative embodiment, the sealing reagent (b1) comprises an acidifying agent.

[0387] Particularly preferably, the acidifying agent is selected from the group consisting of inorganic acids, organic acids and mixtures thereof.

[0388] Good results could be obtained when the 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.

[0389] In a further preferred embodiment, the method is characterized in that the agent (b) comprises as sealing reagent (b1) at least one acidifying agent selected from the group consisting of inorganic acids, the inorganic acids being preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid and mixtures thereof.

[0390] In a further even more preferred embodiment the method is characterized in that the agent (b) comprises sulfuric acid as sealing agent (b1).

[0391] Good results were also obtained when the agent (b) contained at least one organic acid as sealing agent (b1). The organic acid is 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, cyclohexyl 1 ... In one embodiment, the carboxylic acid is selected from the group consisting of 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-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.

[0392] In a further 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, elaicosyl acid, cyclosalicylic ... carboxylic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoic acid, 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.

[0393] In a further even more preferred embodiment the method is characterized in that the agent (b) comprises acetic acid as sealing reagent (b1).

[0394] Suitable acidifying agents also include methanesulfonic acid and / or 1-hydroxyethane-1,1-diphosphonic acid.

[0395] In the above group of sealing agents (b1) in the form of acidifying agents, sulfuric acid and / or acetic acid have proven to be particularly suitable.

[0396] In the context of a further particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing reagent (b1) at least one acidifying agent selected from the group consisting of sulfuric acid, acetic acid and mixtures thereof.

[0397] The agent (b) comprises an acidifying agent as a sealing agent (b1) in a cosmetic carrier, preferably in an aqueous cosmetic carrier.

[0398] The acidifying agent contained in agent (b) has an influence on the pH of agent (b). It has been found that acidic pH values ​​also have a beneficial effect on the dyeing performance and fastness properties of the dyeings obtained in the process.

[0399] For this reason, the agent (b) comprising an acidifying agent as 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, most preferably 4.5 to 5.5.

[0400] The pH value can be measured using conventional methods known in the state of the art, for example pH measurement by combination electrodes using a glass electrode or by using pH test papers.

[0401] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises an acidifying agent as sealing reagent (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.

[0402] For the purposes of the present invention, pH values ​​are those measured at a temperature of 22°C.

[0403] Other ingredients in formulations (a) and (b) The above agents (a) and (b) may also contain one or more optional ingredients.

[0404] The formulation may also contain one or more surfactants. The term surfactant refers to a surface-active substance. A distinction is made between anionic surfactants, which consist of a hydrophobic residue and a negatively charged hydrophilic head group, amphoteric surfactants, which carry 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 are uncharged but have a strong dipole moment and are highly hydrated in aqueous solution.

[0405] Zwitterionic surfactants contain at least one quaternary ammonium group and at least one -COO (-) -or-SO3 (-) These are surface-active compounds carrying a group. 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.

[0406] Amphoteric surfactants have a C8 to 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 inner 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.

[0407] Particularly preferred amphoteric surfactants are N-cocos alkylaminopropionate, cocos acylaminoethylaminopropionate and C 12 ~C 18 -Acylsarcosine.

[0408] The preparation may further contain at least one non-ionic surfactant. Suitable non-ionic surfactants are alkyl polyglycoside and alkylene oxide adducts of 2-30 mol of ethylene oxide per mol of fatty alcohol or fatty acid to fatty alcohols and fatty acids. Preparations with good properties are also obtained when the non-ionic surfactant contains fatty acid esters of ethoxylated glycerol reacted with at least 2 mol of ethylene oxide.

[0409] 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 are those which contain only positive charges. Typically, such surfactants are composed of a hydrophobic portion and a hydrophilic head group, where the hydrophobic portion is typically composed of a hydrocarbon backbone (e.g., one or two linear or branched alkyl chains) and the positive charge(s) reside in the hydrophilic head group. Examples of cationic surfactants are: - quaternary ammonium compounds which may carry one or two alkyl chains with a chain length of 8 to 28 carbon atoms as hydrophobic residues; - 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.

[0410] 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 carrying the cationic charge, the cationic surfactant may also contain other uncharged functional groups, as for example in the case of esterquats. The cationic surfactants are 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 the respective agent.

[0411] In addition, the agent may also contain at least one anionic surfactant. Anionic surfactants are surface active agents that have exclusively anionic charge (neutralized by corresponding counter cations). 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.

[0412] The anionic surfactants are 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.

[0413] The agent (a) and / or the 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 the matting agent is preferably 0.1 to 10% by weight based on the total amount of the agent (a) or the agent (b). Preferably, the agent (a) comprises a matting agent.

[0414] The agent may also contain other active ingredients, auxiliaries and additives, such as solvents; aliphatic 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 lectin 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 in the form of fatty acid condensation products or optionally 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 or bisabo. rolls; 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 and primary, secondary and tertiary phosphates; opacifying agents, such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlescent 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.

[0415] The selection of such other substances is made by the expert according to the desired properties of the agent. Other optional ingredients and the amounts of such ingredients to be used are specified in the relevant manuals known to the expert. The further active ingredients and auxiliary substances are preferably used in the preparations according to the invention in an amount of 0.0001-25% by weight, 0.0005-15% by weight, based on the total weight of each agent.

[0416] Method for dyeing keratinous materials In the procedure according to the invention, agents (a) and (b) are applied to a keratinous material, human hair. Agents (a) and (b) are therefore ready-to-use agents. Agents (a) and (b) are different.

[0417] In principle, agents (a) and (b) can be applied simultaneously or successively, with successive application being preferred.

[0418] The best results were obtained when agent (a) was first applied to the keratinous materials in a first step and agent (b) was applied in a second step.

[0419] Thus, quite particularly preferred is a method for treating keratinous materials, in particular human hair, for colouring the keratinous materials, comprising the following steps in the order given: In a first step, an agent (a) is applied to the keratinous material, the agent (a) comprising: (a1) at least one organosilicon compound selected from the group consisting of silanes having one, two or three silicon atoms, and (a2) at least one substrate comprising a vacuum metallization pigment, at least one colorant compound comprising a flake-based pigment; and In a second step, an agent (b) is applied to the keratinous material, the agent (b) comprising: (b1) at least one sealing agent Contains The method includes:

[0420] Furthermore, in order to impart high dissolution durability over a long period of time to the dyed keratinous material, agents (a) and (b) are particularly preferably applied in one and the same dyeing process, which means that the period between the application of agent (a) and the application of agent (b) is a maximum of several hours.

[0421] In a further preferred embodiment, the method is characterized in that agent (a) is applied first and then agent (b), the period between the application of agent (a) and the application of agent (b) being at most 24 hours, preferably at most 12 hours, particularly preferably at most 6 hours.

[0422] One of the distinguishing features of agent (a) is the content of at least one reactive organosilicon compound (a1). The reactive organosilicon compound(s) (a1) undergo an oligomerization or polymerization reaction as soon as they come into contact with the hair surface, thus imparting functionality. In this way, a first film is formed. The coloring compound (a2) is incorporated into said film so that it is colored. In a second step of the method, a second agent (b) is then applied to the hair. During the application of agent (b) comprising at least one film-forming polymer as sealing agent (b1), said film-forming polymer interacts with the silane film and is thus bound to the keratinous material. During the application of agent (b) comprising at least one alkalizing or acidifying agent as sealing agent (b1), the formation of the silane film is positively influenced.

[0423] In accordance with a further embodiment, the method comprises the steps of: (1) applying agent (a) to a keratinous substance; (2) allowing the agent (a) to act for a period of 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (3) If necessary, rinsing the keratinous materials with water; (4) applying agent (b) to the keratinous material; (5) allowing agent (b) to act for a period of 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (6) Rinse the keratinous material with water. Particularly preferred is a procedure comprising:

[0424] Rinsing of the keratinous material with water in steps (3) and (6) of the method is understood according to the present invention to mean the use of only water in the rinsing method without any other agents besides agents (a) and (b).

[0425] In step (1), agent (a) is first applied to keratinous material, in particular human hair.

[0426] After application, the agent (a) is left to act on the keratinous materials. In this connection, application times on the hair of 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, particularly preferably 30 seconds to 2 minutes, have proven to be particularly beneficial.

[0427] In a preferred embodiment of the method according to the invention, agent (a) may then be rinsed from the keratinous material before agent (b) is applied to the hair in a subsequent step.

[0428] Dyeings with equally good wash-off fastness were obtained when agent (b) was applied to keratinous materials that were still exposed to agent (a).

[0429] In step (4), agent (b) is then applied to the keratinous material. After application, agent (b) is allowed to act on the hair.

[0430] Even if the contact time with agent (b) is short, the process makes it possible to obtain dyeings with particularly good strength and wash-off fastness. Application times on the hair of 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, most preferably 30 seconds to 3 minutes, have proven to be particularly beneficial.

[0431] In step (6), agent (b) (and agent (a) if still present) is then rinsed from the keratinous material with water.

[0432] In this embodiment, the sequence of steps (1) through (6) is preferably carried out within 24 hours.

[0433] Agent (a) contains, together with the organosilicon compound(s), a type of highly reactive compound that, when used, can undergo hydrolysis or oligomerization and / or polymerization. As a result of their high reactivity, such organosilicon compounds form a film on the keratinous materials.

[0434] It is of great advantage to the user to prepare the ready-to-use agent (a) immediately prior to application in order to avoid premature oligomerization or polymerization.

[0435] In yet another embodiment, preferred is a method comprising the steps of: (1) preparing an agent (a) by mixing a first agent (a') and a second agent (a''); the first agent (a') comprises at least one organosilicon compound (a1) from the group of silanes having one, two or three silicon atoms, and the second agent (a″) comprises at least one colorant compound (a2) comprising at least one pigment based on substrate flakes constituting a vacuum metallization pigment; (2) applying agent (a) to a keratinous substance; (3) allowing the agent (a) to act for a period of 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) If necessary, rinsing the keratinous materials with water; (5) applying agent (b) to the keratinous material; (6) allowing agent (b) to act for a period of 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratinous materials with water.

[0436] The agent (a') itself is preferably formulated so as to have a low or no water content, in order to obtain a formulation that is as stable as possible on storage.

[0437] In a preferred embodiment, the multicomponent packaging unit (kit-of-parts) is characterized in that agent (a') has a moisture content of 0.001 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight and very particularly preferably 1.5 to 7% by weight, relative to the total weight of agent (a').

[0438] Agent (a″) comprises water. In a preferred embodiment, the multicomponent packaging unit (kit-of-parts) is characterized in that 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, relative to the total weight of agent (a2).

[0439] Within this embodiment, the ready-to-use agent (a) is then prepared by mixing agents (a') and (a'').

[0440] For example, the user may first stir or shake agent (a') containing organosilicon compound(s) (a1) with the aqueous colorant-containing agent (a''). The user may then apply this mixture of (a') and (a'') to the keratinous material either immediately after preparation or after a short reaction time of 10 seconds to 20 minutes. The user may then apply agent (b) as described above.

[0441] The optionally included silicone polymer (a3) ​​may be included in agent (a') or in agent (a''). Preferably, the silicone polymer (a3) ​​is included in agent (a'').

[0442] In yet another embodiment, preferred is a method comprising the steps of: (1) preparing an agent (a) by mixing a first agent (a') and a second agent (a''); the first agent (a') comprises at least one organosilicon compound (a1) from the group of silanes having one, two or three silicon atoms and also at least one silicone polymer (a3); and the second agent (a″) comprises at least one colorant compound (a2) comprising at least one pigment based on substrate flakes constituting a vacuum metallization pigment; (2) applying agent (a) to a keratinous substance; (3) allowing the agent (a) to act for a period of 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) If necessary, rinsing the keratinous materials with water; (5) applying agent (b) to the keratinous material; (6) allowing agent (b) to act for a period of 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratinous materials with water.

[0443] In the context of a further embodiment, particularly preferred is a method comprising the following steps in the order given: (1) preparing an agent (a) by mixing a first agent (a') and a second agent (a''); the first agent (a') comprises at least one organosilicon compound (a1) from the group of silanes having one, two or three silicon atoms, and the second agent (a″) comprises at least one colorant compound (a2) containing at least one pigment based on substrate flakes constituting a vacuum metallization pigment, and further comprises at least one silicone polymer (a3); (2) applying agent (a) to a keratinous substance; (3) allowing the agent (a) to act for a period of 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) If necessary, rinsing the keratinous materials with water; (5) applying agent (b) to the keratinous material; (6) allowing agent (b) to act for a period of 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratinous materials with water.

[0444] In a further preferred embodiment, the method may also be characterized in that the silicone polymer(s) (a3) ​​are provided in a separately prepared third means (a''').

[0445] Preferred in the context of this further embodiment is a method comprising the following steps in the order given: (1) preparing agent (a) by mixing a first agent (a'), a second agent (a''), and a third agent (a''); The first agent (a') comprises at least one organosilicon compound (a1) from the group of silanes having one, two or three silicon atoms; The second agent (a″) comprises at least one colorant compound (a2) comprising at least one pigment based on substrate flakes constituting a vacuum metallization pigment; and The third agent (a'') comprises at least one silicone polymer (a3); (2) applying agent (a) to a keratinous substance; (3) allowing the agent (a) to act for a period of 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) If necessary, rinsing the keratinous materials with water; (5) applying agent (b) to the keratinous material; (6) allowing agent (b) to act for a period of 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratinous materials with water.

[0446] Multi-component packaged unit (kit of parts) For increased user comfort, preferably all materials required by the user are provided in the form of a multi-component packaged unit (kit-of-parts). A second subject of the invention is therefore a first container comprising an agent (a'), said agent (a') comprising: (a1) a first container containing at least one organosilicon compound selected from the group consisting of silanes having one, two, or three silicon atoms; and a second container comprising an agent (a″), said agent (a″) comprising: (a2) a second container containing at least one colorant compound comprising at least one substrate flake-based pigment comprising a vacuum metallization pigment; and a third container containing an agent (b), said agent (b) comprising: (b1) a third container containing at least one sealing reagent; a multi-component packaged unit (kit of parts) for coloring keratinous materials, the components being packaged separately from one another; The components (a1), (a2) and (b1) are disclosed in detail above.

[0447] The organosilicon compounds (a1) from the group of silanes having one, two or three silicon atoms contained in agent (a) of the kit correspond to the organosilicon compounds also used in agent (a) of the method described above.

[0448] The colorant compound (a2) comprising at least one substrate flake-based pigment comprising a vacuum metal deposition pigment contained in the agent (a'') of the kit corresponds to the VMP substrate flake-based pigment also used in the agent (a) of the method described above.

[0449] The sealing reagent (b1) contained in the means (b) of the kit corresponds to the sealing reagent also used in the means (b) of the method described above.

[0450] In this connection, it is also possible in this case to use optionally included silicone polymers (a3). Incorporated within means (a'), means (a'') or further means (a'').

[0451] In the context of a further embodiment, a multi-component packaging unit (kit-of-parts) for coloring keratinous materials preferably comprises: a first container comprising an agent (a'), said agent (a') comprising: a first container containing at least one organosilicon compound (a1) from the group of silanes having one, two or three silicon atoms and further at least one silicone polymer (a3); a second container comprising an agent (a″), said agent (a″) comprising: (a2) a second container containing at least one colorant compound comprising at least one substrate flake-based pigment comprising a vacuum metallization pigment; and a third container containing an agent (b), said agent (b) comprising: (b1) a third container containing at least one sealing reagent; are packaged separately from each other, The components (a1), (a2), (a3) ​​and (b1) are disclosed in detail above.

[0452] In the context of a further embodiment, a multi-component packaging unit (kit-of-parts) for coloring keratinous materials preferably comprises: a first container comprising an agent (a'), said agent (a') comprising: a first container containing at least one organosilicon compound (a1) from the group of silanes having one, two or three silicon atoms and further at least one silicone polymer (a3); a second container comprising an agent (a″), said agent (a″) comprising: (a2) a second container containing at least one colorant compound comprising at least one substrate flake-based pigment comprising a vacuum metallization pigment; and a third container containing an agent (a'''), said agent (a''') being a water-containing cosmetic carrier, a fourth container containing an agent (b), said agent (b) comprising: (b1) a fourth container containing at least one sealing reagent; are packaged separately from each other, The components (a1), (a2), (a3) ​​and (b1) are disclosed in detail above.

[0453] 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.

[0454] In the context of a further embodiment, a multi-component packaging unit (kit-of-parts) for coloring keratinous materials preferably comprises: a first container comprising an agent (a'), said agent (a') comprising: a first container containing at least one organosilicon compound (a1) from the group of silanes having one, two or three silicon atoms; a second container comprising an agent (a″), said agent (a″) comprising: (a2) a second container containing at least one colorant compound comprising at least one substrate flake-based pigment comprising a vacuum metallized pigment and further comprising at least one silicone polymer (a3); and a third container containing an agent (b), said agent (b) comprising: (b1) a third container containing at least one sealing reagent; are packaged separately from each other, The components (a1), (a2), (a3) ​​and (b1) are disclosed in detail above.

[0455] In the context of a further embodiment, a multi-component packaging unit (kit-of-parts) for coloring keratinous materials preferably comprises: a first container comprising an agent (a'), said agent (a') comprising: a first container containing at least one organosilicon compound (a1) from the group of silanes having one, two or three silicon atoms; a second container comprising an agent (a″), said agent (a″) comprising: (a2) a second container containing at least one colorant compound comprising at least one substrate flake-based pigment comprising a vacuum metallization pigment; a third container comprising an agent (a″), said agent (a″) comprising: a third container comprising at least one silicone polymer (a3), and a fourth container containing an agent (b), said agent (b) comprising: (b1) a fourth container containing at least one sealing reagent; are packaged separately from each other, The components (a1), (a2), (a3) ​​and (b1) are disclosed in detail above.

[0456] With regard to further preferred embodiments of the multi-component packaging unit, the necessary modifications are made to what has been stated with regard to the method (mutatis mutantis). EXAMPLES

[0457] TIFF0007621267000054.tif45170

[0458] TIFF0007621267000055.tif50170

[0459] The ready-to-use agent (a) was prepared by mixing 5 g of agent (a') and 20 g of agent (a''). The pH value of agent (a) was adjusted to a value of 10.5 by adding ammonia or lactic acid. Agent (a) was then left to stand for about 5 minutes.

[0460] TIFF0007621267000056.tif33170

[0461] Agent (a) was massaged into one strand of hair at a time (Kerling, Euro Natural Hair White) and left to act for 1 minute. Agent (a) was then rinsed out with water.

[0462] Subsequently, agent (b) was applied to the hair bundle, left to act for 1 minute, and then rinsed again with water.

[0463] The hair bundle was then visually evaluated, revealing that the hair bundle had high strength and fastness and was colored metallic white. Preferred aspects of the invention include the following. [1] The following steps: - applying an agent (a) to a keratinous material, said agent (a) comprising: (a1) at least one organosilicon compound selected from the group consisting of silanes having one, two or three silicon atoms, and (a2) at least one substrate comprising a vacuum metallization pigment, at least one colorant compound comprising a flake-based pigment; A process comprising: - applying an agent (b) to the keratinous material, said agent (b) comprising: (b1) at least one sealing agent A process including 1. A method for dyeing keratinous material, in particular human hair, comprising: [2] The agent (a) contains at least one organosilicon compound (a1) of formula (I) and / or (II): TIFF0007621267000057.tif1049 During the ceremony -R 1 、R 2 are independently a hydrogen atom or C 1 ~C 6 represents an alkyl group, -L is a straight or branched divalent C 1 ~C 20 is an alkylene group, -R 3 、R 4 are independent of each other, C 1 ~C 6 represents an alkyl group, -a represents an integer from 1 to 3; -b represents an integer equal to 3-a, Here, formula (II) TIFF0007621267000058.tif10111 In the organosilicon compound R5, R5', R5'', R6, R6' and R6'' are independently C 1~C 6 represents an alkyl group, -A, A', A'', A''', and A'''' are independently straight or branched chain 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 represents an alkyl group or a group of formula (III), TIFF0007621267000059.tif1164 -c represents an integer from 1 to 3, -d represents an integer equal to 3-c, -c' represents an integer from 1 to 3, -d' represents an integer equal to 3-c', -c'' represents an integer from 1 to 3, -d'' represents an integer equal to 3-c'', -e represents 0 or 1, -f stands for 0 or 1, -g stands for 0 or 1, -h represents 0 or 1. -However, at least one of e, f, g and h is different from 0. The method according to claim 1, [3] The agent (a) contains at least one organosilicon compound (a1) of formula (I), TIFF0007621267000060.tif945 During the ceremony -R 1 、R 2 Both represent hydrogen atoms, -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 any one of [1] to [2], [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 The method according to any one of [1] to [3], characterized in that the method comprises containing at least one organosilicon compound (a1) represented by formula (I) selected from the group consisting of: [5] The agent (a) contains at least one organosilicon compound (a1) of formula (II), TIFF0007621267000061.tif14116 During the ceremony -e and f both represent the number 1, -g and h both represent the number 0, -A and A' are independently a linear divalent C 1 ~C 6 Represents alkylene -R7 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) The method according to any one of [1] to [4], [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 The method according to any one of [1] to [5], characterized in that the method comprises containing at least one organosilicon compound (a1) represented by formula (II) selected from the group consisting of: [7] The agent (a) contains at least one organosilicon compound (a1) of formula (IV). TIFF0007621267000062.tif1049 During the ceremony -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 of 3-k The method according to any one of claims 1 to 6, characterized in that [8] The agent (a) is -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -dodecyltrimethoxysilane, -dodecyltriethoxysilane, -octadecyltrimethoxysilane, -Octadecyltriethoxysilane and -Mixtures of these The method according to any one of [1] to [7], characterized in that the method comprises 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 flake contains a material selected from the group consisting of metals, metal alloys, and metal oxides.

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

[10] , wherein the base flake contains aluminum.

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

[11] , characterized in that the substrate flake comprises a coating A of at least one low refractive index metal oxide and / or metal oxide hydrate having a refractive index of at most 1.8.

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

[12] , characterized in that the substrate flake comprises a coating B of at least one highly refractive metal oxide having a refractive index of at least 1.9.

[14] The method according to

[13] , characterized in that the substrate flake has a further coating C of at least one metal oxide and / or metal oxide hydrate different from the underlying coating B.

[15] Separately packaged a first container comprising an agent (a'), said agent (a') comprising: (a1) a first container containing at least one organosilicon compound selected from the group consisting of silanes having one, two, or three silicon atoms; and a second container comprising an agent (a″), said agent (a″) comprising: (a2) a second container containing at least one colorant compound comprising at least one substrate flake-based pigment comprising a vacuum metallization pigment; a third container containing an agent (b), said agent (b) comprising: (b1) a third container containing at least one sealing reagent; A kit-of-parts for dyeing keratinous materials, including:

Claims

1. The following steps: applying an agent (a) to the keratinous materials, said agent (a) comprising: (a1) at least one organosilicon compound of formula (I) During the ceremony -R １ , R ２ are independently a hydrogen atom or C １ ~C ６ represents an alkyl group, -L is a straight or branched divalent C １ ~C ２０ is an alkylene group, -R ３ , R ４ are independent of each other, C １ ~C ６ represents an alkyl group, -a represents an integer of 1 to 3; -b represents an integer equal to 3-a; and At least one organosilicon compound of formula (IV) During the ceremony -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 of 3-k; and (a2) at least one colorant compound comprising at least one substrate flake-based pigment comprising a vacuum metallization pigment; A process comprising: applying an agent (b) to said keratinous material, said agent (b) comprising: (b1) at least one sealing agent comprising a compound selected from the group consisting of a film-forming polymer, an alkalizing agent, an acidifying agent, and mixtures thereof; A process including 1. A method for dyeing keratinous material comprising:

2. The agent (a) comprises at least one organosilicon compound of formula (I) and (II) During the ceremony -R １ , R ２ are independently a hydrogen atom or C １ ~C ６ represents an alkyl group, -L is a straight or branched divalent C １ ~C ２０ is an alkylene group, -R ３ , R ４ are independent of each other, C １ ~C ６ represents an alkyl group, -a represents an integer of 1 to 3; -b represents an integer equal to 3-a; Here, formula (II) In the organosilicon compound -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 straight 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 represents an alkyl group or a group of formula (III) -c represents an integer of 1 to 3; -d represents an integer equal to 3-c; -c' represents an integer of 1 to 3; -d' represents an integer equal to 3-c'; -c'' represents an integer of 1 to 3; -d'' represents an integer equal to 3-c'', -e represents 0 or 1; -f represents 0 or 1; -g represents 0 or 1; -h represents 0 or 1; - with the proviso that at least one of e, f, g and h is different from 0 2. The method according to claim 1 .

3. At least one organosilicon compound of formula (I) During the ceremony -R １ , R ２ Both represent hydrogen atoms, -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 The method according to any one of claims 1 to 2, characterized in that

4. At least one organosilicon compound of formula (I) -(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 Selected from the group consisting of 4. The method according to claim 3 .

5. At least one organosilicon compound of formula (II) During the ceremony - e and f both represent the number 1; - g and h both represent the number 0; -A and A' are independently linear divalent C １ ~C ６ Represents alkylene -R7 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) -c represents an integer of 1 to 3; -d represents an integer equal to 3-c; -c' represents an integer of 1 to 3; -d' represents an integer equal to 3-c'; -c'' represents an integer of 1 to 3; -d'' represents an integer equal to 3-c'', -e represents 0 or 1; -f represents 0 or 1; -g represents 0 or 1; -h represents 0 or 1; - with the proviso that at least one of e, f, g and h is different from 0 The method according to claim 2, characterized in that

6. At least one organosilicon compound of formula (II) -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 Selected from the group consisting of 6. The method according to claim 5 .

7. At least one organosilicon compound of formula (IV) During the ceremony -R ９ 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, -R １０ represents a methyl group or an ethyl group, -R １１ represents a methyl group or an ethyl group. -k is an integer from 1 to 3, -m represents an integer of 3-k The method according to any one of claims 1 to 6, characterized in that

8. At least one organosilicon compound of formula (IV) -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -dodecyltrimethoxysilane, - dodecyltriethoxysilane, -Octadecyltrimethoxysilane, -Octadecyltriethoxysilane and - Mixtures of these Selected from the group consisting of 8. The method according to claim 7 .

9. The method according to any one of claims 1 to 8, characterized in that the agent (a) comprises at least two structurally different organosilicon compounds.

10. The method according to any one of claims 1 to 9, characterized in that the substrate flake comprises a material selected from the group consisting of metals, metal alloys and metal oxides.

11. The method according to any one of claims 1 to 10, characterized in that the substrate flake comprises aluminium.

12. 12. The method according to claim 1, wherein the substrate flake comprises a coating A of at least one low refractive index metal oxide and / or metal oxide hydrate having a refractive index of at most 1.

8.

13. 13. The method according to any one of claims 1 to 12, characterized in that the substrate flake comprises a coating B of at least one highly refractive metal oxide having a refractive index of at least 1.

9.

14. 14. The method according to claim 13, characterized in that the substrate flakes have a further coating C of at least one metal oxide and / or metal oxide hydrate different from the underlying coating B.

15. Separately packaged a first container comprising an agent (a′), said agent (a′) comprising: (a1) at least one organosilicon compound of formula (I) During the ceremony -R １ , R ２ are independently a hydrogen atom or C １ ~C ６ represents an alkyl group, -L is a straight or branched divalent C １ ~C ２０ is an alkylene group, -R ３ , R ４ are independent of each other, C １ ~C ６ represents an alkyl group, -a represents an integer of 1 to 3; -b represents an integer equal to 3-a; and At least one organosilicon compound of formula (IV) During the ceremony -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 of 3-k; a first container comprising: a second container comprising an agent (a″), said agent (a″) comprising: (a2) a second container containing at least one colorant compound comprising at least one substrate flake-based pigment comprising a vacuum metallization pigment; a third container containing an agent (b), said agent (b) comprising: (b1) a third container containing at least one sealing agent comprising a compound selected from the group consisting of a film-forming polymer, an alkalizing agent, an acidifying agent, and mixtures thereof; A multi-component package unit for dyeing keratinous materials comprising:

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