Method for dyeing keratinous materials involving the use of organosilicon compounds, effect pigments and film-forming polymers III

Abstract

The subject of the present invention is the following: - applying an agent (a) to the keratinous material, said agent (a) comprising at least one organosilicon compound, and - applying an agent (b) to the keratinous material, said agent (b) comprising: (b1) at least one colorant compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer Processes including The present application also discloses a multi-component package unit comprising the two agents (a) and (b) in two separately packaged containers.

Description

[Technical Field]

[0001] The subject of the present application is a method for dyeing keratinous materials, in particular human hair, which comprises the application of two different agents (a) and (b): agent (a) comprises at least one organosilicon compound; and agent (b) comprises at least one coloring compound containing at least one selected pigment.

[0002] A second subject of the present application is a multi-component packaging unit (kit of parts) for coloring keratinous materials, in particular human hair, comprising agents (a) and (b) packaged separately in two different containers. [Background technology]

[0003] Changing the shape and color of keratinous materials, especially human hair, is an important area of ​​modern cosmetics. To change hair color, experts know a variety of coloring systems depending on the coloring requirements. Oxidative dyes are usually used for permanent and solid dyeing, and have good fastness properties and good gray coverage. Such colorants contain oxidation dye precursors, so-called developer components, and coupler components, which together form the actual dye under the influence of an oxidizing agent such as hydrogen peroxide. Oxidative dyes are characterized by very long-lasting color results.

[0004] When using direct dyes, the pre-formed dye diffuses from the colorant into the hair fiber. Compared to oxidative dyes, the color obtained with direct dyes is shorter-lasting and washes out quickly. The color of direct dyes typically remains on the hair for 5 to 20 washes.

[0005] It is known that the use of color pigments can cause short-term color changes in hair and / or skin.Color pigments are generally understood to be insoluble coloring substances.They exist in the form of small particles in the dye formulation in an undissolved state 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 containing a surfactant.Various products of this type are available on the market under the name of hair mascara.

[0006] Until now, the use of oxidative dyes has been the only option for consumers seeking particularly long-lasting hair coloring. However, despite numerous optimization attempts, the unpleasant ammonia and amine odors of oxidative hair dyes cannot be completely avoided. In addition, the hair damage still associated with the use of oxidative dyes has a negative effect on the user's hair. Therefore, the search for alternative, high-performance dyeing methods remains a challenge.

[0007] EP 2168633 addresses the problem of producing long-lasting pigmented hair coloring. It teaches that when a combination of pigment, organosilicon compound, hydrophobic polymer and solvent is applied to hair, it is possible to produce a coloring that is said to be particularly durable against 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 decorative cosmetic preparations such as nail polish.They are characterized, among other things, by an attractive angle-dependent color appearance (goniochromism) and a metallic-like luster.

[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. To this end, it is desirable that the effect pigments used have high dye buildup and can be applied to the hair in a thin layer. [Prior art documents] [Patent documents]

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

[0012] The object of the present invention was therefore to provide a dyeing system having fastness properties comparable to those of oxidative dyeing, in particular the wash-off and rub-fastness properties should be excellent, but the use of oxidative dye precursors normally used for this purpose should be avoided. [Means for solving the problem]

[0013] Surprisingly, it has now been found that this problem can be successfully 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 material (hair), where agent (a) comprises at least one organosilicon compound and agent (b) comprises at least one selected pigment (b1) and a film-forming polymer (b2).

[0014] When these two agents (a) and (b) are used in a dyeing process, keratinous materials can be dyed with particularly high fastness. DETAILED DESCRIPTION OF THE INVENTION

[0015] The first object of the present invention is to provide a method for the prevention of pulmonary embolism by: - applying an agent (a) to the keratinous material, said agent (a) comprising at least one organosilicon compound, and - applying an agent (b) to the keratinous material, said agent (b) comprising: (b1) at least one coloring compound comprising at least one substrate platelet-based pigment constituting a vacuum metallization pigment; and (b2) at least one film-forming polymer Processes including A method for coloring keratinous materials, particularly human hair, comprising:

[0016] 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.

[0017] 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.

[0018] 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.

[0019] So the following: - applying an agent (a) to the keratinous material, said agent (a) comprising at least one organosilicon compound, and - applying an agent (b) to the keratinous material, said agent (b) comprising: (b1) at least one color-forming compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer The process includes the steps of: The two means (a) and (b) disclose different methods for dyeing keratinous materials, in particular human hair.

[0020] Agent (a) Agent (a) is characterized in that it contains at least one organosilicon compound, in particular at least one organosilane. The organosilicon compound or organosilane contained in agent (a) is a reactive compound.

[0021] Composition (a) comprises an organosilicon compound, particularly an organosilane, in a cosmetic carrier, which may be in a hydrated, low-moisture, or anhydrous state. The cosmetic carrier may also be liquid, gel-like, creamy, paste-like, powdery, or even solid (e.g., in the form of a tablet or compressed preparation). Preferably, the cosmetic carrier of formulation (a) is an aqueous or aqueous-alcoholic carrier. For hair coloring, such carriers are, for example, creams, emulsions, gels, or surfactant-containing foaming solutions, such as shampoos, aerosol foams, foam formulations, or other preparations suitable for application to hair.

[0022] The cosmetic carrier preferably contains water, meaning that the carrier contains at least 2% by weight of water relative to its weight. Preferably, the water content is greater than 5% by weight, more preferably greater than 10% by weight, and even more preferably greater than 15% by weight. The cosmetic carrier may also be hydroalcoholic. An aqueous / alcoholic solution in the context of the present invention is an aqueous solution containing 2 to 70% by weight of a C1 to C4 alcohol, more specifically ethanol or isopropanol. The agent may further contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol, or 1,2-propylene glycol. All water-soluble organic solvents are preferred.

[0023] The term "coloring agent" is used in the context of the present invention to denote a method for coloring keratinous materials, especially human hair, using pigments and / or direct dyes. During this coloring process, the coloring compounds are deposited on the surface of the keratinous materials or diffused into the keratinous fibers in the form of a particularly uniform and smooth film. The film is formed in situ by oligomerization or polymerization of the organosilicon compound and by the interaction of the organosilicon compound with the colorant compound.

[0024] Organosilicon Compounds As an essential component of the present invention, agent (a) comprises at least one organosilicon compound. Preferred organosilicon compounds are selected from silanes containing one, two or three silicon atoms.

[0025] 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 preferably compounds containing 1 to 3 silicon atoms.The organosilicon compounds preferably contain 1 or 2 silicon atoms.

[0026] Agent (a) particularly preferably comprises at least one organosilicon compound selected from silanes containing one, two or three silicon atoms.

[0027] According to IUPAC rules, the term silane refers to a group of chemical compounds based on a silicon skeleton and hydrogen. In organosilanes, the hydrogen atoms are completely or partially replaced by organic groups, such as (substituted) alkyl and / or alkoxy groups. In organosilanes, some of the hydrogen atoms may also be replaced by hydroxy groups.

[0028] In one particularly preferred embodiment, the method comprises applying an agent (a) to the keratinous material, the agent (a) comprising at least one organosilicon compound selected from silanes containing one, two or three silicon atoms.

[0029] Agent (a) particularly preferably comprises at least one organosilicon compound selected from silanes having one, two or three silicon atoms, which organosilicon compound further comprises one or more basic chemical functions and one or more hydroxyl or hydrolyzable groups per molecule.

[0030] In one very particularly preferred embodiment, the method comprises applying an agent (a) to the keratinous material, said agent (a) comprising at least one organosilicon compound 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 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 is preferably a C1-C6 alkoxy group, particularly an ethoxy group or a methoxy group. It is preferred that the hydrolyzable group is directly bonded to the silicon atom. For example, when the hydrolyzable group is an ethoxy group, the organosilicon compound preferably contains the structural unit R'R''R'''Si-O-CH2-CH3. The R', R'' and R''' groups represent the valences of the remaining three bonds of the silicon atom that are not used.

[0033] One very particularly preferred example of the method is characterized in that the agent (a) comprises at least one organosilicon compound selected from silanes containing one, two or three silicon atoms, preferably the organosilicon compound 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 agent (a) comprises at least one organosilicon compound of formula (I) and / or (II).

[0035] In another very particularly preferred embodiment, the method comprises applying an agent (a) 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 independently represent a hydrogen atom or a C1-C6 alkyl group; -L is a straight or branched chain 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'' independently represent a C1-C6 alkyl group; -A, A', A'', A''', and A'''' are, independently of one another, straight-chain 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 between 1 and 3, -d represents an integer of 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 of 3-c'', -e represents 0 or 1, -f represents 0 or 1, -g represents 0 or 1, -h represents 0 or 1, -wherein at least one of e, f, g and h is different from 0.

[0036] The substituents R1, R2, R3, R4, R5, R5', R5'', R6, R6', R6'', R7, R8, L, A, A', A'', A''' and A'''' in the compounds of formula (I) and (II) are illustrated by way of example below.

[0037] 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. Furthermore, due to the chain length of three carbon atoms, the divalent alkylene group may be branched. Branched divalent C3-C 20 Examples of alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0038] In the organosilicon compound of formula (I), R1R2N-L-Si(OR3) a (R4) b (I), The R1 and R2 groups independently represent a hydrogen atom or a C1-C6 alkyl group, and in particular, both R1 and R2 groups represent a hydrogen atom.

[0039] The central part of the organosilicon compound is a linear or branched divalent C1-C 20 There is a structural unit or linker -L- that represents an alkylene group.

[0040] Preferably, -L- is a linear divalent C1-C 20 It represents an alkylene group. More preferably, -L- represents a straight-chain 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-).

[0041] 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

[0042] 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.

[0043] Here, a represents an integer between 1 and 3, and b represents an integer 3-a. If a represents the number 3, b is 0. If a represents the number 2, b is 1. If a represents the number 1, b is 2.

[0044] When agent (a) comprises at least one organosilicon compound of formula (I) in which the R3, R4 radicals, independently of one another, represent a methyl or ethyl radical, dyeings with the best wash-off fastness can be obtained.

[0045] Furthermore, dyeings with the best wash-off fastness can 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.

[0046] In another preferred embodiment, the method comprises the step of: In 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 by containing at least one organosilicon compound of formula (I).

[0047] In another preferred embodiment, the method comprises the step of: R1R2N-L-Si(OR3) a (R4) b (I), In the formula -R1 and R2 both represent hydrogen atoms, -L represents a linear divalent C1-C6 alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or an ethylene group (-CH2-CH2-), -R3 represents a hydrogen atom, an ethyl group, or a methyl group; -R4 represents a methyl group or an ethyl group; -a represents the number 3, -b represents the number 0, It is characterized by containing at least one organosilicon compound of formula (I).

[0048] When b is 0, the R4 group is absent in the compound of formula (I).

[0049] Thus, in a further preferred embodiment, the method comprises the step of: R1R2N-L-Si(OR3) a (R4) b (I), In the formula -R1 and R2 both represent hydrogen atoms, -L represents a linear divalent C1-C6 alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or an ethylene group (-CH2-CH2-), -R3 represents a hydrogen atom, an ethyl group, or a methyl group; -a represents the number 3, -b represents the number 0, It is characterized by containing at least one organosilicon compound of formula (I).

[0050] The organosilicon compounds of formula (I) that are particularly suitable for solving this problem are -(3-aminopropyl)triethoxysilane TIFF0007755486000001.tif3474-(3-aminopropyl)trimethoxysilane TIFF0007755486000002.tif3464-1-(3-aminopropyl)silanetriol TIFF0007755486000003.tif2161-(2-aminoethyl)triethoxysilane TIFF0007755486000004.tif3463-(2-aminoethyl)trimethoxysilane TIFF0007755486000005.tif3457-1-(2-aminoethyl)silanetriol TIFF0007755486000006.tif2151-(3-Dimethylaminopropyl)triethoxysilane TIFF0007755486000007.tif3474-(3-Dimethylaminopropyl)trimethoxysilane TIFF0007755486000008.tif3467-1-(3-dimethylaminopropyl)silanetriol TIFF0007755486000009.tif2161-(2-Dimethylaminoethyl)triethoxysilane TIFF0007755486000010.tif3466-(2-dimethylaminoethyl)trimethoxysilane, and / or TIFF0007755486000011.tif3457-1-(2-dimethylaminoethyl)silanetriol The file is TIFF0007755486000012.tif2654.

[0051] In a further preferred embodiment, the method comprises the step of: (3-aminopropyl)triethoxysilane (3-aminopropyl)trimethoxysilane 1-(3-aminopropyl)silanetriol (2-aminoethyl)triethoxysilane (2-aminoethyl)trimethoxysilane 1-(2-aminoethyl)silanetriol (3-Dimethylaminopropyl)triethoxysilane (3-Dimethylaminopropyl)trimethoxysilane 1-(3-dimethylaminopropyl)silanetriol (2-Dimethylaminoethyl)triethoxysilane (2-Dimethylaminoethyl)trimethoxysilane 1-(2-dimethylaminoethyl)silanetriol, and mixtures thereof The present invention is characterized in that it contains at least one organosilicon compound of formula (I) selected from the group consisting of:

[0052] Organosilicon compounds of formula (I) are commercially available.

[0053] For example, (3-aminopropyl)trimethoxysilane can be purchased from Sigma-Aldrich, and (3-aminopropyl)triethoxysilane is also commercially available from Sigma-Aldrich.

[0054] In a further embodiment, agent (a) is at least one organosilicon compound 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) Includes:

[0055] The organosilicon compounds of formula (II) each have a silicon-containing group (RO) at each of their two ends. c (R6) d Si- and -Si(R6') d’ (OR5') c’ It carries the following.

[0056] The central portion of the molecule of formula (II) contains -(A) e -group and -[NR7-(A')] f -group and -[O-(A'')] g -group and -[NR8-(A''')] h - group is present, where each of the residues e, f, g and h can independently represent the 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 compounds of formula (II) according to the invention comprise at least one group from the group consisting of -(A)- and -[NR7-(A')]- and -[O-(A'')]- and -[NR8-(A''')]-.

[0057] Two terminal structural units (RO) c (R6) d Si- and -Si(R6') d’ (OR5') c’ In the formula, R5, R5', and R5'' groups each independently represent a hydrogen atom or a C1 to C6 alkyl group. R6, R6', and R6'' groups each independently represent a C1 to C6 alkyl group.

[0058] Here, a represents an integer between 1 and 3, and d represents an integer between 3 and c. If c represents the number 3, d is 0. If c represents the number 2, d is 1. If c represents the number 1, d is 2.

[0059] 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.

[0060] Dyeings with the best wash-off fastness values ​​could be obtained when residues c and c' both represent the value 3. In this case, d and d' both represent the value 0.

[0061] In another preferred embodiment, the method 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' independently represent a methyl group or an ethyl group; -c and c' together represent the number 3, -d and d' both represent the number 0, It is characterized by containing at least one organosilicon compound of formula (II).

[0062] 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

[0063] 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 represent -(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).

[0064] In this context, the presence of certain specific groups has been found to be particularly beneficial in terms of increasing the water-washing resistance. 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.

[0065] When e and f both represent the number 1 and g and h both represent the number 0, the organosilicon compound has the formula (IIb): (R5O) c (R6) d Si-(A)-[NR7-(A')]-Si(R6') d’ (OR5') c’ (IIb) is equivalent to

[0066] 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 straight-chain divalent C1-C alkylene group. 20 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-).

[0067] If the residue f represents the number 1, the organosilicon compounds of formula (II) according to the invention contain a group of structure -[NR7-(A')]-.

[0068] 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''')]-.

[0069] 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.

[0070] Highly preferably, R7 and R8 independently 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).

[0071] When the residue f represents the number 1 and the residue h represents the number 0, the organosilicon compound according to the invention contains the group [NR7-(A')] but not the group -[NR8-(A'')]. Also, when the group R7 represents a group of formula (III), the agent (a) contains an organosilicon compound having three reactive silane groups.

[0072] In another preferred embodiment, the method comprises the step of: (a) comprising at least one organosilicon compound 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' independently represent 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:

[0073] In a further preferred embodiment, the method 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 (-CH2-), an ethylene group (-CH2-CH2-) or a propylene group (-CH2-CH2-CH2), -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 containing at least one organosilicon compound of formula (II).

[0074] The organosilicon compounds of formula (II) suitable for solving this problem are -3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007755486000013.tif38111-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007755486000014.tif46130-N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007755486000015.tif38111-N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007755486000016.tif46130-2-[bis[3-(trimethoxysilyl)propyl]amino]-ethanol TIFF0007755486000017.tif46111-2-[bis[3-(triethoxysilyl)propyl]amino]ethanol TIFF0007755486000018.tif54130-3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007755486000019.tif61111-3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007755486000020.tif64125-N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine TIFF0007755486000021.tif49111-N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine TIFF0007755486000022.tif54130-N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine TIFF0007755486000023.tif46111-N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The file is TIFF0007755486000024.tif51130.

[0075] Organosilicon compounds of formula (II) are commercially available.

[0076] Bis(trimethoxysilylpropyl)amine, which has the CAS number 82985-35-1, can be purchased from Sigma-Aldrich.

[0077] Bis[3-(triethoxysilyl)propyl]amine, which has the CAS number 13497-18-2, can be purchased, for example, from Sigma-Aldrich.

[0078] 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.

[0079] 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine, which has the CAS number 18784-74-2, can be purchased, for example, from Fluorochem or Sigma-Aldrich.

[0080] In another preferred embodiment, the method comprises the step of: 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine 3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine N-methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine 2-[bis[3-(trimethoxysilyl)propyl]amino]-ethanol 2-[bis[3-(triethoxysilyl)propyl]amino]ethanol 3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine, and / or N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The present invention is characterized in that it contains at least one organosilicon compound of formula (II) selected from the group consisting of:

[0081] In further dyeing trials, it was also found that the agent (a) applied to the keratinous material in this manner was of formula (IV) R9Si(OR 10 ) k (R 11 ) m (IV) It has been found to be particularly suitable when the composition contains at least one organosilicon compound of the formula:

[0082] The organosilicon compound of formula (IV) may also be referred to as an alkylalkoxysilane or alkylhydroxysilane silane. 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.

[0083] In another preferred embodiment, the method further comprises the step of: (a) comprising at least one 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:

[0084] In a further preferred embodiment, the method comprises the step of: (a) comprising, in addition to the organosilicon compound 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:

[0085] In a further preferred embodiment, the method comprises the step of: (a) comprising, in addition to the organosilicon compound 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:

[0086] In a further preferred embodiment, the method comprises the steps of: (a) comprising, in addition to the organosilicon compounds of formula (I) and / or (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:

[0087] In the organosilicon compound of formula (IV), the R group is C1-C 18 This C1 to C alkyl group 18 The alkyl group is saturated and can be straight or branched. Preferably, R is a straight chain 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.

[0088] In the organosilicon compound of formula (IV), R 10 The group represents a hydrogen atom or a C1-C6 alkyl group. 10 represents a methyl group or an ethyl group.

[0089] In the organosilicon compound of form (IV), R 11 The group represents a C1 to C6 alkyl group. R11 represents a methyl group or an ethyl group.

[0090] 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.

[0091] The best wash-off fastness dyeings were obtained when the process used an agent (a) containing at least one organosilicon compound corresponding to formula (IV) in which the residue k has the value 3. In this case, the remaining m has the value 0.

[0092] Organosilicon compounds of formula (IV) that are particularly suitable for solving the problems according to the invention are -Methyltrimethoxysilane TIFF0007755486000025.tif3428-Methyltriethoxysilane TIFF0007755486000026.tif4138-Ethyltrimethoxysilane TIFF0007755486000027.tif3438-Ethyltriethoxysilane TIFF0007755486000028.tif4146-n-Hexyltrimethoxysilane TIFF0007755486000029.tif3474-n-Hexyltriethoxysilane TIFF0007755486000030.tif4185-n-Octyltrimethoxysilane TIFF0007755486000031.tif3492-n-Octyltriethoxysilane TIFF0007755486000032.tif41102-n-dodecyltrimethoxysilane, and / or TIFF0007755486000033.tif34130-n-Dodecyltriethoxysilane TIFF0007755486000034.tif43140n-octadecyltrimethoxysilane and / or n-octadecyltriethoxysilane.

[0093] In a further preferred embodiment, the method 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 of formula (IV) selected from the group consisting of:

[0094] In the course of research leading to the present invention, it was found that even when agent (a) contains two structurally different organosilicon compounds, it is possible to obtain a particularly stable and uniform film on keratinous materials.

[0095] In another preferred embodiment, the method according to the invention is characterized in that the agent (a) comprises at least two structurally different organosilicon compounds.

[0096] In one preferred embodiment, the method is characterized in that an agent (a) comprising at least one organosilicone compound of formula (I) and at least one organosilicone compound of formula (IV) is applied to the keratinous material.

[0097] In one obviously very particularly preferred embodiment, the method comprises applying an agent (a) to the keratinous material, the agent comprising at least one organosilicon compound of formula (I) selected from the group consisting of (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and further comprising at least one organosilicon compound of formula (IV) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.

[0098] The organosilicon compounds are reactive compounds. In this context, it has been found to be advantageous when agent (a) contains one or more organosilicon compounds in a total amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 5.0 to 10% by weight, relative to the total weight of agent (a).

[0099] In this connection, it has proven particularly advantageous when agent (a) comprises one or more organosilicon compounds of formula (I) and / or (II) in a total amount of 0.1 to 20% by weight, preferably 0.2 to 15% by weight, particularly preferably 0.2 to 3% by weight, relative to the total weight of agent (a).

[0100] It has further been found to be particularly preferred when agent (a) contains one or more organosilicon compounds of formula (IV) in a total amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 2 to 8% by weight, relative to the total weight of agent (a).

[0101] 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:

[0102] In this embodiment, agent (a) contains one or more organosilicon compounds of a first group in a total amount of 0.5 to 3 wt.%, wherein the organosilicon compounds of the first group are selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane, and / or (2-dimethylaminoethyl)triethoxysilane.

[0103] In this embodiment, agent (a) contains one or more organosilicon compounds of a second group in a total amount of 3.2 to 10 wt. % selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, and / or octadecyltriethoxysilane.

[0104] Even the addition of a small amount of water will cause 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 can 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 can 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 can be present in agent (a).

[0105] 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, by eliminating water and / or elimination of alkanol.Condensation product can 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.

[0106] Particularly good results have been obtained when organosilicon compounds of formula (I) and / or (II) are used in the method.As mentioned above, the hydrolysis / condensation is initiated even at trace amounts of water, so the condensation products of organosilicon compounds (I) and / or (II) are also included in this embodiment.

[0107] Particularly durable strain was obtained when an alkaline agent (a) was used. Preferably, agent (a) contains water and has a pH of 7 to 11.5, preferably 7.5 to 11, more preferably 8 to 10.5.

[0108] In another very particularly preferred embodiment, the method is characterized in that the agent (a) has a pH of 7 to 11.5, preferably 7.5 to 11, particularly preferably 8 to 10.5.

[0109] Agent (b) The agent (b) is characterized by the presence of at least one colorant compound (b1) and at least one film-forming polymer (b2). The colorant compound (b1) comprises at least one substrate platelet-based pigment comprising a vacuum metallized pigment.

[0110] The substrate platelets have an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, and very particularly preferably at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred ranges for substrate platelet thickness are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm, and 10 to 20 nm. Preferably, each substrate platelet has as uniform a thickness as possible.

[0111] Due to the low thickness of the substrate platelets, the pigments exhibit particularly high hiding power.

[0112] The substrate platelet has a monolithic structure. Monolithic in this context means that it consists of a single closed unit without cracks, layers, or inclusions, although structural variations may occur within the substrate platelet. The substrate platelet preferably has a uniform structure, i.e., there is no concentration gradient within the platelet. In particular, the substrate platelet does not have a layered structure and does not have any particles or particles distributed within it.

[0113] The size of the substrate platelets can be adjusted for each application purpose, in particular for the desired effect on keratinous materials. Typically, the substrate platelets have an average maximum diameter of about 2 to 200 μm, in particular about 5 to 100 μm.

[0114] 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, and more preferably greater than 750. The average size of the uncoated substrate platelet is the d50 value of the uncoated substrate platelet. Unless otherwise stated, the d50 value was measured by quixel wet dispersion using a Sympatec Helos instrument. To prepare the sample, the sample to be analyzed was pre-dispersed in isopropanol for 3 minutes.

[0115] The substrate platelet can be made of any material that can be formed into a platelet shape.

[0116] The substrate platelet can be of natural origin, but can also be synthetically produced.The materials that the substrate platelet can be made of include metal and metal alloy, metal oxide, preferably aluminum oxide, inorganic compounds, and minerals, such as mica and (semi)precious stones, and plastics.Preferably, the substrate platelet is made of metal (alloy).

[0117] Any metal suitable for metallic luster pigments can be used.Such metals include iron and steel, and any (semi)metals that are durable to air and water, such as platinum, zinc, chromium, molybdenum, and silicon, and their alloys, such as aluminum bronze and brass.Preferred metals are aluminum, copper, silver, and gold.Preferred substrate platelets include aluminum platelets and brass platelets, and aluminum substrate platelets are particularly preferred.

[0118] Vacuum metallization pigments (VMP) are obtained, for example, by peeling off metals, metal alloys, or metal oxides in the form of a suitable coating. They are characterized by a particularly thin substrate platelet thickness in the range of 5 to 50 nm and a particularly smooth surface with high reflectivity. The substrate platelets constituting vacuum metallization pigments are also referred to as VMP substrate platelets in the context of this application. Aluminum VMP substrate platelets are obtained, for example, by peeling off aluminum in the form of a metallization coating.

[0119] Metal or metal alloy substrate platelets may be passivated, for example, by anodic oxidation (oxide layer) or chromate treatment.

[0120] Uncoated VMP substrate platelets, especially those made of metals or metal alloys, are highly reflective of incident light, resulting in light-dark flop but not color.

[0121] The color may be produced, for example, by optical interference effects. Such pigments may be based on substrate platelets having at least one coating. These exhibit interference effects due to the overlap of light rays that are refracted and reflected differently.

[0122] Thus, a preferred pigment is based on a coated VMP substrate platelet. The substrate platelet preferably has at least one coating B of a highly refractive metal oxide with a coating thickness of at least 50 nm. Preferably, another coating A is present between coating B and the substrate platelet surface. Optionally, a further coating C is present on layer B, which is different from the underlying layer B.

[0123] Suitable materials for coatings A, B, and C are any substances that can be applied to the substrate platelet in a permanent, film-like manner and, in the case of coatings A and B, have the required optical properties. Generally, the coating on the substrate platelet surface is sufficient to provide a pigment with a glossy effect. For example, only the top and / or bottom surfaces of the substrate platelet may be coated, but not the sides. Preferably, the entire surface of the substrate platelet, including the optionally passivated sides, is covered by coating B. Thus, the substrate platelet is completely covered by coating B. This improves the optical properties of the pigment and increases its mechanical and chemical durability. The same applies to layer A and, if present, preferably layer C.

[0124] Although several coatings A, B and / or C may be present in each case, the coated substrate platelet preferably has only one coating A, B and, if present, C in each case.

[0125] Coating B is composed of at least one highly refractive metal oxide. The highly refractive material has a refractive index of at least 1.9, preferably at least 2.0, and 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.

[0126] Coating B has a thickness of at least 50 nm. Preferably, the thickness of Coating B is 400 nm or less, more preferably 300 nm or less.

[0127] 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-FeO, red), cobalt(II) oxide (blue), chromium(III) oxide (green), titanium(III) oxide (blue, usually present in admixture 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.

[0128] Coating B may also contain selectively absorbing dyes, preferably in an amount of 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, in each case relative to the total amount of coating B. Suitable dyes are organic and inorganic dyes which are stably incorporated into the metal oxide coating.

[0129] 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.

[0130] 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.

[0131] Preferably, the distance between the substrate platelet surface and the inner surface of coating B is at most 100 nm, particularly preferably at most 50 nm, and particularly preferably at most 20 nm. By ensuring that the thickness of coating A, and thus the distance between the substrate platelet surface and coating B, is within the ranges specified above, it is possible to ensure that the pigment has high hiding power.

[0132] When the VMP substrate platelet-based pigment has only Layer A, the pigment preferably has an aluminum VMP substrate platelet and a silica Layer A. When the VMP substrate platelet-based pigment has Layers A and B, the pigment preferably has an aluminum VMP substrate platelet, a silica Layer A, and an iron oxide Layer B.

[0133] According to one 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 (dioxide), 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.

[0134] 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.

[0135] Layers A and C perform the functions of antiseptic and chemical and physical stabilization. Particularly preferred are silica or alumina applied by a sol-gel process. This method involves dispersing an uncoated VMP substrate platelet or a VMP substrate platelet already coated with Layers A and / or B in a solution of a metal alkoxide, such as tetraethyl orthosilicate or aluminum triisopropanolate (typically in an organic solvent or a mixture of organic solvent and water, where at least 50% by weight is an organic solvent, such as a C1-C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, thereby forming a metal oxide film on the surface of the (coated) substrate platelet.

[0136] 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 (e.g., annealing to convert the formed hydroxide-containing layer into an oxide layer).

[0137] 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).

[0138] Pigments based on coated VMP substrate platelets preferably have a thickness of 70 to 500 nm, particularly preferably 100 to 400 nm, particularly preferably 150 to 320 nm, for example 180 to 290 nm. Due to the low thickness of the substrate platelets, the pigments exhibit particularly high hiding power. The low thickness of the coated substrate platelets can be achieved by maintaining a low thickness for the uncoated substrate platelets, but also by adjusting the thickness of Coating A and, if present, Coating C, to as small a value as possible. The thickness of Coating B determines the color tone of the pigment.

[0139] The adhesion and abrasion resistance of the coated VMP substrate platelet-based pigment on the keratinous material can be significantly improved by further modifying the outermost layer, layer A, B, or C, with an organic compound, such as a 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 platelet. The organic compound is preferably a functional silane compound capable of bonding to the metal oxide-containing layer A, B, or C. This can be either a monofunctional or bifunctional compound. Examples of bifunctional organic compounds include methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyltris(methox-yethoxy)silane, 3-methacryloxypropyltris(butoxy ... Examples of suitable silanes include tris(propoxy)silane, 3-methacryloxypropyltris(butoxy)silane, 3-acryloxypropyltris(methoxyethoxy)silane, 3-acryloxypropyltris(butoxyethoxy)silane, 3-acryloxypropyltris(butoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane, phenylvinyldiethoxysilane, and 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 pigment based on the coated VMP substrate platelet (i.e., to the outermost metal oxide-containing layer) or to the metal surface if it is 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 varying degrees of hydrophobicity can be obtained. Examples of such silanes include hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Particularly preferred are pigments based on silica-coated aluminum substrate platelets that have been surface-modified with monofunctional silanes. Octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane, and hecadecyltriethoxysilane are particularly preferred. The modification / hydrophobization of surface properties leads to improvements in adhesion, abrasion resistance, and orientation in applications.

[0140] It has also been shown that VMP substrate platelet-based pigments having such surface modifications exhibit better compatibility with the organosilicon compounds and / or their condensation or polymerization products used.

[0141] Particularly good results have been obtained when agent (b) comprises one or more VMP substrate platelet 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, and very preferably 0.5 to 4.5% by weight, relative to the total weight of agent (b).

[0142] Substrate platelet-based pigments which constitute vacuum metallized pigments are available, for example, under the names Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

[0143] VMP substrate platelet-based pigments have a defined particle size in terms of thickness and particle area, which allows complete coverage of keratinous materials when used in the correct amount. Also, dyeings with VMP substrate platelet-based pigments exhibit extremely high rub-fastness and wash-off fastness due to their smooth surface structure.

[0144] In addition to the substrate platelet-based pigment that constitutes the vacuum metallized pigment, agent (b) may comprise further colorant compounds selected from the group consisting of pigments and / or direct dyes.

[0145] Pigments within the meaning of the present invention are colored compounds having a water solubility of less than 0.5 g / L, preferably less than 0.1 g / L, and even more preferably less than 0.05 g / L at 25°C. Water solubility 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 undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be visually evaluated, perhaps due to a high load 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.

[0146] Suitable color pigments can be of inorganic and / or organic origin.

[0147] In one preferred embodiment, the method is characterized in that agent (b) comprises at least one further colorant compound selected from the group consisting of inorganic and / or organic pigments.

[0148] Preferred color pigments are selected from synthetic or natural inorganic pigments.Naturally occurring inorganic color pigments can be made from, for example, chalk, ochre, 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.

[0149] 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 colored pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), reddish-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).

[0150] Colored pearlescent pigments are also particularly preferred. 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 the metal oxide.

[0151] 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 (glimmer), which are coated with one or more of the above-mentioned metal oxides. The color of each pigment can be changed by changing the thickness of the metal oxide layer.

[0152] Also preferred are synthetically produced mica platelets based on synthetic fluorphlogopite (INCI: Synthetic Fluorphlogopite) coated with metal oxides. The synthetic fluorphlogopite platelets are coated with, for example, tin oxide, iron oxide, and / or titanium dioxide. The metal oxide layer may further contain a pigment, such as iron(II / III) hexacyanilide or carmine red. Such mica pigments are available, for example, from Eckart under the name SYNCRYSTAL.

[0153] In a further preferred embodiment, the method is characterized in that agent (b) comprises at least one further colorant compound from the group of 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.

[0154] In a further preferred embodiment, the method is characterized in that agent (b) comprises at least one further colorant compound selected from the group of pigments consisting of mica or glimmer-based pigments reacted with one or more metal oxides selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxides (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).

[0155] Other suitable pigments are metal oxide-coated platelet-shaped borosilicate-based pigments, which are coated with, for example, tin oxide, iron oxide, silicon dioxide, and / or titanium dioxide. Such borosilicate-based pigments are available, for example, from Eckart under the name MIRAGE or from BASF SE under the name Reflecks.

[0156] 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.

[0157] Particularly preferred color pigments having the trade name Colorona® are, for example: Colorona Copper, Merck, Mica, CI 77491 (Iron Oxides) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona Patina Silver, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona RY, Merck, CI 77891 (Titanium Dioxide), Mica, CI 75470 (CARMINE) Colorona Oriental Beige, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Dark Blue, Merck, mica, titanium dioxide, ferric ferrocyanide Colorona Chameleon, Merck, CI 77491 (iron oxide), mica Colorona Aborigine Amber, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Blackstar Blue, Merck, CI 77499 (iron oxides), mica Colorona Patagonian Purple, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) Colorona Red Brown, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Russet, Merck, CI 77491 (Titanium Dioxide), Mica, CI 77891 (Iron Oxides) Colorona Imperial Red, Merck, Mica, Titanium Dioxide (CI 77891), D&C Red No. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (Titanium Dioxide), Mica, CI 77288 (Chromium Oxide 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 Oxides) Colorona Bronze, Merck, Mica, CI 77491 (Iron Oxides) Colorona Bronze Fine, Merck, Mica, CI 77491 (Iron Oxides) Colorona Fine Gold MP 20, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Sienna Fine, Merck, CI 77491 (iron oxides), mica Colorona Sienna, Merck, Mica, CI 77491 (Iron Oxides) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, CI 77491 (Iron Oxides), Tin Oxide Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxides, Mica, CI 77891, CI 77491(EU) Colorona Mica Black, Merck, CI 77499 (Iron Oxides), Mica, CI 77891 (Titanium Dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Blackstar Gold, Merck, Mica, CI 77499 (Iron Oxides) Colorona SynCopper, Merck, synthetic fluorphlogopite and iron oxide Colorona SynBronze, Merck, synthetic fluorphlogopite and iron oxide is.

[0158] Other particularly preferred color 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 is.

[0159] Particularly preferred colour pigments also have the trade name Unipure®, for example: Unipure Red LC 381 EM, Sensitive CI 77491 (iron oxide), silica Unipure Black LC 989 EM, Sensitive, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensitive, CI 77492 (Iron Oxide), Silica is.

[0160] 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 is.

[0161] In a further embodiment, agent (b) may also comprise one or more additional colorant compounds selected from the group consisting of organic pigments.

[0162] 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, diketopyrrolopyorrole, indigo, thioindido, dioxazine and / or triarylmethane compounds.

[0163] Examples of particularly suitable organic pigments include 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 12130, CI 12140, CI 121565, CI 121570, CI 12160, CI 12170, CI 12170, CI 12180, CI 12190, CI 12191, CI 12192, CI 12193, CI 12194, CI 12195, CI 12196, CI 12197, CI 12198, CI 12199, CI 12200, CI 12201, CI 12202, CI 12203, CI 12204, CI 12205, CI 12206, 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.

[0164] In another particularly preferred embodiment, the method further comprises the step of: wherein composition (b) is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments having Color Index Numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments having Color Index Numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments having Color Index Numbers CI 61565, CI 61570, CI 74260, orange pigments having Color Index Numbers CI 11725, CI 15510, CI 45370, CI 71105, and the like. 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915, CI 75470, and mixtures thereof.

[0165] The organic pigment may also be a colored coating. In the sense of the present invention, the term colored lacquer refers to particles containing an adsorbed dye layer, and the particles and dye units are insoluble under the above conditions. The particles may be, for example, inorganic substrates, such as aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or aluminum.

[0166] For example, alizarin pigmented varnish can be used.

[0167] Due to their excellent lightfastness and heat resistance, it is particularly preferred to use the above-mentioned pigments in agent (b) of the method. It is also preferred if the pigments used have a certain particle size. According to the present 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, and more preferably 14 to 30 μm. 50 It is preferable that the average particle size D 50 can be measured, for example, using dynamic light scattering (DLS).

[0168] In addition to the VMP substrate platelet-based pigment, agent (b) may comprise, as further colorant compounds (b1), other effect pigments, such as lamellar substrate platelet-based pigments and / or lenticular substrate platelet-based pigments.

[0169] The further pigments may be used in amounts of 0.001 to 20% by weight, 0.05 to 5% by weight, in each case relative to the total weight of agent (b).

[0170] As an additional coloring compound, the agent (b) used in the method may also contain one or more direct dyes.Direct action dyes are dyes that are applied directly to hair and do not require oxidative methods for color formation.Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols.

[0171] Direct dyes within the meaning of the present invention are those that have a solubility in water of more than 0.5 g / L at 25° C. (760 mmHg) and are therefore not considered pigments.

[0172] Preferably, direct dyes within the meaning of the present invention have a solubility in water of more than 1.0 g / L at 25° C. (760 mmHg).

[0173] Direct dyes can be divided into anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

[0174] In a further preferred embodiment, the method is characterized in that agent (b) comprises at least one anionic direct dye, cationic direct dye and / or non-ionic direct dye as further coloring compound.

[0175] In another preferred embodiment, the method is characterized in that the agent (b) comprises at least one anionic direct dye, cationic direct dye and / or non-ionic direct dye.

[0176] 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, and / or Basic Red 76.

[0177] As the nonionic direct dyes, nonionic nitro dyes and quinone dyes as well as neutral azo dyes can be used. Suitable nonionic direct dyes include 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-hydroxy-2-methyl ... 2-(2-hydroxyethyl)aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2'-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

[0178] In a further preferred embodiment, the method is characterized in that agent (b) comprises at least one direct dye selected from the group consisting of anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

[0179] In the course of the research that led to the present invention, it was found that dyeings of particularly high colour strength can be produced using an agent (b) comprising at least one anionic direct dye.

[0180] In one obviously very particularly preferred embodiment, the agent (b) used in the method is therefore characterized in that it comprises at least one anionic direct dye.

[0181] 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 to its deprotonated form (-COO - , -SO3 - The proportion of the protonated form increases with decreasing pH. When a direct dye is used in the form of its salt, the carboxylic acid group or sulfonic acid group exists in a deprotonated form and is neutralized with a corresponding stoichiometric equivalent of cation to maintain electrical neutrality. The acid dyes of the present invention can also be used in the form of their sodium salts and / or potassium salts.

[0182] Acid dyes within the meaning of the present invention are those that have a solubility in water at 25° C. (760 mmHg) of more than 0.5 g / L and are therefore not considered pigments. Preferably, acid dyes within the meaning of the present invention have a solubility in water at 25° C. (760 mmHg) of more than 1.0 g / L.

[0183] Alkaline earth salts (e.g., calcium and magnesium salts) 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.

[0184] An essential feature of acid dyes is the ability to form an anionic charge, the carboxylic or sulfonic acid group responsible for this is usually linked to a different chromophore system, suitable chromophore systems being 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.

[0185] In one embodiment of the method, therefore, preference is given to using an agent (b), characterized in that it 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, each dye from the above groups having at least one carboxylic acid group (-COOH), sodium carboxylate group (-COONa), potassium carboxylate group (-COOK), sulfonic acid group (-SOH), sodium sulfonate group (-SONa) and / or potassium sulfonate group (-SOK).

[0186] For example, one or more compounds from the following group 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; KATSU 201; 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 Erythrosin 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, CI44090, 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.

[0187] The solubility of a direct dye in water can be measured, for example, as follows: Add 0.1 g of the direct dye to a beaker. Add a stir bar. Then add 100 ml of water. Heat the mixture to 25°C while stirring with a magnetic stirrer. Allow to stir for 60 minutes. Then visually evaluate the aqueous mixture. If there is still undissolved residue, increase the amount of water, for example, in 10 ml increments. Add water until the amount of dye used is completely dissolved. If the dye-water mixture cannot be visually evaluated due to high dye loading, filter the mixture. If a percentage of undissolved dye remains on the filter paper, repeat the solubility test 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 1.0 g / L.

[0188] 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).

[0189] Acid Yellow 3 is a mixture of the monosulfonic acid sodium salt and disulfonic acid sodium salt of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione, and has a solubility in water of 20 g / L (25°C).

[0190] 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).

[0191] 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.

[0192] 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 at 25 °C.

[0193] 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.

[0194] 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.).

[0195] Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, and its solubility in water has been shown to be greater than 10 g / L (25° C.).

[0196] 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).

[0197] One example of a very particularly preferred method is where the agent (b) 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, 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 Ba and at least one anionic direct dye selected from the group consisting of Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 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, D&C Brown 1, and mixtures thereof.

[0198] The direct dyes, especially the anionic direct dyes, can be used in various amounts in agent (b) depending on the desired color intensity. Particularly good results have been obtained when agent (b) contains one or more direct dyes 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 (b).

[0199] In a further preferred embodiment, the method is characterized in that agent (b) comprises one or more direct dyes 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, most preferably 0.5 to 4.5% by weight, relative to the total weight of agent (b).

[0200] In a further preferred embodiment, the method is characterized in that the agent (b) comprises one or more anionic direct dyes 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, most preferably 0.5 to 4.5% by weight, relative to the total weight of the agent.

[0201] The agent (b) used in the method is further characterized in that it comprises at least one film-forming polymer (b2).

[0202] 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 synthetic polymer that is produced by polymerizing one type of monomer or by polymerizing structurally different types of monomers.When a polymer is produced by polymerizing one type of monomer, it is called a homopolymer.When structurally different types of monomers are used in polymerization, the resulting polymer is called a copolymer.

[0203] The maximum molecular weight of the polymer depends on the degree of polymerization (number of polymerized monomers) and the batch size, which is determined by the polymerization method. In the context of the present invention, the maximum molecular weight of the film-forming hydrophobic polymer (b2) 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.

[0204] 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 fiber. The formation of a film can be demonstrated, for example, by viewing the keratinous material treated with the polymer under a microscope.

[0205] The film-forming polymer (b2) in the agent (b) may be hydrophilic or hydrophobic.

[0206] In the first embodiment, it may be preferable to use at least one hydrophobic film-forming polymer in agent (b).

[0207] A hydrophobic polymer is a polymer that has a solubility in water of less than 1% by weight at 25° C. (760 mmHg).

[0208] 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. Draw up to 100 g with water. Add a stir bar and heat the mixture to 25°C while stirring with a magnetic stirrer. Allow to stir for 60 minutes. The aqueous mixture is then visually evaluated. 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.

[0209] These include acrylic acid type polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose polymers, nitrocellulose polymers, silicone polymers, acrylamide type polymers and polyisoprene.

[0210] Particularly suitable film-forming hydrophobic polymers are, for example, polymers from the group of acrylic acid copolymers, methacrylic acid copolymers, 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.

[0211] In a further preferred embodiment, the method is characterized in that the agent (b) comprises at least one film-forming hydrophobic polymer (b2) selected from the group consisting of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of 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.

[0212] Film-forming hydrophobic polymers selected from the group of synthetic polymers, polymers obtainable by radical polymerization or natural polymers have proven to be particularly suitable for solving the problem according to the invention.

[0213] 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 10It can be selected from homopolymers or copolymers of esters or amides of (meth)acrylic acid having hydroxyalkyl groups.

[0214] 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.

[0215] Further film-forming hydrophobic polymers can be selected from homopolymers or copolymers of (meth)acrylamides, N-alkyl(meth)acrylamides, those with C2 to C18 alkyl groups, such as N-ethylacrylamide, N-tert-butylacrylamide, le N-octylacrylamide, N-di(C1 to C4)alkyl(meth)acrylamides.

[0216] Other preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid, or their C1-C6 alkyl esters, which are sold under the INCI Declaration "Acrylate Copolymer." A suitable commercial product is, for example, Aculyn® 33 from Rohm & Haas. Copolymers of acrylic acid, methacrylic acid, or their C1-C6 alkyl esters and esters of ethylenically unsaturated acids and alkoxylated fatty alcohols are also preferred. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid, and itaconic acid; suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20.

[0217] 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 / palmethylene-25 acrylate copolymer) or Rohme und The commercially available product is Soltex OPT (Acrylates / C12-22 Alkyl Methacrylate Copolymer) manufactured by Haas.

[0218] 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.

[0219] Also particularly suitable are 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.

[0220] Suitable olefin-based polymers include homopolymers and copolymers of ethylene, propylene, butene, isoprene, and butadiene.

[0221] In another embodiment, the film-forming hydrophobic polymer may be a block copolymer containing at least one block of styrene or a derivative of styrene. Such a block copolymer may be a copolymer containing one or more blocks in addition to the styrene block, such as styrene / ethylene, styrene / ethylene / butylene, styrene / butylene, styrene / isoprene, or styrene / butadiene. Such polymers are commercially available from BASF under the trade name "Luvitol HSB."

[0222] Surprisingly, it has been found that particularly intense and wash-off-fast colorations can be obtained when agent (b) comprises at least one film-forming polymer (b2) 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.

[0223] In a further preferred embodiment, the method is characterized in that the agent (b) comprises at least one film-forming polymer (b2) 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.

[0224] In a further embodiment, it may be preferable to use at least one hydrophilic film-forming polymer (b2) in agent (b).

[0225] 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.

[0226] 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. Bring to 100 g with water. Add a stir bar and heat the mixture to 25°C while stirring with a magnetic stirrer. Allow to stir for 60 minutes. The aqueous mixture is then visually evaluated. 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 wt%.

[0227] Nonionic, anionic and cationic polymers can be used as film-forming hydrophilic polymers.

[0228] 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.

[0229] Furthermore, it is particularly preferred to use polyvinylpyrrolidone (PVP) and / or vinylpyrrolidone-containing copolymers as film-forming hydrophilic polymers.

[0230] In another very particularly preferred embodiment, the method is characterized in that agent (b) comprises at least one film-forming hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone (PVP) and copolymers of polyvinylpyrrolidone.

[0231] It is further preferred if 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 (b9) was also particularly good.

[0232] 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.

[0233] 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 approximately 40,000 g / mol.

[0234] Other particularly suitable polyvinylpyrrolidones are the substances known under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60, LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115, available from BASF.

[0235] The use of film-forming hydrophilic polymers (b2) from the group of polyvinylpyrrolidone copolymers also resulted in particularly good wash-off fastness coloring results.

[0236] 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 nonionic polymers.

[0237] Among 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.

[0238] 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.

[0239] 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.

[0240] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises at least one film-forming hydrophilic polymer (b2) 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.

[0241] Another fussy copolymer of vinylpyrrolidone is the polymer known by the INCI designation Maltodextrin / VP Copolymer.

[0242] 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, with particularly good wash-off fastness properties.

[0243] In another embodiment, agent (b) may comprise at least one non-ionic film-forming hydrophilic polymer (b2).

[0244] According to the present invention, a nonionic polymer is understood to be a polymer that does not have structural units with permanent cationic or anionic groups that must be compensated by counterions under standard conditions in a protic solvent, such as water, and remains electron neutral. Cationic groups include quaternized ammonium groups, but do not include protonated amines. Anionic groups include carboxylic acid groups and sulfonic acid groups.

[0245] 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 are products comprising at least one polymer selected from the group consisting of:

[0246] When copolymers of N-vinylpyrrolidone and vinyl acetate are used, it is again preferred if the molar ratio of structural units of the N-vinylpyrrolidone monomer to structural units of the polymer of the vinyl acetate monomer 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, from BASF SE under the trademarks Luviskol® VA 37, Luviskol® VA 55, Luviskol® VA 64 and Luviskol® VA 73.

[0247] 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.

[0248] 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.

[0249] 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).

[0250] 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 and FC 905 and HM 552, vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, in which the third monomer component is an acrylic acid ester and an acrylic acid amide, such as those commercially available under the name Aquaflex® SF 40, Examples include:

[0251] 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.

[0252] 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 to 5 wt. % 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 highly preferred to use Polyquaternium-46 in combination with a cationic guar compound and Polyquaternium-11.

[0253] 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.

[0254] Examples of suitable film-forming hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum, carob gum.

[0255] Examples of suitable film-forming hydrophilic polymers from the group of polysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.

[0256] Suitable film-forming hydrophilic polymers from the acrylamide group are, for example, polymers prepared from (meth)acrylamido-C1-C4-alkylsulfonic acid or salt monomers. Corresponding polymers may be selected from polymers of polyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid, polyacrylamidopropanesulfonic acid, poly2-acrylamido-2-methylpropanesulfonic acid, poly-2-methylacrylamido-2-methylpropanesulfonic acid and / or poly-2-methylacrylamido-n-butanesulfonic acid.

[0257] 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.

[0258] 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".

[0259] Another preferred polymer of this type is a crosslinked poly-2-acrylamido-2 methyl-propanesulfonic acid polymer, partially neutralized with ammonia, sold under the trade name Hostacerin AMPS by Clariant.

[0260] In another expressly very particularly preferred embodiment, the method is characterized in that the agent (b) comprises at least one anionic film-forming polymer (b2).

[0261] In this context, the best results are obtained when the agent (b) comprises at least one film-forming polymer (b2) comprising at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II), JPEG0007755486000035.jpg32155 formula M is a hydrogen atom or ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium.

[0262] In a further preferred embodiment, the method according to the invention is characterized in that the agent (b) comprises at least one film-forming polymer (b2) comprising at least one structural unit of the formula (PI) and at least one structural unit of the formula (P-II), JPEG0007755486000036.jpg30156 formula M is a hydrogen atom or ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium.

[0263] When M represents a hydrogen atom, the structural units of formula (PI) are mainly acrylic acid units.

[0264] When M represents an ammonium counterion, the structural unit of formula (PI) is mainly an ammonium salt of acrylic acid.

[0265] When M represents a sodium counterion, the structural unit of formula (PI) is mainly composed of a sodium salt of acrylic acid.

[0266] When M represents a potassium counter ion, the structural unit of formula (PI) is mainly composed of a potassium salt of acrylic acid.

[0267] When M represents a half equivalent of a magnesium counter ion, the structural unit of formula (PI) is based on the magnesium salt of acrylic acid.

[0268] When M represents a half equivalent of a calcium counter ion, the structural unit of formula (PI) is mainly composed of a calcium salt of acrylic acid.

[0269] The film-forming polymer (b2) is preferably used in agent (b) in a certain range of amounts. In this context, it has been found particularly advantageous for solving the problem according to the invention when agent (b) comprises one or more film-forming polymers (b2) in a total amount of 0.1 to 18% by weight, preferably 1 to 16% by weight, more preferably 5 to 14.5% by weight, and very particularly preferably 8 to 12% by weight, relative to the total weight of agent (b).

[0270] In a further preferred embodiment, the method is characterized in that the agent (b) comprises one or more film-forming polymers (b2) in a total amount of 0.1 to 18% by weight, preferably 1 to 16% by weight, more preferably 5 to 14.5% by weight, very particularly preferably 8 to 12% by weight, relative to the total weight of agent (b).

[0271] Other ingredients in agent (a) and / or (b) The agents (a) and / or (b) described above may further comprise one or more optional ingredients.

[0272] Agents (a) and / or (b) may further 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 have no charge but have a strong dipole moment and are highly hydrated in aqueous solution.

[0273] Zwitterionic surfactants contain at least one quaternary ammonium group and at least one -COO group in the molecule. (-) -or-SO3 (-)These are surface-active compounds bearing a hydroxyl group. Particularly suitable zwitterionic surfactants are 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-hydroxyethylimidazoline, each having 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. One example of a preferred zwitterionic surfactant is a fatty acid amide derivative known by the INCI name cocamidopropyl betaine.

[0274] Amphoteric surfactants have C8 to C 24 These surfactants are surface-active compounds that contain, in addition to an alkyl or acyl group, at least one free amino group and at least one -COOH or -SOH group and are capable of forming an intramolecular salt. Examples of suitable amphoteric surfactants include 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 approximately 8 to 24 carbon atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines, and sulfobetaines.

[0275] Particularly preferred amphoteric surfactants are N-cocos alkylaminopropionate, cocos acylaminoethylaminopropionate and C 12 ~C 18 -acyl sarcosine.

[0276] Agents (a) and / or (b) may also contain at least one nonionic surfactant. Suitable nonionic surfactants are alkyl polyglycoside and alkylene oxide addition products of 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid to fatty alcohols and fatty acids. Preparations with good properties are also obtained when the nonionic surfactant contains a fatty acid ester of ethoxylated glycerol reacted with at least 2 moles of ethylene oxide.

[0277] Furthermore, the agent (a) and / or (b) may also contain at least one cationic surfactant. Cationic surfactants are surfactants, i.e., surface-active compounds, each having one or more positive charges. Cationic surfactants contain only positive charges. Typically, such surfactants are composed of a hydrophobic part and a hydrophilic head group, where the hydrophobic part is usually composed of a hydrocarbon backbone (e.g., one or two linear or branched alkyl chains), and the positive charge is located 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 - a tertiary sulfonium salt.

[0278] 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 in the case of esterquats, for example. The cationic surfactant is used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight, and most preferably 1 to 15% by weight, based on the total weight of the respective agent.

[0279] Furthermore, the agents (a) and / or (b) may also contain at least one anionic surfactant. Anionic surfactants are surface active agents that have an exclusively anionic charge (neutralized by the corresponding counter cation). Examples of anionic surfactants are fatty acids, alkyl sulfates, alkyl ether sulfates and ether carboxylic acids, with 12 to 20 carbon atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

[0280] The anionic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight, very preferably 1 to 15% by weight, relative to the total weight of the respective agent (a) and / or (b).

[0281] To adjust the desired pH, the agents (a) and / or (b) may also contain at least one alkalizing and / or acidifying agent. The pH values ​​for the purposes of the present invention are those measured at a temperature of 22°C.

[0282] As alkalizing agents, agents (a) and / or (b) may contain, for example, ammonia, alkanolamines and / or basic amino acids.

[0283] The alkanolamines that can be used in the agents (a) and / or (b) are preferably selected from primary amines having a C2-C6 alkyl radical 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, and 2-amino-2-methylpropane-1,3-diol.

[0284] 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 agent (a) and / or (b) comprise, as alkalizing agent, an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol.

[0285] For the purposes of the present invention, an amino acid is an organic compound that contains in its structure at least one protonatable amino group and at least one -COOH or one -SOH group. Preferred amino acids are aminocarboxylic acids, in particular α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0286] According to the present invention, a basic amino acid is an amino acid with an isoelectric point pI greater than 7.

[0287] The basic α-aminocarboxylic acid contains at least one asymmetric carbon atom. In the context of the present invention, both possible enantiomers can be used equally as specific compounds or as mixtures thereof, especially as racemates. However, it is particularly preferred to use the naturally occurring preferred isomer form, usually the L-form.

[0288] The basic amino acid is preferably selected from the group formed by arginine, lysine, ornithine and histidine, particularly preferably arginine and lysine. In another particularly preferred embodiment, the agent according to the invention is therefore characterized in that the alkalizing agent is a basic amino acid from the group of arginine, lysine, ornithine and / or histidine.

[0289] Agents (a) and / or (b) may also contain an alkalizing agent, in particular an inorganic alkalizing agent. Applicable inorganic alkalizing agents 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.

[0290] Very 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.

[0291] Acidifying agents familiar to those skilled in the art are, for example, organic acids such as citric acid, acetic acid, maleic acid, lactic acid, malic acid or tartaric acid and dilute mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.

[0292] Agent (a) and / or (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 agent (a) or agent (b). Preferably, agent (b) comprises a matting agent.

[0293] It may be particularly preferred that agent (a) further comprises at least one colorant compound selected from the group consisting of pigments and / or direct dyes.

[0294] The colorant compounds from the group of pigments and / or direct dyes that can be used in agent (a) can in principle correspond to the colorant compounds also used in agent (b).

[0295] In a more preferred embodiment, the method is characterized in that agent (a) comprises at least one colorant compound selected from the group consisting of inorganic pigments and / or organic pigments.

[0296] In another particularly preferred embodiment, the method further comprises the step of: (a) comprising: a) a composition selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments having Color Index Numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160; yellow pigments having Color Index Numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005; green pigments having Color Index Numbers CI 61565, CI 61570, CI 74260; orange pigments having Color Index Numbers CI 11725, CI 15510, CI 45370, CI 71105; 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915, CI 75470, and mixtures thereof.

[0297] Agents (a) and / or (b) may also contain other active ingredients, auxiliaries and additives, such as solvents; aliphatic components, such as C8-C 30 Fatty acid triglycerides, C8-C 30 Fatty acid monoglycerides, C8-C 30 fatty acid diglycerides and / or hydrocarbons; polymers; structurants, such as glucose or sodium chloride, 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 plant 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 salts thereof or bicarbonate. It may also contain saborol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarin, 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; pearlizing agents, such as ethylene glycol mono- and distearate and PEG-3-distearate; and blowing agents, such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0298] The selection of such other substances is made by a specialist 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 specialist. The additional active ingredients and auxiliary substances are preferably used in the agent (a) and / or (b) in an amount of 0.0001 to 25% by weight, 0.0005 to 15% by weight, in each case based on the total weight of the respective agent.

[0299] Method for dyeing keratinous materials In the procedure according to the invention, agents (a) and (b) are applied to keratinous material, human hair. Agents (a) and (b) are therefore ready-to-use agents. Agents (a) and (b) are different.

[0300] In principle, agents (a) and (b) can be applied simultaneously or successively, with successive application being preferred.

[0301] The best results were obtained when agent (a) was applied to the keratinous materials as a pre-treatment agent and then agent (b) was applied as a coloring agent.

[0302] Particularly preferred is therefore a method for dyeing keratinous material, in particular human hair, comprising the following steps in the order given: - in a first step, an agent (a) is applied to the keratinous material, said agent (a) comprising at least one organosilicon compound, and In a second step, an agent (b) is applied to the keratinous material, said agent (b) comprising: (b1) at least one colorant compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer The method includes:

[0303] Furthermore, in order to impart high dissolution durability to the dyed keratinous material over a long period of time, agents (a) and (b) are particularly preferably applied in one and the same dyeing method, which means that the period between the application of agent (a) and the application of agent (b) is a maximum of several hours.

[0304] In a further preferred embodiment, the method is characterized in that agent (a) is applied first, followed by agent (b), and the period between application of agent (a) and application of agent (b) is at most 24 hours, preferably at most 12 hours, particularly preferably at most 6 hours.

[0305] In the method according to the invention, keratinous material, in particular human hair, is first treated with agent (a), followed by application of the actual coloring agent (b), which comprises a colorant compound, to the keratinous material.

[0306] Preferably, the agent (a) itself does not contain a coloring agent or coloring compound. One of the characteristic features of the pretreatment agent (a) is that it contains at least one reactive organosilicon compound. The reactive organosilicon compound (a) functionalizes the hair surface as soon as it comes into contact with it. In this way, a first, still uncolored film is formed. In the second step of the method, the coloring agent (b) is then applied to the hair. During the application of the coloring agent (b), the coloring compound interacts with the film formed by the organosilicon compound, and is thus bound to the keratinous material.

[0307] In accordance with a further embodiment, the following steps are performed in the order shown: (1) applying agent (a) to a keratinous material; (2) allowing agent (a) to act for a period of 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (3) If necessary, rinse the keratinous material 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; and (6) Rinse the keratinous material with water. Particularly preferred is a procedure comprising:

[0308] Rinsing of the keratinous material with water in steps (3) and (6) of the method is understood to mean, according to the present invention, the use of only water in the rinsing method without any other agents other than agents (a) and (b).

[0309] In step (1), agent (a) is first applied to keratinous material, in particular human hair.

[0310] After application, the agent (a) is left to act on the keratinous material. In this connection, exposure times to the keratinous material, human hair, of 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, most preferably 30 seconds to 2 minutes have been found to be particularly suitable.

[0311] In one preferred embodiment of the method, agent (a) can then be rinsed from the keratinous material before applying agent (b) to the hair in a subsequent step.

[0312] Dyeings with equally good wash-off fastness were obtained when agent (b) was applied to keratinous materials that were still exposed to agent (a).

[0313] In step (4), agent (b) is then applied to the keratinous material. After application, agent (b) is allowed to act on the hair.

[0314] Even if the contact times with agent (b) are short, the process makes it possible to obtain dyeings having particularly good strength and wash-off fastness. Contact times of 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, and most preferably 30 seconds to 3 minutes on keratinous materials, on human hair, have been found to be particularly suitable.

[0315] In step (6), agent (b) (and agent (a) if still present) is then rinsed from the keratinous material with water.

[0316] Multi-component package unit (kit of parts) In the method according to the invention, the agents (a) and (b) are applied to the keratinous materials, ie the two agents (a) and (b) are each ready-to-use agents.

[0317] 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).

[0318] A second subject of the invention is therefore a first container containing an agent (a), said agent (a) comprising at least one organosilicon compound, and a second container containing agent (b), said agent (b) comprising: (b1) at least one colorant compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer a second container containing It is a multi-component package unit (kit of parts) for coloring keratinous materials, in which the components are packaged separately and comprehensively.

[0319] The organosilicon compound contained in agent (a) of the kit corresponds to the organosilicon compound used in agent (a) of the above method.

[0320] The colorant compounds from the group of pigments and / or direct dyes contained in agent (b) of the kit correspond to the colorant compounds from the group of pigments and / or direct dyes also used in agent (b) of the method described above.

[0321] Agent (a) contains, in addition to the organosilicon compound, a reactive compound of the type described above that can undergo hydrolysis and / or oligomerization and / or polymerization in the presence of moisture. As a result of their high reactivity, such organosilicon compounds form a film on keratinous materials.

[0322] To avoid premature hydrolysis, oligomerization and / or polymerization, it may be preferable to prepare the ready-to-use agent (a) immediately prior to use.

[0323] In the context of a further embodiment, a multi-component packaging unit (kit of parts) for coloring keratinous materials preferably comprises: a first container containing an agent (a1), said agent (a1) comprising at least one organosilicon compound; a second container containing an agent (a2), said agent (a2) containing water, a third container containing agent (b), said agent (b) comprising: (b1) at least one colorant compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer a third container containing It is a multi-component package unit (kit of parts) for coloring keratinous materials, in which the components are packaged separately and comprehensively.

[0324] In order to obtain a formulation that is as stable as possible during storage, the agent (a1) itself is preferably packaged with low or no water content.

[0325] In a preferred embodiment, the multicomponent packaging unit (kit of parts) is characterized in that the agent (a1) has a water content of less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, and very particularly preferably less than 0.01% by weight, relative to the total weight of the agent (a1).

[0326] Agent (a2) comprises water. In a preferred embodiment, the multicomponent packaging unit (kit of parts) is characterized in that agent (a2) 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).

[0327] Within this version, the ready-to-use agent (a) is then prepared by mixing agents (a1) and (a2).

[0328] For example, the user may first mix or shake the organosilicon compound-containing agent (a1) with the water-containing agent (a2). The user may then apply this mixture of (a1) and (a2) 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.

[0329] With regard to the further preferred embodiment of the multi-component packaging unit, the same applies mutatis mutandis to the method. Preferred aspects of the present invention include the following. [1] The following: - applying an agent (a) to the keratinous material, said agent (a) comprising at least one organosilicon compound and - applying an agent (b) to the keratinous material, said agent (b) comprising: (b1) at least one colorant compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer Processes including 1. A method for dyeing keratinous material, in particular human hair, comprising: [2] The method according to [1], characterized in that the agent (a) comprises at least one organosilicon compound selected from silanes having one, two or three silicon atoms, the organosilicon compound preferably containing one or more basic chemical functionalities and one or more hydroxyl or hydrolyzable groups per molecule. [3] The agent (a) comprises at least one organosilicon compound of formula (I) and / or (II), R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b(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 chain divalent C 1 ~C 20 is an alkylene group, -R 3 is a hydrogen atom or C 1 ~C 6 is an alkyl group, -R 4 is C 1 ~C 6 represents an alkyl group, -a represents an integer from 1 to 3, -b is an integer equal to 3-a, Here, in the organosilicon compound of formula (II), (R 5 O) c (R 6 ) d Si-(A) e -[NR 7 -(A’)] f -[O-(A'')] g -[NR 8 -(A’’’)] h -Si(R 6 ’) d’ (OR 5 ’) c’ (II), R5, R5', and R5'' are independently a hydrogen atom or C 16 represents an alkyl group, R6, R6' and R6'' are independently C 16 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 hydrogen atoms, 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), -(A'''')-Si(R 6 ’’) d ''(OR 5 ’’) c ''(III), -c represents an integer between 1 and 3, -d represents an integer of 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 of 3-c'', -e represents 0 or 1, -f represents 0 or 1, -g represents 0 or 1, -h represents 0 or 1, However, at least one of e, f, g, and h must be different from 0. The method according to [1] or [2], [4] The agent (a) comprises at least one organosilicon compound of formula (I), R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b (I)、 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 represents a hydrogen atom, an ethyl group, or a methyl group, -R 4 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 [3], characterized in that [5] The agent (a) (3-aminopropyl)triethoxysilane (3-aminopropyl)trimethoxysilane 1-(3-aminopropyl)silanetriol (2-aminoethyl)triethoxysilane (2-aminoethyl)trimethoxysilane 1-(2-aminoethyl)silanetriol (3-Dimethylaminopropyl)triethoxysilane (3-Dimethylaminopropyl)trimethoxysilane 1-(3-dimethylaminopropyl)silanetriol (2-Dimethylaminoethyl)triethoxysilane (2-Dimethylaminoethyl)trimethoxysilane 1-(2-dimethylaminoethyl)silanetriol, and A mixture of these The method according to any one of [1] to [4], characterized in that the method comprises using at least one organosilicon compound represented by formula (I) selected from the group consisting of: [6] the agent (a) comprises at least one organosilicon compound of formula (II), (R 5 O) c (R 6 ) d Si-(A) e -[NR 7 -(A’)] f -[O-(A'')] g -[NR 8 -(A’’’)] h -Si(R 6 ’) d’ (OR 5 ’) 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 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 [5], characterized in that [7] The agent (a) 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine 3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine N-methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine 2-[bis[3-(trimethoxysilyl)propyl]amino]-ethanol 2-[bis[3-(triethoxysilyl)propyl]amino]-ethanol -3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine, and A mixture of these The method according to any one of [1] to [6], characterized in that the method comprises using at least one organosilicon compound represented by formula (II) selected from the group consisting of: [8] The agent (a) comprises at least one organosilicon compound of formula (IV), R 9 Si(OR 10 ) k (R 11 ) m (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 The method according to any one of [1] to [7], [9] The agent (a) Methyltrimethoxysilane Methyltriethoxysilane Ethyltrimethoxysilane Ethyltriethoxysilane Hexyltrimethoxysilane Hexyltriethoxysilane Octyltrimethoxysilane Octyltriethoxysilane Dodecyltrimethoxysilane Dodecyltriethoxysilane Octadecyltrimethoxysilane Octadecyltriethoxysilane, and A mixture of these The method according to any one of [1] to [8], characterized in that the method comprises using at least one organosilicon compound represented by formula (IV) selected from the group consisting of:

[10] The method according to any one of [1] to [9], wherein the substrate platelet comprises 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 substrate platelet contains aluminum.

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

[11] , characterized in that the substrate platelet 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 platelet 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 platelet 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 containing an agent (a), said agent (a) comprising at least one organosilicon compound, and a second container containing agent (b), said agent (b) comprising: (b1) at least one colorant compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer a second container containing Kit-of-parts for dyeing keratinous materials, including: [Example]

[0330] 1. Compound The following formulations were made (all numbers in weight % unless otherwise stated): TIFF0007755486000037.tif39153

[0331] The silane was mixed with a portion of water and the mixture was left for 30 minutes. The pH was then adjusted to the desired value by adding citric acid / ammonia. Water was then added to make up to 100 g. TIFF0007755486000038.tif67153

[0332] 2. Application A lock of hair (Kerling, Euro Natural Hair White) was immersed in medium (a) and left for 1 minute.

[0333] Excess formulation (a) was then removed from each tress. Each tress was briefly rinsed with water. Excess water was rubbed off from each tress.

[0334] Next, each hair tress was immersed in agent (b) and left for 1 minute. After that, excess agent (b) was removed from each hair tress. Each hair tress was rinsed briefly with water. Excess water was rubbed off from each hair tress.

[0335] The hair bundle was then visually evaluated, and it was found to have high strength and durability, and to have a metallic white color.

Claims

1. below: applying an agent (a) to the keratinous material, said agent (a) being of formula (I): R １ R ２ N-L-Si(OR ３ ) ａ (R ４ ) ｂ (I) [In formula (I) -R １ , R ２ are independently a hydrogen atom or C １ ~C ６ represents an alkyl group, -L is a straight or branched chain divalent C １ ~C ２０ is an alkylene group, -R ３ is a hydrogen atom or C １ ~C ６ is an alkyl group, -R ４ is C １ ~C ６ represents an alkyl group, -a represents an integer of 1 to 3; -b is an integer equal to 3-a. and at least one organosilicon compound of formula (IV): R ９ Si(OR １０ ) ｋ (R １１ ) ｍ (IV) [In formula (IV) -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. At least one organosilicon compound of and applying an agent (b) to the keratinous material, said agent (b) comprising: (b1) at least one colorant compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer Processes including wherein the agent (a) and the agent (b) are applied in the order indicated above; A method for dyeing keratinous materials.

2. The agent (a) is a compound represented by the formula (II): (R ５ O) ｃ (R ６ ) ｄ Si-(A) ｅ -[NR ７ -(A')] ｆ -[O-(A'')] ｇ -[NR ８ -(A''')] ｈ -Si(R ６ ') ｄ’ (OR ５ ') ｃ’ (II) [In formula (II), R5, R5', and R5'' are independently a hydrogen atom or C １～６ represents an alkyl group, R6, R6' and R6'' are independently C １～６ 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), -(A'''')-Si(R ６ '') ｄ '' (OR ５ '') ｃ '' (--I) -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 of 3-c''; -e represents 0 or 1; -f represents 0 or 1; -g represents 0 or 1; -h represents 0 or 1; provided that at least one of e, f, g, and h is different from 0.

2. The method of claim 1, comprising at least one organosilicon compound of the formula:

3. The agent (a) is a compound of formula (I): R １ R ２ N-L-Si(OR ３ ) ａ (R ４ ) ｂ (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 represents a hydrogen atom, an ethyl group, or a methyl group, -R ４ represents a methyl group or an ethyl group, -a represents the number 3, -b represents the number 0.

3. The method according to claim 1, further comprising the step of:

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 1-(2-dimethylaminoethyl)silanetriol, and ・Mixtures of these 4. The method according to claim 1, further comprising the step of:

5. said agent (a) comprising at least one organosilicon compound of formula (II), (R ５ O) ｃ (R ６ ) ｄ Si-(A) ｅ -[NR ７ -(A')] ｆ -[O-(A'')] ｇ -[NR ８ -(A''')] ｈ -Si(R ６ ') ｄ’ (OR ５ ') ｃ’ (II), During the ceremony R5, R5', and R5'' are independently a hydrogen atom or C １～６ represents an alkyl group, R6, R6' and R6'' are independently C １～６ represents an alkyl group, - A and A' are independently a linear divalent C １ ~C ６ represents alkylene, - A", A"' and A"" are independently straight or branched chain divalent C １ ~C ２０ represents an alkylene group, -R ７ represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III), -(A'''')-Si(R ６ '') ｄ '' (OR ５ '') ｃ '' (--I) -R ８ is 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 of 3-c''; - e and f both represent the number 1; - g and h both represent the number 0 The method according to any one of claims 2 to 4, characterized in that

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 N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine, and ・Mixtures of these Formula (II) selected from the group consisting of: (R ５ O) ｃ (R ６ ) ｄ Si-(A) ｅ -[NR ７ -(A')] ｆ -[O-(A'')] ｇ -[NR ８ -(A''')] ｈ -Si(R ６ ') ｄ’ (OR ５ ') ｃ’ (II) [In formula (II), R5, R5', and R5'' are independently a hydrogen atom or C １～６ represents an alkyl group, R6, R6' and R6'' are independently C １～６ 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), -(A'''')-Si(R ６ '') ｄ '' (OR ５ '') ｃ '' (--I) -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 of 3-c''; -e represents 0 or 1; -f represents 0 or 1; -g represents 0 or 1; -h represents 0 or 1; provided that at least one of e, f, g, and h is different from 0.

6. The method according to claim 2, further comprising the step of:

7. The agent (a) is ・Methyltrimethoxysilane ・Methyltriethoxysilane ・Ethyltrimethoxysilane ・Ethyltriethoxysilane ・Hexyltrimethoxysilane ・Hexyltriethoxysilane ・Octyltrimethoxysilane ・Octyltriethoxysilane ・Dodecyltrimethoxysilane ・Dodecyltriethoxysilane ・Octadecyltrimethoxysilane octadecyltriethoxysilane, and ・Mixtures of these 7. The method according to claim 1, further comprising the step of:

8. The method of any one of claims 1 to 7, characterized in that the substrate platelet comprises a material selected from the group consisting of metals, metal alloys and metal oxides.

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

10. 10. The method according to any one of claims 1 to 9, characterized in that the substrate platelet 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.

11. 11. The method according to any one of claims 1 to 10, characterized in that the substrate platelet comprises a coating B of at least one highly refractive metal oxide having a refractive index of at least 1.

9.

12. 12. The method according to claim 11, characterized in that the substrate platelet has a further coating C of at least one metal oxide and / or metal oxide hydrate different from the underlying coating B.

13. Separately packaged a first container containing an agent (a), said agent (a) having formula (I): R １ R ２ N-L-Si(OR ３ ) ａ (R ４ ) ｂ (I) [In formula (I) -R １ , R ２ are independently a hydrogen atom or C １ ~C ６ represents an alkyl group, -L is a straight or branched chain divalent C １ ~C ２０ is an alkylene group, -R ３ is a hydrogen atom or C １ ~C ６ is an alkyl group, -R ４ is C １ ~C ６ represents an alkyl group, -a represents an integer of 1 to 3; -b is an integer equal to 3-a. and at least one organosilicon compound of formula (IV): R ９ Si(OR １０ ) ｋ (R １１ ) ｍ (IV) [In formula (IV) -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 containing at least one organosilicon compound of a second container containing an agent (b), said agent (b) comprising: (b1) at least one colorant compound comprising at least one substrate platelet-based pigment comprising a vacuum metallized pigment; and (b2) at least one film-forming polymer a second container containing A kit of parts for dyeing keratinous materials, comprising:

Images