Method for coloring keratinous materials comprising the use of an organosilicon compound, two colorant compounds, and a post-treatment agent

Abstract

The present invention relates to a method for dyeing keratinous materials, in particular human hair, comprising the steps of: applying an agent (a) to the keratinous materials, wherein the agent (a) comprises: (a1) at least one organosilicon compound selected from the group consisting of silanes, the compound having 1, 2 or 3 silicon atoms, and (a2) a first dyeing compound comprising at least one pigment based on lenticular substrate flakes, and (a3) ​​a second dyeing compound; and applying an agent (b) to the keratinous materials, wherein the agent (b) comprises: (b1) at least one sealing agent. The present invention further discloses a multi-component packaged kit (kit of parts) for dyeing keratinous materials.

Description

[Technical Field]

[0001] The subject of the present application is a method for treating keratinous materials, in particular human hair, comprising the application of two agents (a) and (b). Agent (a) is characterized in that it comprises at least one organosilicon compound (a1), a first colorant compound (a2) comprising at least one pigment based on lenticular substrate platelets, and a second colorant compound (a3). Agent (b) comprises at least one sealing agent (b1).

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

[0003] A further subject of the present application is a multi-component packaging unit (kit of parts) for dyeing keratinous materials, in particular human hair, comprising at least four separately assembled agents (a'), (a'', (a''') and (b). Agents (a'), (a'') and (a''') can be used to prepare agent (a) used in the above process. [Background technology]

[0004] Changing the shape and color of keratin fibers, especially hair, is an important area of modern cosmetics. To change hair color, experts know a variety of coloring systems (coloring methods) tailored to the coloring requirements. For long-lasting, intense dyeing with good fastness and good gray coverage, oxidation dyes are usually used. These dyes usually contain an oxidation dye precursor, a so-called developer component, and a coupler component, which react with each other to form the actual dye under the influence of an oxidizing agent such as hydrogen peroxide. Oxidation dyes are characterized by extremely long-lasting coloring results.

[0005] When using direct dyes, the dye already produced diffuses from the colorant into the hair fiber. Compared to oxidative dyes, dyes obtained with direct dyes have a shorter retention period and faster washability. Dye with direct dyes usually remains on the hair for 5 to 20 washes.

[0006] While good to very good gray coverage can usually be achieved with oxidative dyes, the gray coverage achievable with direct dyes has not yet been satisfactory.

[0007] The use of color pigments to change the color of hair and / or skin for a short period of time is known. Color pigments are generally understood to be insoluble coloring substances. Color pigments are present in the dye composition in the form of small particles without dissolving and simply adhere externally to the hair fiber and / or skin surface. Therefore, they can usually be removed without residue by washing several times with a detergent containing a surfactant. Various products of this type are commercially available under the name of "hair mascara."

[0008] While oxidation dyes can usually achieve good to very good gray coverage, direct dyes have not yet achieved satisfactory gray coverage. However, despite numerous optimization attempts, oxidation hair dyes cannot completely avoid the unpleasant ammonia or amine odor. Hair damage associated with the use of oxidation dyes still adversely affects users' hair.

[0009] Furthermore, consumers with gray hair desire optimal gray coverage from coloring. Optimal gray coverage is understood to mean completely hiding or covering gray hair. When a dye with optimal gray coverage is applied to a person with, for example, 50% gray hair (50% of the hair is gray and 50% of the hair is still pigmented), there is a uniform coloring result after application of the dye, i.e., the color difference between gray hair and non-gray hair is no longer noticeable after dyeing.

[0010] EP 2168633 B1 addresses the problem of producing long-lasting hair colorings using pigments. This document teaches that when a combination of pigments, organosilicon compounds, film-forming polymers, and solvents is applied to hair, it is possible to produce colorings that are particularly resistant to abrasion and / or shampooing.

[0011] It is necessary to provide hair dyes containing pigments which, on the one hand, have high wash and rub fastness and, on the other hand, do not adversely affect hair properties such as manageability and feel. To this end, it is desirable to obtain intense colorations with optimal gray coverage due to good lift of the pigment on keratinous materials. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] European Patent No. 2168633 Summary of the Invention [Problem to be solved by the invention]

[0013] The object of the present invention was therefore to provide a method for coloring using pigments that have fastness comparable to that of oxidation coloring and optimal gray coverage, but which does not require the use of commonly used oxidation dye precursors for this purpose. [Means for solving the problem]

[0014] Surprisingly, it has now been found that the aforementioned problems can be successfully solved when coloring keratinous materials, particularly human hair, by applying at least two agents (a) and (b) to the keratinous materials (hair). The first agent (a) comprises a first colorant compound (a2) and a second colorant compound (a3), each of which comprises at least one organosilicon compound from the group of silanes containing one, two, or three silicon atoms, and at least one pigment based on lenticular substrate platelets. The second agent (b) comprises at least one sealant.

[0015] When the two agents (a) and (b) were used in the dyeing process, it was possible to dye keratinous materials with particularly high color strength and high fastness properties.

[0016] A first subject of the present invention is a method for coloring keratinous materials, in particular human hair, comprising the following steps: applying an agent (a) to the keratinous material, wherein the agent (a) (a1) at least one organosilicon compound selected from the group consisting of silanes containing one, two or three silicon atoms; (a2) a first colorant compound comprising at least one lenticular substrate platelet-based pigment; and (a3) a second colorant compound; including, applying an agent (b) to the keratinous material, wherein the agent (b) (b1) comprising at least one sealant; The method includes:

[0017] In the research leading to the present invention, it has been found that the preferential sequential application of agents (a) and (b) can produce a very stable and wash-fast coloring on keratinous materials.Without being limited to this theory, it is believed herein that the simultaneous application of organosilicon compound (a1), selected first colorant compound (a2) and second colorant compound (a3) results in the formation of a particularly uniformly colored film on keratinous materials.The application of second agent (b) seals the film applied to keratinous materials, thereby making it more resistant to washing and / or abrasion.

[0018] In this way, the colorant compounds can be permanently fixed to the keratin materials, so that very wash-fast colorings are obtained which have good resistance to abrasion and / or shampooing.

[0019] By combining the first colorant compound (a2) containing at least one pigment based on lenticular substrate platelets with the second colorant compound (a3), it was possible to achieve colorings with optimal gray coverage, and very rub- and wash-fast dyeings with good resistance to abrasion and / or shampooing were obtained. DETAILED DESCRIPTION OF THE INVENTION

[0020] <Keratin substance> Keratinous materials include hair, skin, nails (e.g., fingernails and / or toenails). Wool, fur, and feathers also fall within the definition of keratinous materials.

[0021] Preferably, keratinous materials are understood to be human hair, human skin and human nails, in particular fingernails and toenails. In particular, keratinous materials are understood to be human hair.

[0022] <Agents (a) and (b)> In the method of the present disclosure, agents (a) and (b) are applied to keratinous materials, in particular human hair. The two agents (a) and (b) are different from each other.

[0023] In other words, a first subject of the present invention is a method for treating keratinous materials, in particular human hair, comprising the following steps: applying an agent (a) to the keratinous material, wherein the agent (a) (a1) at least one organosilicon compound selected from the group consisting of silanes containing one, two or three silicon atoms; (a2) a first colorant compound comprising at least one lenticular substrate platelet-based pigment; and (a3) a second colorant compound; including, applying an agent (b) to the keratinous material, wherein the agent (b) (b1) comprising at least one sealant; The method includes:

[0024] <Agent (a)> Preferably, composition (a) comprises the essential components (a1), (a2) and (a3) of the present invention in a cosmetic carrier, particularly preferably in an aqueous or aqueous-alcoholic cosmetic carrier. This cosmetic carrier can be a liquid, gel or cream. Pasty, solid or powdery cosmetic carriers can also be used to prepare agent (a). For hair treatment, especially hair coloring, such carriers are, for example, creams, emulsions, gels or surfactant-containing foam solutions, such as shampoos, foam aerosols, foam compositions or other preparations suitable for application to hair.

[0025] Preferably, the cosmetic carrier contains at least 2% by weight of water, based on its weight. More preferably, the water content is greater than 10% by weight, even more preferably greater than 20% by weight, and particularly preferably greater than 40% by weight. The cosmetic carrier may also be aqueous-alcoholic. An aqueous / alcoholic solution in the context of the present invention is an aqueous solution containing 2 to 70% by weight of a C1-C4 alcohol, more particularly ethanol or isopropanol. The agent may further contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol, or 1,2-propylene glycol. Preferably, all of these organic solvents are water-soluble.

[0026] <Organosilicon compounds from the silane group (a1)> As component (a1) essential to the present invention, agent (a) comprises at least one organosilicon compound from the group of silanes containing one, two or three silicon atoms.

[0027] Particularly preferably, the agent (a) comprises at least one organosilicon compound (a1) selected from silanes containing one, two or three silicon atoms, said organosilicon compound containing one or more hydroxyl and / or hydrolyzable groups per molecule.

[0028] These organosilicon compounds (a1) or organosilanes contained in the agent (a) are reactive compounds.

[0029] Organosilicon compounds, also known as organosilicon compounds, are compounds having a direct silicon-carbon bond (Si-C) or a compound in which carbon is bonded to a silicon atom via an oxygen, nitrogen, or sulfur atom. The organosilicon compounds of the present invention are compounds containing 1 to 3 silicon atoms. The organosilicon compounds preferably contain 1 or 2 silicon atoms.

[0030] According to the IUPAC method, the term "silane chemical compound" is based on a silicon skeleton and hydrogen. In organosilanes, all or some of the hydrogen atoms are replaced by organic groups such as (substituted) alkyl and / or alkoxy groups. In organosilanes, some of the hydrogen atoms may be replaced by hydroxyl groups.

[0031] In a particularly preferred embodiment, the method comprises applying to the keratinous material an agent (a), said agent (a) comprising at least one organosilicon compound (a1) selected from silanes containing one, two or three silicon atoms, said organosilicon compound further comprising one or more hydroxyl or hydrolyzable groups per molecule.

[0032] In a very particularly preferred embodiment, the method comprises applying an agent (a) to the keratinous material, said agent (a) comprising at least one organosilicon compound (a1) selected from silanes containing one, two or three silicon atoms, said organosilicon compound further comprising one or more basic chemical functional groups and one or more hydroxyl or hydrolyzable groups per molecule.

[0033] The basic group or basic chemical functionality may be, for example, an amino group, an alkylamino group, a dialkylamino group, or a trialkylamino 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.

[0034] 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 comprises the structural unit R'R''R'''Si-O-CH2-CH3. The groups R', R'' and R''' represent the three remaining free valences of the silicon atom.

[0035] A very particularly preferred method is characterized in that agent (a) comprises at least one organosilicon compound selected from silanes having one, two or three silicon atoms, said organosilicon compound preferably comprising one or more basic chemical functional groups and one or more hydroxyl or hydrolyzable groups per molecule.

[0036] In particular, good results have been obtained when the agent (a) comprises at least one organosilicon compound (a1) of formula (I) and / or (II).

[0037] The compounds represented by formulas (I) and (II) are organosilicon compounds selected from silanes having one, two or three silicon atoms, said organosilicon compounds containing one or more hydroxyl and / or hydrolyzable groups per molecule.

[0038] In another very particularly preferred embodiment, the method comprises applying an agent to keratinous materials (or human hair), the agent (a) being of formula (I) and / or (II): TIFF0007719088000001.tif10161[In the formula, -R1 and R2 independently represent a hydrogen atom or a C1-C6 alkyl group; -L is a straight or branched chain divalent C-C 20 is an alkylene group, -R3 is a hydrogen atom or a C1-C6 alkyl group; -R4 represents a C1-C6 alkyl group; -a represents an integer from 1 to 3, -b represents the integer 3-a] TIFF0007719088000002.tif10161[In the formula, -R5, R 5' , R 5'' each independently represents a hydrogen atom or a C1-C6 alkyl group; -R6, R 6' and R 6'' each independently represents a C1-C6 alkyl group; -A, A', A'', A''', and A'''' are independently straight or branched chain divalent C-C 20 represents an alkylene group, R7 and R8 are independently a hydrogen atom, a C1-C6 alkyl group, a hydroxy C1-C6 alkyl group, a C2-C6 alkenyl group, an amino C1-C6 alkyl group, or a group of formula (III): TIFF0007719088000003.tif10161[In the formula, -c represents an integer from 1 to 3, -d represents the integer 3-c, -c' represents an integer of 1 to 3, -d' represents the integer 3-c', -c'' represents an integer from 1 to 3, -d'' represents the integer 3-c''; -e represents 0 or 1, -f represents 0 or 1, -g represents 0 or 1, -h represents 0 or 1, - provided that at least one of the groups e, f, g and h is different from 0] represents a group represented by the formula: The present invention is characterized in that it contains at least one organosilicon compound (a) represented by the following formula:

[0039] The substituents R1, R2, R3, R4, R5, R in the compounds of formula (I) and (II) 5' , R 5'' , R6, R 6' , R 6'' , R7, R8, L, A, A', A'', A''', and A'''' are described below as examples. Examples of C1-C6 alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, and t-butyl, as well as n-pentyl and n-hexyl groups. Propyl, ethyl, and methyl are preferred alkyl groups. Examples of C2-C6 alkenyl groups include vinyl, allyl, but-2-enyl, but-3-enyl, and isobutenyl, with vinyl and allyl being preferred C2-C6 alkenyl groups. Preferred examples of hydroxy C1-C6 alkyl groups include 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 include aminomethyl, 2-aminoethyl, and 3-aminopropyl groups. The 2-aminoethyl group is particularly preferred. A linear divalent C1-C 20 Examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), propylene (-CH2-CH2-CH2-), and butylene (-CH2-CH2-CH2-CH2-). The propylene group (-CH2-CH2-CH2-) is particularly preferred. Due to the chain length of three C 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-).

[0040] Formula (I): In the organosilicon compound represented by TIFF0007719088000004.tif10161, the groups R1 and R2 independently represent a hydrogen atom or a C1-C6 alkyl group. Highly preferably, the groups R1 and R2 both represent a hydrogen atom.

[0041] The central part of the organosilicon compound is the structural unit or linker -L-, which is a linear or branched divalent C-C 20 Represents an alkylene group.

[0042] Divalent C1-C 20The alkylene group may alternatively be a divalent or double bonded C-C 20 They are sometimes referred to as alkylene groups, which means that each L group can form two bonds: one bond from the amino group R1R2N to the linker L, and the second bond between the linker L and the silicon atom.

[0043] Preferably, -L- is a C-C linear double bond (i.e., divalent). 20 It represents an alkylene group. More preferably, -L- represents a straight-chain divalent C1-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 group (-CH2-CH2-CH2-CH2-). In particular, L represents a propylene group (-CH2-CH2-CH2-).

[0044] A straight chain propylene group (-CH2-CH2-CH2-) may alternatively be referred to as a propane-1,3-diyl group.

[0045] Formula (I): The organosilicon compound represented by TIFF0007719088000005.tif10161 has a silicon-containing group -Si(OR3) at each end. a (R4) b It has.

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

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

[0048] Particularly resistant films can be produced when the agent (a) comprises at least one organosilicon compound (a1) of formula (I) in which the radicals R3, R4 independently represent methyl or ethyl radicals.

[0049] When using the method for dyeing keratin materials, dyeings with the best washfastness can also be obtained when agent (a) comprises at least one organosilicon compound of formula (I) in which the radicals R3, R4, independently of one another, represent a methyl or ethyl radical.

[0050] Furthermore, dyeings with the best washing fastness properties can be obtained when agent (a) comprises at least one organosilicon compound of formula (I) in which a represents the number 3. In this case, b represents the number 0.

[0051] In a further preferred embodiment, the agent (a) used in the process is characterized in that it comprises at least one organosilicon compound (a1) of formula (I), in which: R3 and R4 each independently represent a methyl group or an ethyl group; -a represents the number 3, -b represents the number 0.

[0052] In another preferred embodiment, the method comprises the step of: TIFF0007719088000006.tif10161[In the formula, -R1 and R2 both represent hydrogen atoms; -L represents a linear divalent C1-C6 alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or an ethylene group (-CH2-CH2-), -R3 represents a hydrogen atom, an ethyl group, or a methyl group; -R4 represents a methyl group or an ethyl group; -a represents the number 3, -b represents the number 0] The composition is characterized by containing at least one organosilicon compound (a1) represented by the following formula:

[0053] Organosilicon compounds of formula (I) which are particularly suitable for solving the problems according to the invention are: - (3-aminopropyl)triethoxysilane TIFF0007719088000007.tif3065- (3-Aminopropyl)trimethoxysilane TIFF0007719088000008.tif3058- 1-(3-aminopropyl)silanetriol TIFF0007719088000009.tif1442- (2-aminoethyl)triethoxysilane TIFF0007719088000010.tif3057- (2-Aminoethyl)trimethoxysilane TIFF0007719088000011.tif3050- 1-(2-aminoethyl)silanetriol TIFF0007719088000012.tif1436- (3-Dimethylaminopropyl)triethoxysilane TIFF0007719088000013.tif3067- (3-Dimethylaminopropyl)trimethoxysilane TIFF0007719088000014.tif3059- 1-(3-dimethylaminopropyl)silanetriol TIFF0007719088000015.tif2057- (2-Dimethylaminoethyl)triethoxysilane TIFF0007719088000016.tif3058- (2-Dimethylaminoethyl)trimethoxysilane and TIFF0007719088000017.tif3050- 1-(2-dimethylaminoethyl)silanetriol The file is TIFF0007719088000018.tif2549.

[0054] In a further preferred embodiment, the method further comprises the step of: - (3-aminopropyl)triethoxysilane - (3-aminopropyl)trimethoxysilane - 1-(3-aminopropyl)silanetriol - (2-aminoethyl)triethoxysilane - (2-aminoethyl)trimethoxysilane - 1-(2-aminoethyl)silanetriol - (3-Dimethylaminopropyl)triethoxysilane - (3-Dimethylaminopropyl)trimethoxysilane - 1-(3-dimethylaminopropyl)silanetriol - (2-Dimethylaminoethyl)triethoxysilane (2-dimethylaminoethyl)trimethoxysilane and / or - 1-(2-dimethylaminoethyl)silanetriol The composition is characterized by containing at least one organosilicon compound (a1) selected from the group consisting of:

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

[0056] In a further embodiment, the agent has formula (II): It contains at least one organosilicon compound (a1) represented by TIFF0007719088000019.tif10161.

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

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

[0059] Two terminal structural units (RO) c (R6) d Si- and -Si(R 6' ) d' (OR 5' ) c' In the formula, the groups R5, R 5' , R 5'' are each independently a hydrogen atom or a C1-C6 alkyl group. 6' and R 6'' independently represent a C1-C6 alkyl group.

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

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

[0062] The dyes with the most stable films or the best washfastness could be obtained when the groups c and c' both represent the number 3. In this case, d and d' both represent the number 0.

[0063] In another preferred embodiment, the method comprises the step of: TIFF0007719088000020.tif10161[In the formula, -R5 and R5' each independently represents a methyl group or an ethyl group; -c and c' together represent the number 3, -d and d' both represent the number 0] The present invention is characterized in that it contains at least one organosilicon compound (a1) represented by the following formula:

[0064] When c and c' are both the number 3 and d and d' are both the number 0, the organosilicon compounds of the present invention have the formula (IIa): Equivalent to TIFF0007719088000021.tif10161.

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

[0066] In this regard, the presence of certain atomic groups has proven to be particularly beneficial in terms of increasing cleaning performance. Particularly good results have been obtained when at least two of e, f, g and h represent the number 1. Very preferably, e and f together represent the number 1. Furthermore, g and h together represent the number 0.

[0067] When e and f both represent the number 1 and g and h both represent the number 0, the organosilicon compound in the present invention has the formula (IIb): Equivalent to TIFF0007719088000022.tif10161.

[0068] The groups A, A', A'', A''' and A'''' are independently linear or divalent C-C 20Preferably, the groups A, A', A'', A''', and A'''' are each independently a linear divalent C-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. Particularly preferably, 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-). Very preferably, the groups A, A', A'', A''' and A'''' represent a propylene group (-CH2-CH2-CH2-).

[0069] Divalent C1-C 20 The alkylene group may alternatively be a divalent or divalent C-C 20 They are sometimes referred to as alkylene groups, which means that each of the atomic groups A, A', A'', A''', and A'''' can form two bonds.

[0070] A straight chain propylene group (-CH2-CH2-CH2-) may alternatively be referred to as a propane-1,3-diyl group.

[0071] When the group f represents the number 1, the organosilicon compound of formula (II) comprises the structural group -[NR7-(A')]-.

[0072] When the group h represents the number 1, the organosilicon compound of formula (II) comprises the structural group -[NR8-(A''')]-.

[0073] wherein the groups 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 represented by formula (III): Represents the group shown in TIFF0007719088000023.tif10161.

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

[0075] When the group f represents the number 1 and the group h represents the number 0, the organosilicon compound contains the atomic group [NR7-(A')] but does not contain the atomic group [NR8-(A''')]. When the group R7 represents exactly the atomic group shown in formula (III), the agent (a) contains an organosilicon compound having three reactive silane groups.

[0076] In another preferred embodiment, the method comprises the step of: JPEG0007719088000024.jpg10161[In the formula, - e and f together represent the number 1, - g and h together 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 represented by formula (III). The composition is characterized by containing at least one organosilicon compound (a1) represented by the following formula:

[0077] In a further preferred embodiment, the method comprises the step of: [In the formula, - e and f together represent the number 1, - g and h together represent the number 0, -A and A' each independently represent a methylene group (-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 represented by formula (III). The present invention is characterized in that it contains at least one organosilicon compound represented by the formula:

[0078] Organosilicon compounds of formula (II) suitable for solving the problem according to the present invention are: - 3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007719088000025.tif39113- 3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007719088000026.tif45130- N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007719088000027.tif39113- N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007719088000028.tif45130- 2-[bis[3-(trimethoxysilyl)propyl]amino]ethanol TIFF0007719088000029.tif47113- 2-[bis[3-(triethoxysilyl)propyl]amino]ethanol TIFF0007719088000030.tif53130- 3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007719088000031.tif60113- 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007719088000032.tif63126- N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine TIFF0007719088000033.tif48113- N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine TIFF0007719088000034.tif54130- N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine TIFF0007719088000035.tif45113- N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The file is TIFF0007719088000036.tif51130.

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

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

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

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

[0083] 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine, which has the CAS number 18784-74-2, can be purchased, for example, from Fluorochem or Sigma-Aldrich.

[0084] In a further preferred embodiment, the method comprises the step of: - 3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine - 3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine - N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine - N-methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine - 2-[bis[3-(trimethoxysilyl)propyl]amino]ethanol - 2-[bis[3-(triethoxysilyl)propyl]amino]ethanol - 3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine - 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine - N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine - N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine, and / or - N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The composition is characterized by containing at least one organosilicon compound (a1) selected from the group consisting of:

[0085] In further tests, in particular dyeing tests, it has been found that the agent (a) applied to the keratin material in the process has the formula (IV): It has also been found to be particularly advantageous if the composition contains at least one organosilicon compound of the type shown in TIFF0007719088000037.tif10161.

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

[0087] Formula (IV): TIFF0007719088000038.tif10161[In the formula, -R9 is C1-C 18represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The organosilicon compounds represented by the formula: are also called silanes of the alkyl-alkoxy-silane or alkyl-hydroxy-silane type.

[0088] In a further preferred embodiment, the method comprises: The agent (a) is represented by the formula (IV): TIFF0007719088000039.tif10161[In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The composition is characterized by containing at least one organosilicon compound (a1) represented by the following formula:

[0089] In a further preferred embodiment, the method comprises the step of: (a) adding, in addition to the organosilicon compound or compounds of formula (I), a compound of formula (IV): TIFF0007719088000040.tif10161[In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The present invention is characterized in that it contains at least one further organosilicon compound represented by the formula:

[0090] In a further preferred embodiment, the method comprises the step of: (a) adding, in addition to the organosilicon compound or compound of formula (II), a compound of formula (IV): TIFF0007719088000041.tif10161[In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The present invention is characterized in that it contains at least one further organosilicon compound represented by the formula:

[0091] In a further preferred embodiment, the method comprises the step of: (a) adding, in addition to the organosilicon compound or compounds of formula (I) and / or (II), a compound of formula (IV): TIFF0007719088000042.tif10161[In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The present invention is characterized in that it contains at least one further organosilicon compound represented by the formula:

[0092] In the organosilicon compound of formula (IV), the group R9 is C1-C 18 This C1-C alkyl group 18 The alkyl group is saturated and can be linear or branched. Preferably, R is a linear C-C 18R9 represents an alkyl group. Preferably, R9 represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, or an n-octadecyl group. Particularly preferably, R9 represents a methyl group, an ethyl group, an n-hexyl group, or an n-octyl group.

[0093] In the organosilicon compound of formula (IV), the group R 10 represents a hydrogen atom or a C1-C6 alkyl group. Particularly preferably, R 10 represents a methyl group or an ethyl group.

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

[0095] Furthermore, k represents an integer from 1 to 3, and m represents the integer 3-k. When k represents the number 3, m is equal to 0. When k represents the number 2, m is equal to 1. When k represents the number 1, m is equal to 2.

[0096] When an agent (a) containing at least one organosilicon compound (a1) corresponding to formula (IV) is used in the process, where the radical k is the number 3, particularly stable films are obtained, i.e. dyeings with particularly good washfastness properties. In this case, the radical m is the number 0.

[0097] Organosilicon compounds of formula (IV) that are particularly suitable for solving the problem according to the invention are - Methyltrimethoxysilane TIFF0007719088000043.tif3430- Methyltriethoxysilane TIFF0007719088000044.tif4139- Ethyltrimethoxysilane TIFF0007719088000045.tif3439- Ethyltriethoxysilane TIFF0007719088000046.tif4147- n-Hexyltrimethoxysilane TIFF0007719088000047.tif3475- n-Hexyltriethoxysilane TIFF0007719088000048.tif4184- n-Octyltrimethoxysilane TIFF0007719088000049.tif3494- n-Octyltriethoxysilane TIFF0007719088000050.tif41102- n-Dodecyltrimethoxysilane, and / or TIFF0007719088000051.tif34130- n-Dodecyltriethoxysilane TIFF0007719088000052.tif43140n-octadecyltrimethoxysilane and / or n-octadecyltriethoxysilane.

[0098] In another preferred embodiment, the method comprises the step of: -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Propyltrimethoxysilane -Propyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -Dodecyltrimethoxysilane -Dodecyltriethoxysilane -Octadecyltrimethoxysilane -Octadecyltriethoxysilane The composition is characterized by containing at least one organosilicon compound (a1) represented by formula (IV) selected from the group consisting of:

[0099] The organosilicon compounds are reactive compounds. In this regard, it has been found to be advantageous if agent (a) comprises one or more organosilicon compounds (a1) in a total amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 8% by weight, based on the total weight of agent (a).

[0100] In a further preferred embodiment, the method is characterized in that the agent (a) comprises one or more organosilicon compounds (a1) in a total amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 8% by weight, based on the total weight of the agent (a).

[0101] To obtain particularly good dyeing results, it is particularly advantageous to use organosilicon compounds of formula (I) and / or (II) in agent (a) in specific ranges of amounts. Particularly preferably, agent (a) contains one or more organosilicon compounds of formula (I) and / or (II) in a total amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the total weight of agent (a).

[0102] In a further preferred embodiment, the method is characterized in that the agent (a) comprises one or more organosilicon compounds of formula (I) and / or (II) in a total amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the total weight of agent (a).

[0103] Furthermore, it has also proven particularly advantageous when the organosilicon compounds of formula (IV) are present in agent (a) in a specific range of amounts. Particularly preferably, agent (a) contains one or more organosilicon compounds of formula (IV) in a total amount of 0.1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 4 to 9% by weight, based on the total weight of agent (a).

[0104] In a further preferred embodiment, the method is characterized in that agent (a) comprises one or more organosilicon compounds of formula (IV) in a total amount of 0.1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3.2 to 10% by weight, based on the total weight of agent (a).

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

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

[0107] In a preferred embodiment, the method is characterized in that an agent (a) comprising at least one organosilicon compound of formula (I) and at least one organosilicon compound of formula (IV) is applied to keratinous materials.

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

[0109] In a further preferred embodiment, the method comprises the step of: - 0.5 to 5% by weight of at least one first organosilicon compound (a1) selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane and (2-dimethylaminoethyl)triethoxysilane, and - 3.2 to 10% by weight of at least one second organosilicon compound (a1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane The present invention is characterized by comprising:

[0110] In this embodiment, agent (a) contains 0.5 to 3 wt.% total of one or more first group organosilicon compounds selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane, and / or (2-dimethylaminoethyl)triethoxysilane.

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

[0112] For organosilicon compounds having at least one hydrolyzable group, even the addition of a small amount of water will cause hydrolysis.This hydrolysis product and / or the organosilicon compound having at least one hydroxyl group can react with each other in a condensation reaction.Therefore, 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).

[0113] Condensation products are understood to be products formed by the reaction of at least two or more organosilicon compounds, each having at least one hydroxyl group or hydrolyzable group per molecule, with the elimination of water and / or alkanol. The condensation products may be, for example, dimers, trimers, or oligomers, with the condensation products in equilibrium with the monomers. Depending on the amount of water used or consumed in the hydrolysis, the equilibrium shifts from the monomeric organosilicon compounds to the condensation products.

[0114] Particularly good results were obtained when organosilicon compounds represented by formula (I) and / or (II) were used in this method. As already mentioned above, since hydrolysis / condensation begins even with a trace amount of water, the hydrolysis products and / or condensation products of organosilicon compounds (I) and / or (II) are also included in this embodiment.

[0115] <First colorant compound containing at least one lenticular substrate platelet pigment (a2)> When applying agent (a) to keratinous materials, an organosilicon compound (a1), preferably containing one or more hydroxyl or hydrolyzable groups per molecule, is first hydrolyzed in the presence of water and oligomerized or polymerized. The hydrolysis product or oligomer thus formed has a particularly high affinity for the surface of keratinous materials. If colorant compounds are also present in agent (a), they are incorporated into the resulting oligomer or polymer, forming a colored film. Following the application of agent (a), agent (b) is applied, whereby the sealing agent contained in agent (b) seals the colored film. The sequential application of agents (a) and (b) results in a color that is particularly resistant to external influences.

[0116] As an essential component (a2) of the present invention, the agent (a) used in the dyeing method comprises a first colorant compound comprising at least one pigment based on the lenticular substrate platelet.

[0117] The substrate platelets have an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred ranges for the thickness of the substrate platelets are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm, and 10 to 20 nm. Preferably, each substrate plate has as uniform a thickness as possible.

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

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

[0120] The size of the substrate platelets can be adapted to the respective application purpose, in particular 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.

[0121] In preferred designs, the aspect ratio, expressed by 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 platelets is the d50 value of the uncoated substrate platelets. Unless otherwise noted, the d50 values were measured using a Sympatec Helos instrument using a Quixel wet dispersion. For sample preparation, the sample to be analyzed was pre-dispersed in isopropanol for 3 minutes.

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

[0123] They may be naturally occurring or synthetically produced. Materials from which the substrate platelets can be made include metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi)precious stones, and plastics. Preferably, the substrate platelets are made of metal (alloys).

[0124] Any metal suitable for metallic luster pigments can be used.Such metals include iron and steel, as well as all air-resistant and water-resistant (semi)metals such as platinum, zinc, chromium, molybdenum and silicon, and their alloys such as aluminum bronze and brass.Preferred metals are aluminum, copper, silver and gold.Preferred substrate platelets include aluminum platelets and brass platelets, and aluminum substrate platelets are particularly preferred.

[0125] Lenticular substrate platelets have essentially regular rounded edges, giving them the appearance of being called "silver dollars." Due to their regular structure, pigments based on lenticular substrate platelets have a predominant proportion of reflected light.

[0126] The metal or metal alloy substrate plate may be passivated, for example, by anodizing (oxide layer) or chromate treatment.

[0127] Uncoated lenticular substrate platelets, especially those made of metal or metal alloys, reflect a high proportion of the incident light, resulting in a light-dark flop but no color impression.

[0128] The color impression can be produced, for example, by light interference effects. Such pigments can be based on at least a single coated substrate platelet. They exhibit interference effects due to the superposition of different refracted and reflected light rays.

[0129] Therefore, a preferred pigment is based on a coated lenticular substrate platelet. The substrate platelet preferably has at least one coating B of a high refractive index metal oxide with a coating thickness of at least 50 nm. Preferably, another coating A is present between coating B and the surface of the substrate platelet. If necessary, a further coating C, different from the layer B immediately below, is present on layer B.

[0130] Suitable materials for coatings A, B, and C are all substances that can be applied to the substrate platelet in a permanent manner, such as a film, and that, in the case of coatings A and B, have the required optical properties. Generally, to obtain a pigment with a glossy effect, it is sufficient to coat only a portion of the surface of the substrate platelet. For example, only the upper and / or lower surfaces of the substrate platelet may be coated, while the side surfaces may be omitted. Preferably, the entire surface of the optionally passivated substrate platelet, including the side surfaces, is covered with coating B. Thus, the substrate platelet is completely covered with coating B. This improves the optical properties of the pigment and its mechanical and chemical resistance. The above also applies to layer A and, preferably, layer C, if present.

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

[0132] Coating B is composed of at least one highly refractive metal oxide. The highly refractive material has a refractive index of at least 1.9, preferably at least 2.0, more preferably at least 2.4. Preferably, Coating B comprises at least 95% by weight, more preferably at least 99% by weight, of the highly refractive metal oxide.

[0133] 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.

[0134] Suitable high refractive index metal oxides 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 index oxides such as titanium dioxide and / or zirconium oxide are also suitable.

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

[0136] Coating A preferably comprises at least one low refractive index metal oxide and / or metal oxide hydrate. Preferably, Coating A comprises at least 95% by weight, more preferably at least 99% by weight, of a low refractive index metal oxide (hydrate). The low refractive index material has a refractive index of 1.8 or less, preferably 1.6 or less.

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

[0138] Particularly preferred pigments based on lenticular substrate flakes comprise, in addition to lenticular substrate flakes made of aluminum, only one coating A made of silicon dioxide.

[0139] Preferably, the distance between the surface of the substrate platelet and the inner surface of Coating B is at most 100 nm, particularly preferably at most 50 nm, and especially preferably at most 20 nm. By arranging the thickness of Coating A and the distance between the surface of the substrate platelet and Coating B within the ranges specified above, it is therefore possible to ensure that the pigment has high hiding power.

[0140] When the pigment based on a lenticular substrate platelet has only one layer A, it is preferred that the pigment has an aluminum lenticular substrate platelet and a silica layer A. When the pigment based on a lenticular substrate platelet has a layer A and a layer B, it is preferred that the pigment has an aluminum lenticular substrate platelet, a silica layer A and an iron oxide layer B.

[0141] Instead of a metal oxide, layer B may comprise a metal particle-carrying layer on the surface of which metal particles are vapor-deposited. In a preferred embodiment, the metal particles directly cover part of the metal particle-carrying layer. In this embodiment, the effect pigment has areas where no metal particles are present, i.e. areas that are not covered by metal particles.

[0142] The metal particle support layer includes a metal layer and / or a metal oxide layer.

[0143] When the metal particle support layer includes a metal layer and a metal oxide layer, the arrangement of these layers is not particularly limited.

[0144] The metal particle support layer preferably includes at least a metal layer, and more preferably the metal layer includes an element selected from tin (Sn), palladium (Pd), platinum (Pt), and gold (Au).

[0145] The metal layer can be formed, for example, by adding an alkali to a metal salt solution containing the metal.

[0146] When the metal particle support layer includes a metal oxide layer, it preferably does not contain silicon dioxide. The metal oxide layer preferably contains an oxide of at least one element selected from the group consisting of Mg (magnesium), Sn (tin), Zn (zinc), Co (cobalt), Ni (nickel), Fe (iron), Zr (zirconium), Ti (titanium) and Ce (cerium). Particularly preferably, the metal particle support layer iii) in the form of a metal oxide layer contains metal oxides of Sn, Zn, Ti and Ce.

[0147] A metal particle-supported layer in the form of a metal oxide layer can be produced, for example, by hydrolyzing an alkoxide of a metal that forms the metal of the metal oxide by a sol-gel method.

[0148] The thickness of the metal layer is preferably 30 nm or less.

[0149] The metal particles may contain at least one element selected from the group consisting of aluminum (Al), titanium (Ti), chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), gold (Au), and alloys thereof. It is particularly preferred that the metal particles contain at least one element selected from copper (Cu), nickel (Ni), and silver (Ag).

[0150] The average particle size of the metal particles is preferably 50 nm or less, more preferably 30 nm or less, and the distance between the metal particles is preferably 10 nm or less.

[0151] Suitable methods for forming metal particles include vacuum deposition, sputtering, chemical vapor deposition (CVD), electroless plating, etc. Of these methods, electroless plating is particularly preferred.

[0152] According to a preferred embodiment, the pigment further comprises a coating C of a metal oxide (hydrate) different from the underlying 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.

[0153] According to a preferred embodiment, the pigment further comprises a coating C of a metal oxide (hydrate) different from the underlying 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.

[0154] Coating C preferably has a thickness of 10 to 500 nm, more preferably 50 to 300 nm. For example, by providing coating C based on TiO2, better interference can be achieved while maintaining high hiding power.

[0155] Layers A and C serve, inter alia, to provide corrosion protection and chemical and physical stabilization. Particularly preferred layers A and C are silicon dioxide or alumina applied by a sol-gel process. This method involves dispersing an uncoated lenticular substrate platelet or a lenticular 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 an organic solvent or a mixture of organic solvent and water containing at least 50% by weight of an organic solvent such as a C1-C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, thereby forming a film of metal oxide on the surface of the (coated) substrate platelet.

[0156] Layer B can be produced, for example, by hydrolysis of one or more organometallic compounds and / or precipitation 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).

[0157] Coatings A, B and / or C may each be composed of a mixture of two or more metal oxides (hydrates), although each coating is preferably composed of one metal oxide (hydrate).

[0158] Pigments based on coated lenticular 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 platelet, the pigment exhibits particularly high hiding power. The low thickness of the coated substrate platelet is achieved in particular by keeping the thickness of the uncoated substrate platelet low, 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 impression of the pigment.

[0159] The adhesion and abrasion resistance of pigments based on coated lenticular substrate platelets on keratin materials can be significantly improved by further modifying the outermost layer, layer A, B, or C, depending on the structure, with organic compounds such as silanes, phosphate esters, titanates, borates, or carboxylic acids. In this case, the organic compounds are bonded to the surface of the outermost layer, preferably the metal oxide-containing layer A, B, or C. The outermost layer refers to the layer spatially furthest from the lenticular substrate platelet. The organic compounds are preferably functional silane compounds capable of bonding to the metal oxide-containing layer A, B, or C. These can be monofunctional or bifunctional compounds. Examples of bifunctional organic compounds include methacryloxypropenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltriethoxysilane, 3-methacryloxypropyltris(methoxyethoxy)silane, 3-methacryloxypropyltris(butoxyethoxy)silane, 3-methacryloxypropyltris(butoxyethoxy)silane, and 3-methacryloxypropyltriethoxysilane. Examples of suitable silanes include pyritris(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, monofunctional silanes, particularly alkylsilanes or arylsilanes, can be used for modification. These silanes have only one functional group and can be covalently bonded to the surface pigments (i.e., to the outermost metal oxide-containing layer) of the coated lenticular substrate platelet, or to the metal surface if the substrate is not completely coated.The hydrocarbon residue of the silane faces away from the pigment. Depending on the type and nature of the hydrocarbon residue of the silane, various degrees of hydrophobicity of the pigment can be achieved. Examples of such silanes include hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Particularly preferred are pigments based on silane-coated aluminum substrate platelets surface-modified with monofunctional silanes. Octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane are particularly preferred. The altered surface properties / hydrophobicity result in improved adhesion, abrasion resistance, and orientation during application.

[0160] Pigments based on lenticular substrate platelets with such surface modifications have also been shown to exhibit better compatibility with the organosilicon compounds and / or their condensation or polymerization products used.

[0161] Particularly good results have been obtained when agent (a) comprises one or more pigments based on the lenticular substrate platelet in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, and very preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0162] Pigments based on lenticular substrate platelets are available, for example, from Schlenk Metallic Pigments GmbH.

[0163] Due to their regular structure, dyeings with pigments based on lenticular substrate platelets exhibit high fastness to rubbing and washing and provide optimal grey coverage.

[0164] <Second Colorant Compound (a3)> As a third component essential to the present invention, agent (a) comprises a second colorant compound (a3), which is preferably selected from the group of pigments.

[0165] In a preferred embodiment, the method is characterized in that the agent (a) comprises at least one second colorant compound (a3) from the group of the pigments.

[0166] A pigment within the meaning of the present invention is a colorant compound having a solubility in water at 25°C of less than 0.5 g / L, preferably less than 0.1 g / L, and even more preferably less than 0.05 g / L. Water solubility can be measured, for example, by the following method: 0.5 g of pigment is weighed into a beaker. A beaker glass is added. 1 liter of distilled water is then added. The mixture is heated to 25°C for 1 hour while stirring on a magnetic stirrer. If undissolved pigment components are still visible in the mixture after this time, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be visually evaluated due to the high intensity of the pigment, which may be finely dispersed, the mixture is filtered. If some undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0167] Suitable color pigments can be of inorganic and / or organic origin.

[0168] In a preferred embodiment, the method is characterized in that the agent (a) comprises at least one second colorant compound (a3) from the group of inorganic and / or organic pigments.

[0169] Preferred color pigments are selected from synthetic or natural inorganic pigments. Naturally occurring inorganic color pigments can be produced, for example, from chalk, ochre, umber, green earth, calcined Siena or graphite. In addition, black pigments such as black iron oxide, colored pigments such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments can be used as inorganic color pigments.

[0170] Particularly suitable are colored metal oxides, metal hydroxides and metal oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and / or molybdates. Particularly preferred colored pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, pigment blue 29), chromium oxide hydrate (CI 77289), Prussian blue (iron ferrocyanide, CI 77510) and / or carmine (cochineal).

[0171] Also, the second colorant compound from the group of particularly preferred pigments according to the present invention is a colored pearlescent pigment. These are usually mica and / or mica-based and may be coated with one or more metal oxides. Micas belong to the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. To produce pearlescent pigments combined with metal oxides, mica, mainly muscovite or phlogopite, is coated with the metal oxide.

[0172] As an alternative to natural mica, synthetic mica coated with one or more metal oxides can also be used as pearlescent pigments. Particularly preferred pearlescent pigments are based on natural or synthetic mica and coated with one or more of the above-mentioned metal oxides. By varying the thickness of the metal oxide layer, the color of each pigment can be changed.

[0173] Also preferred mica pigments are synthetically produced mica platelets coated with metal oxides, particularly synthetic fluorphlogopite (INCI). The synthetic fluorphlogopite platelets are coated with, for example, tin oxide, iron oxide, and / or titanium dioxide. The metal oxide layer can also contain pigments such as iron(II / III) hexacyanide or carmine red. Such mica pigments are available, for example, from Eckart under the name SYNCRYSTAL.

[0174] In a very particularly preferred embodiment, the invention is characterized in that the agent (a) comprises as second coloring compound (a3) at least one inorganic pigment, which is preferably selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or from colored mica-based or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0175] In a further preferred embodiment, the invention is characterized in that the agent (a) comprises at least one second colorant compound (a3) selected from mica or mica-based pigments reacted with one or more metal oxides selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron 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 Prussian blue (iron ferrocyanide, CI 77510).

[0176] Examples of particularly suitable color pigments are commercially available from Merck under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron®, from Sensient under the trade names Ariabel® and Unipure®, from Eckart Cosmetic Colors under the trade names Prestige® and SynCrystal, and from Sunstar under the trade name Sunshine®.

[0177] Particularly preferred color pigments under the trade name Colorona® are, for example: Colorona Copper, Merck, Mica, CI 77491 (Iron Oxides) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxide), Alumina Colorona Patina Silver, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona RY, Merck, CI 77891 (Titanium Dioxide), Mica, CI 75470 (Carmine) Colorona Oriental Beige, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Dark Blue, Merck, mica, titanium dioxide, ferric ferrocyanide Colorona Chameleon, Merck, CI 77491 (iron oxide), mica Colorona Aboriginal Amber, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Blackstar Blue, Merck, CI 77499 (iron oxide), mica Colorona Patagonian Purple, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) Colorona Red Brown, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Russet, Merck, CI 77491 (Titanium Dioxide), Mica, CI 77891 (Iron Oxides) Colorona Imperial Red, Merck, Mica, Titanium Dioxide (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (Titanium Dioxide), Mica, CI 77288 (Chromium Oxide Green) Colorona Light Blue, Merck, Mica, Titanium Dioxide (CI 77891), Ferric Ferrocyanide (CI 77510) Colorona Red Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Gold Plus MP 25, Merck, Mica, Titanium Dioxide (CI 77891), Iron Oxide (CI 77491) Colorona Carmine Red, Merck, mica, titanium dioxide, carmine Colorona Blackstar Green, Merck, Mica, CI 77499 (Iron Oxides) Colorona Bordeaux, Merck, Mica, CI 77491 (Iron 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 oxide), 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 fluorogopite and iron oxide Colorona SynBronze, Merck, synthetic fluorogopite and iron oxide

[0178] Other particularly preferred color pigments under the trade name Xirona® are, for example: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Le Rouge, Merck, iron oxide (and) silica

[0179] Additionally, particularly preferred color pigments under the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensitive CI 77491 (iron oxide), Silica Unipure Black LC 989 EM, Sensitive, CI 77499 (Iron Oxide), Silica Unipure Yellow LC 182 EM, Sensitive, CI 77492 (Iron Oxide), Silica

[0180] Particularly preferred pigments under the trade name Flamenco (registered trademark) are, for example: Flamenco® Summit Turquoise T30D, BASF, titanium dioxide and mica Flamenco® Super Violet 530Z, BASF, mica and titanium dioxide

[0181] In a further embodiment, agent (a) may comprise, as second colorant compound (a3), one or more colorant compounds from the group of the organic pigments.

[0182] Organic pigments are correspondingly insoluble organic dyes or colorants which may be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketo-pyrrolopyrrole, indigo, thioindigo, dioxazine and / or triarylmethane compounds.

[0183] Examples of particularly suitable organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a color index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a color index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a color index of CI 61565, CI 61570, CI 74260, orange pigments with a color index of CI 11725, CI 15510, CI 45370, CI 71105, and 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 1220 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470 red pigments.

[0184] In another particularly preferred embodiment, the method comprises the step of: the agent (a) containing as second colored compound (a3) carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a Color Index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a Color Index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a Color Index of CI 61565, CI 61570, CI 74260, orange pigments with a Color Index of CI 11725, CI 15510, CI 45370, CI 71105, 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470 red pigments.

[0185] The organic pigment may be a color paint. In the sense of the present invention, the term "color lacquer" refers to particles comprising a layer of absorbed dye, and the particles and dye units are insoluble under the above conditions. The particles may be, for example, inorganic materials, such as aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or aluminum.

[0186] For example, alizarin color varnish can be used as the color varnish.

[0187] Furthermore, it is preferred if the pigment used as the second colorant compound (a3) has a specific particle size. On the one hand, this particle size results in a uniform distribution of the pigment in the formed polymer film, and on the other hand, it avoids a feeling of roughness on the hair or skin after application of the cosmetic agent (a). Therefore, according to the present invention, at least one pigment has an average particle size D of 1.0 to 50 μm, preferably 5.0 to 45 μm, preferably 10 to 40 μm, in particular 14 to 30 μm. 50 It is advantageous to have an average particle size D 50 can be measured, for example, using dynamic light scattering (DLS).

[0188] In a further preferred embodiment, the method is characterized in that agent (a) comprises second colorant compounds in the form of pigments in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, very particularly preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0189] Alternatively or in addition to a pigment, the second colorant compound (a3) may comprise a direct dye.

[0190] For example, it is preferred that agent (a) further comprises at least one colorant compound selected from the group consisting of direct dyes.

[0191] Direct dyes in the sense of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 0.5 g / L and are therefore not considered pigments. Preferably, direct dyes in the sense of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 1 g / L.

[0192] Direct dyes can be classified into anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

[0193] In another preferred embodiment, the method is characterized in that the agent (a) further comprises at least one anionic direct dye, cationic direct dye and / or non-ionic direct dye.

[0194] Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, Basic Violet 2, Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347 / Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51, and Basic Red 76.

[0195] As non-ionic direct dyes, non-ionic nitro and quinone dyes and natural azo dyes can be used. Suitable non-ionic direct dyes are those described under the following international names or trade names: HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black. 9 known compounds, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)-aminophenol, 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2 -nitrobenzene, 4-amino-3-nitrophenol, 1-(2'-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

[0196] Anionic direct dyes are also called acid dyes. Acid dyes are direct dyes that have at least one carboxylic acid group (-COOH) and / or at least one sulfonic acid group (-SO3H). Depending on the pH value, the protonated forms of the carboxylic acid or sulfonic acid groups (-COOH, -SO3H) are converted to their deprotonated forms (-COO - , -SO3 -The proportion of the protonated form increases with decreasing pH. When direct dyes are used in the form of their salts, the carboxylic or sulfonic acid groups are present in deprotonated form and neutralized with the corresponding stoichiometrically equivalent cation to maintain electrical neutrality. Acid dyes may also be used in the form of their sodium and / or potassium salts.

[0197] Acid dyes within the meaning of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 0.5 g / L and are therefore not considered pigments. Preferably, acid dyes within the meaning of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 1 g / L.

[0198] Alkaline earth salts (e.g., calcium and magnesium) or aluminum salts of acid dyes often have lower solubilities than the corresponding alkali salts. If the solubility of these salts is less than 0.5 g / L (25°C, 760 mmHg), they are not included in the definition of direct dyes.

[0199] An essential feature of acid dyes is their ability to form an anionic charge, the resulting carboxylic or sulfonic acid group usually being attached to a variety of chromophore systems. Suitable chromophore systems are found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthan dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.

[0200] 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, Japan Yellow 403, CI 10316, COLIPA n°B001), Acid Yellow 3 (COLIPA n°C 54, D&C Yellow No. 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n°C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA n°filmbilC015), Acid Orange 10 (CI 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1; CI 20170; KATSU201; sodium salt-free; Brown No. 201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D&C Brown No. 1), Acid Red 14(CI14720), Acid Red 18(E124, Red 18; CI 16255), Acid Red 27(E 123, CI 16185, C-Rot 46, Echtrot D, FD&C Red Nr.2、Food Red 9、Naphthol red S)、Acid Red 33(Red 33、Fuchsia Red、D&C Red 33、CI 17200)、Acid Red 35(CI C.I.18065)、Acid Red 51(CI 45430、Pyrosin B、Tetraiodfluorescein、Eosin J、Iodeosin)、Acid Red 52(CI 45100、Food Red 106、Solar Rhodamine B、Acid Rhodamine B、Red n°106 Pontacyl Brilliant Pink)、Acid Red 73(CI 27290)、Acid Red 87(Eosin、CI 45380)、Acid Red 92(COLIPA n°C 53、CI 45410)、Acid Red 95(CI 45425、Erythtosine,Simacid Erythrosine Y)、Acid Red 184(CI 15685)、Acid Red 195、Acid Violet 43(Jarocol Violet 43、Ext. D&C Violet n°2、C.I. 60730、COLIPA n°063)、Acid Violet 49(CI 42640)、Acid Violet 50(CI 50325)、Acid Blue 1(Patent Blue、CI 42045)、Acid Blue 3(Patent Blue V、CI 42051)、Acid Blue 7(CI 42080)、Acid Blue 104(CI 42735)、Acid Blue 9(E 133、Patent Blue AE、Amino blue AE、Erioglaucin A、CI 42090、C.I. Food Blue 2)、Acid Blue 62(CI 62045)、Acid Blue 74(E 132、CI 73015)、Acid Blue 80(CI 61585)、Acid Green 3(CI 42085、Foodgreen1)、Acid Green 5(CI 42095)、Acid Green 9(C.I.42100)、Acid Green 22(C.I.42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brilliant Acid Green BS, CI 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n°401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n°B15), Acid Black 52(CI 15711), Food Yellow 8(CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1. .

[0201] For example, the water solubility of an anionic direct dye can be measured as follows: Add 0.1 g of anionic direct dye to a beaker. Add a glass beaker. Then add 100 mL of water. Heat the mixture to 25°C while stirring on a magnetic stirrer. Stir for 60 minutes. The aqueous mixture is then visually evaluated. If undissolved residue is still present, increase the amount of water, for example, in 10 mL increments. Add water until the amount of dye used is completely dissolved. If the dye strength is too high to visually evaluate the dye-water mixture, filter the mixture. If some undissolved dye remains on the filter paper, repeat the solubility test with more water. If 0.1 g of anionic direct dye dissolves in 100 mL of water at 25°C, the solubility of the dye is 1 g / L.

[0202] Acid Yellow 1 is referred to as 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water (25° C.) of at least 40 g / L. Acid Yellow 3 is a mixture of the mono- and disulfonic acid sodium salts of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a solubility in water (25°C) of 20 g / L. Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, and its solubility in water is greater than 40 g / L (25°C). Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylic acid and is highly soluble in water at 25°C. Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonate. Its solubility in water is greater than 7 g / L at 25 °C. Acid Red 18 is the trisodium salt of 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonate and has very high water solubility of greater than 20% by weight. Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate, and its solubility in water is 2.5 g / L (25° C.). Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, and its solubility in water is greater than 10 g / L (25° C.). Acid Blue 9 is the disodium salt of 2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonate and has a solubility in water of greater than 20% by weight (25°C).

[0203] A very particularly preferred method is therefore characterized in that the agent (a) comprises as second colorant compound (a3) at least one colorant compound from the group of the anionic direct dyes selected from the group consisting of: Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1.

[0204] <pH value of agent (a)> It has proven to be preferable if agent (a) is constituted in the form of a hydrating agent adjusted to an alkaline pH.

[0205] To adjust the pH value, agent (a) may comprise at least one alkalizing agent.

[0206] To adjust the desired pH, agent (a) may therefore comprise at least one alkalizing agent. pH values for the purposes of the present invention are pH values measured at a temperature of 22°C.

[0207] As an alkalizing agent, agent (a) may include, for example, ammonia, alkanolamines and / or basic amino acids.

[0208] The alkanolamine that can be used in the composition is preferably selected from the primary amines having a C2-C6 alkyl backbone and 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.

[0209] Particularly preferred alkanolamines are selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol. Thus, a particularly preferred embodiment is characterized in that the agent comprises as alkalizing agent an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol.

[0210] For the purposes of the present invention, an amino acid is an organic compound containing at least one protic amino group and at least one -COOH or -SOH group in its structure. Preferred amino acids are aminocarboxylic acids, in particular α-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0211] Basic amino acids are those with an isoelectric point pI greater than 7.0.

[0212] 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 mixtures thereof, especially as racemates. However, it is particularly advantageous to use the originally preferred isomer (usually L-configuration).

[0213] The basic amino acid is preferably selected from the group formed by arginine, lysine, ornithine and histidine, particularly preferably arginine and lysine. In a further particularly preferred embodiment, the agent is therefore characterized in that the alkalizing agent is a basic amino acid selected from the group consisting of arginine, lysine, ornithine and / or histidine.

[0214] In addition, the product may contain other alkalizing agents, in particular inorganic alkalizing agents, which may be used according to the invention are preferably selected from the group formed by sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

[0215] 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.

[0216] Agent (a) is preferably adjusted to a pH value in the alkaline range, although it may nevertheless be necessary in principle to also use a small amount of an acidifying agent for fine-tuning the desired pH value. Suitable acidifying agents according to the invention are, for example, citric acid, lactic acid, acetic acid, or diluted mineral acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, etc.).

[0217] However, during the research leading to the present invention, it was found that the presence of an alkalizing agent or the adjustment of alkaline pH is essential for the formation of a durable film on keratinous materials. The presence of an excessive amount of acid can adversely affect the strength of the film. For this reason, it was found preferable to keep the amount of acid used in agent (a) as low as possible. For this reason, it is advantageous that the total amount of organic and / or inorganic acid contained in agent (a) does not exceed a certain value.

[0218] In a further preferred embodiment, the method is characterized in that the total amount of organic acids from the group consisting of citric acid, tartaric acid, malic acid and lactic acid contained in agent (a) is less than 1% by weight, preferably less than 0.7% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.1% by weight, and most preferably less than 0.01% by weight.

[0219] In a further preferred embodiment, the method is characterized in that the total amount of inorganic acids from the group consisting of hydrochloric acid, sulfuric acid and phosphoric acid contained in agent (a) is less than 1% by weight, preferably less than 0.7% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.1% by weight, very particularly preferably less than 0.01% by weight.

[0220] The maximum total amount of acid contained in agent (a) given above is always based on the total weight of agent (a).

[0221] <Agent (b)> The method for treating keratinous materials comprises, in addition to the application of agent (a), the application of agent (b), which agent (b) is characterized in that it contains at least one sealing agent (b1).

[0222] The agent (b) is a post-treatment agent, and applying the agent (b) to the keratin material treated with the agent (a) has the effect of prolonging the coloring obtained by the method. In particular, the use of the agent (b) can improve the wash fastness and rub fastness of the dyed product obtained by the method.

[0223] Preferably, the sealant comprises a compound selected from the group consisting of a film-forming polymer, an alkalizing agent, an acidifying agent, and mixtures thereof.

[0224] It may be preferred that the sealant comprises a film-forming polymer.

[0225] The polymer is a macromolecule having a molecular weight of at least 1000 g / mol, preferably at least 2500 g / mol, particularly preferably at least 5000 g / mol, and consisting of identical repeating organic units. The polymer of the present invention may be a synthetically produced polymer prepared by polymerizing one type of monomer, or a synthetically produced polymer prepared by polymerizing structurally different types of monomers. When a polymer is produced by polymerizing one type of monomer, the polymer is called a homopolymer. When structurally different types of monomers are polymerized, the resulting polymer is called a copolymer.

[0226] The maximum molecular weight of the polymer depends on the degree of polymerization (number of polymerized monomers) and the batch size, and is determined by the polymerization method. In the present invention, the maximum molecular weight of the film-forming polymer as the sealing agent (b1) is 10 7 g / mol or less, preferably 10 6 g / mol or less, particularly preferably 10 5 It is preferably g / mol or less.

[0227] 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 keratinous materials or keratinous fibers. Film formation can be demonstrated, for example, by observing the polymer-treated keratinous materials under a microscope.

[0228] The film-forming polymer (b1) in agent (b) can be hydrophilic or hydrophobic.

[0229] In a first embodiment, it may be preferable to use at least one hydrophobic film-forming polymer in agent (b).

[0230] A hydrophobic polymer is a polymer that has a solubility in water at 25° C. (760 mmHg) of less than 1% by weight.

[0231] For example, the water solubility of a film-forming, hydrophobic polymer can be measured by the following method: Place 1 g of polymer in a beaker. Bring to 100 g with water. Add a beaker glass and heat the mixture to 25°C while stirring on a magnetic stirrer. Stir for 60 minutes. Then visually assess the aqueous mixture. If the polymer-water mixture cannot be visually assessed due to the high turbidity of the mixture, filter the mixture. If some undissolved polymer remains on the filter paper, the solubility of the polymer is less than 1% by weight.

[0232] These include acrylic type polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose polymers, nitrocellulose polymers, silicone polymers, acrylamide type polymers, and polyisoprene.

[0233] Particularly suitable film-forming, hydrophobic polymers are, for example, polymers from the group of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and / or polyamides.

[0234] In a further preferred embodiment, the agent (b) is characterized in that it comprises as sealing agent (b1) at least one film-forming, hydrophobic polymer selected from the group consisting of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and / or polyamides.

[0235] 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.

[0236] Other particularly suitable film-forming hydrophobic polymers are cycloolefins, homopolymers or copolymers of olefins such as butadiene, isoprene or styrene, vinyl ethers, vinyl amides, at least one C-C 20 Alkyl, aryl or C2-C 10 It may be selected from esters or amides of (meth)acrylic acid having a hydroxyalkyl group.

[0237] Other film-forming hydrophobic polymers may be selected from homo- or copolymers of isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isopentyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and / or mixtures thereof.

[0238] Further film-forming hydrophobic polymers include (meth)acrylamides, N-alkyl-(meth)acrylamides, especially C-C 18 It may be selected from those having alkyl groups, such as homopolymers or copolymers of N-ethyl-acrylamide, N-tert-butylacrylamide, 1E-N-octylacrylamide, N-di(C1-C4)alkyl(meth)acrylamide, and the like.

[0239] Other preferred anionic copolymers are copolymers of acrylic acid, methacrylic acid, or their C1-C6 alkyl esters, such as those sold under the INCI name 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 with alkoxylated fatty alcohols are also preferred. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid, and itaconic acid, and suitable alkoxylated fatty alcohols are, in particular, Steareth-20 or ceteth-20.

[0240] Very particularly preferred polymers on the market are, for example, Aculyn® 22 (acrylates / Steareth-20 methacrylate copolymer), Aculyn® 28 (acrylates / Beheneth-25 methacrylate copolymer), Structure 2001® (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 / Palmeth25 acrylate copolymer) or Soltex OPT (acrylates / C12-22 alkyl methacrylate copolymer) sold by Rohme und Haas.

[0241] Suitable polymers based on vinyl monomers may include, for example, homopolymers and copolymers of N-vinylpyrrolidone, vinylcaprolactam, vinyl-(C1-C6)alkyl-pyrrole, vinyloxazole, vinylthiazole, vinylpyrimidine or vinylimidazole.

[0242] Also particularly suitable are octylacrylamide / acrylates / butylaminoethyl methacrylate copolymers, such as those sold under the trade names AMPHOMER® or LOVOCRYL® 47 by NATIONAL STARCH, or acrylates / octylacrylamide copolymers sold under the trade names DERMACRYL® LT and DERMACRYL® 79 by NATIONAL STARCH.

[0243] Suitable olefinic polymers include homopolymers and copolymers of ethylene, propylene, butene, isoprene, and butadiene.

[0244] 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. These block copolymers may contain, in addition to the styrene block, one or more blocks of styrene / ethylene, styrene / ethylene / butylene, styrene / butylene, styrene / isoprene, styrene / butadiene, etc. Such polymers are commercially available from BASF under the trade name "Luvitol HSB."

[0245] Surprisingly, it has been found that particularly strong and wash-fast colorations can be obtained when agent (b) comprises as sealant (b1) at least one film-forming polymer selected from the group consisting of homopolymers and copolymers of acrylic acid, homopolymers and copolymers of methacrylic acid, homopolymers and copolymers of acrylic acid esters, homopolymers and copolymers of methacrylic acid esters, homopolymers and copolymers of acrylic acid amides, homopolymers and copolymers of methacrylic acid amides, homopolymers and copolymers of vinylpyrrolidone, homopolymers and copolymers of vinyl alcohol, homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of ethylene, homopolymers and copolymers of propylene, homopolymers and copolymers of styrene, polyurethanes, polyesters and polyamides.

[0246] In a further preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one film-forming polymer selected from the group consisting of homopolymers and copolymers of acrylic acid, homopolymers and copolymers of methacrylic acid, homopolymers and copolymers of acrylic acid esters, homopolymers and copolymers of methacrylic acid esters, homopolymers and copolymers of acrylic acid amides, homopolymers and copolymers of methacrylic acid amides, homopolymers and copolymers of vinylpyrrolidone, homopolymers and copolymers of vinyl alcohol, homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of ethylene, homopolymers and copolymers of propylene, homopolymers and copolymers of styrene, polyurethanes, polyesters and polyamides.

[0247] In a further embodiment, it may be preferred to use at least one hydrophilic film-forming polymer as sealing agent (b1) in agent (b).

[0248] 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.

[0249] The water solubility of a film-forming hydrophilic polymer can be measured, for example, by the following method: Place 1 g of polymer in a beaker. Draw up to 100 g with water. Add a beaker glass and heat the mixture to 25°C while stirring on a magnetic stirrer. Stir for 60 minutes. Then evaluate the aqueous mixture visually. A completely dissolved polymer will appear macroscopically homogeneous. If the polymer-water mixture cannot be evaluated visually 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%.

[0250] As film-forming, hydrophilic polymers, non-ionic, anionic and cationic polymers can be used.

[0251] 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.

[0252] Furthermore, it is particularly preferred to use polyvinylpyrrolidone (PVP) and / or vinylpyrrolidone-containing copolymers as film-forming hydrophilic polymers.

[0253] In another very particularly preferred embodiment, the agent (b) is characterized in that it comprises as sealing agent (b1) at least one film-forming, hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone (PVP) and copolymers of polyvinylpyrrolidone.

[0254] It is further preferred if agent (b) contains polyvinylpyrrolidone (PVP) as the film-forming hydrophilic polymer. Surprisingly, the wash fastness of the colorations obtained with agent (b) containing PVP was also very good.

[0255] Particularly suitable polyvinylpyrrolidones are available, for example, under the name Luviskol® K from BASF SE, in particular under the name Luviskol® K 90 or Luviskol® K 85 from BASF SE.

[0256] Another particularly suitable polyvinylpyrrolidone (PVP) is the polymer PVP K30, available from Ashland (ISP, POI Chemical). PVP K30 is a polyvinylpyrrolidone that is highly soluble in cold water and has the CAS number 9003-39-8. The molecular weight of PVP K30 is approximately 40,000 g / mol.

[0257] Other particularly suitable polyvinylpyrrolidones are the substances available from BASF 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.

[0258] The use of film-forming hydrophilic polymers (b1) from the group of copolymers of polyvinylpyrrolidone also leads to particularly good, wash-fast colouring results.

[0259] 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.

[0260] Of the vinylpyrrolidone-containing copolymers, styrene / VP copolymer and / or vinylpyrrolidone / vinyl acetate copolymer and / or VP / DMAPA acrylate copolymer and / or VP / vinylcaprolactam / DMAPA acrylate copolymer are very preferably used in cosmetics.

[0261] Vinylpyrrolidone-vinyl acetate copolymer is sold by BASF SE under the name Luviskol® VA. For example, VP / vinylcaprolactam / DMAPA acrylate copolymer is sold by Ashland Inc. under the trade name Aquaflex® SF-40. For example, VP / DMAPA acrylate copolymer is sold by Ashland Inc. under the name Styleze CC-10, which is a highly preferred vinylpyrrolidone-containing copolymer.

[0262] Other suitable copolymers of polyvinylpyrrolidone may be obtained by reaction of N-vinylpyrrolidone with at least one further monomer from the group consisting of N-vinylformamide, vinyl acetate, ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactone and / or vinyl alcohol.

[0263] In another very particularly preferred embodiment, the agent (b) is characterized in that it comprises as sealing agent (b1) at least one film-forming, hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / styrene copolymer, vinylpyrrolidone / ethylene copolymer, vinylpyrrolidone / propylene copolymer, vinylpyrrolidone / vinyl caprolactam copolymer, vinylpyrrolidone / vinyl formamide copolymer and / or vinylpyrrolidone / vinyl alcohol copolymer.

[0264] Another suitable copolymer of vinylpyrrolidone is the polymer known by the INCI name Maltodextrin / VP Copolymer.

[0265] Furthermore, when a non-ionic film-forming hydrophilic polymer is used as the film-forming hydrophilic polymer, intensely colored keratinous materials, especially hair, having very good wash fastness can be obtained.

[0266] In another embodiment, agent (b) may comprise at least one non-ionic, film-forming, hydrophilic polymer as sealing agent (b1).

[0267] According to the present invention, nonionic polymers are understood to be polymers that do not have structural units containing permanent cationic or anionic groups that must be compensated by counterions to maintain electroneutrality under standard conditions in protic solvents (e.g., water). Cationic groups include quaternized ammonium groups, but do not include protonated amines. Anionic groups include carboxylic acid groups and sulfonic acid groups.

[0268] Agent (b) may be a non-ionic, film-forming, hydrophilic polymer such as: - polyvinylpyrrolidone, - copolymers of N-vinylpyrrolidone with vinyl esters of carboxylic acids containing 2 to 18 carbon atoms, in particular copolymers of N-vinylpyrrolidone with vinyl acetate; - copolymers of N-vinylpyrrolidone, N-vinylimidazole and methacrylamide, - copolymers of N-vinylpyrrolidone, N-vinylimidazole and acrylamide, - copolymers of N-vinylpyrrolidone and N,N-di(C1-C4)alkylamino-(C2-C4)alkylacrylamide, It is particularly preferred that the polymer comprises at least one polymer selected from the group consisting of:

[0269] When a copolymer of N-vinylpyrrolidone and vinyl acetate is used, the molar ratio of structural units contained in the N-vinylpyrrolidone monomer to structural units contained in the vinyl acetate monomer is preferably in the range of 20:80 to 80:20, particularly 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.

[0270] Another particularly preferred polymer is selected from the group having the INCI name VP / methacrylamide / vinylimidazole copolymer, which is available from BASF SE under the trade name Luviset Clear.

[0271] Another particularly preferred non-ionic, film-forming, hydrophilic polymer is a copolymer of N-vinylpyrrolidone and N,N-dimethylaminopropyl methacrylamide, which is sold, for example, by the company ISP under the INCI name VP / DMAPA acrylate copolymer, e.g., Styleze® CC 10.

[0272] The cationic polymer is a copolymer of N-vinylpyrrolidone, N-vinylcaprolactam, N-(3-dimethylaminopropyl) methacrylamide and 3-(methacryloylamino)propyl-lauryldimethylammonium chloride (INCI name: Polyquaternium-69), which is sold, for example, by the company ISP under the trade name AquaStyle® 300 (28-32% by weight of active substance in an ethanol-water mixture, molecular weight 350,000).

[0273] Other suitable film-forming hydrophilic polymers include vinylpyrrolidone-vinylimidazolium methchloride copolymers offered under the names Luviquat® FC 370, FC 550 and INCI name Polyquaternium-16, as well as FC 905 and HM 552; vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, which have acrylic esters and acrylic amides as third monomeric building blocks, such as those sold under the name Aquaflex® SF 40, Examples include:

[0274] Polyquaternium-11 is a reaction product of diethyl sulfate and a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. Suitable commercial products are available from BASF SE under the names Dhyquart® CC 11 and Luviquat® PQ 11 PN, or from Ashland Inc. under the names Gafquat 440, Gafquat 734, Gafquat 755, or Gafquat 755N.

[0275] Polyquaternium-46 is a reaction product of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulfate, and is available, for example, from BASF SE under the trade name Luviquat® Hold. Polyquaternium-46 is preferably used in an amount of 1 to 5 wt. % based on the total weight of agent (b). Polyquaternium-46 is particularly preferably used in combination with a cationic guar compound. Polyquaternium-46 is even more preferably used in combination with a cationic guar compound and Polyquaternium-11.

[0276] Suitable anionic film-forming, hydrophilic polymers may be, for example, acrylic acid polymers, which may be in uncrosslinked or crosslinked form. Such products are commercially 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.

[0277] Examples of suitable film-forming, hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum, carob gum.

[0278] Examples of suitable film-forming hydrophilic polymers from the group of polysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose, and carboxymethyl cellulose.

[0279] Suitable film-forming, hydrophilic polymers from the acrylamide group are, for example, polymers prepared from (meth)acrylamido-C1-C4-alkylsulfonic acid or salt thereof monomers. Corresponding polymers may be selected from polymers of polyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid, polyacrylamidopropanesulfonic acid, poly2-acrylamido-2-methylpropanesulfonic acid, poly2-methylacrylamido-2-methylpropanesulfonic acid, and / or poly2-methylacrylamido-n-butanesulfonic acid.

[0280] Preferred polymers of poly(meth)acrylamide-C1-C4-alkylsulfonic acid are crosslinked and at least 90% neutralized. These polymers may be crosslinked or uncrosslinked.

[0281] Crosslinked and fully or partially neutralized polymers of the poly-2-acrylamido-2-methylpropanesulfonic acid type are known by the INCI names "ammonium polyacrylamido-2-methyl-propanesulfonate" or "ammonium polyacryldimethyltauramide".

[0282] Another preferred polymer of this type is a cross-linked poly-2-acrylamido-2 methyl-propanesulfonic acid polymer, which is partially neutralized with ammonia, sold under the trade name Hostacerin AMPS by Clariant.

[0283] In another expressly very particularly preferred embodiment, the method is characterized in that the agent (b) comprises at least one anionic film-forming polymer (b1).

[0284] In the present specification, the agent (b) is a sealing agent (b1) represented by the formula (PI): TIFF0007719088000053.tif26155, and at least one structural unit represented by formula (P-II): At least one structural unit indicated by TIFF0007719088000054.tif26155 [In the formula, M is a hydrogen atom or ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium. The best results were obtained when the composition contained at least one film-forming polymer including

[0285] In a further preferred embodiment, the method comprises the step of: the agent (b) being a sealing agent (b1) of the formula (PI): TIFF0007719088000055.tif26155, and at least one structural unit represented by formula (P-II): At least one structural unit indicated by TIFF0007719088000056.tif26155 [In the formula, M is a hydrogen atom or ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium. The film-forming polymer is characterized by comprising at least one film-forming polymer comprising:

[0286] When M represents a hydrogen atom, the structural unit represented by formula (PI) is based on an acrylic acid unit. When M represents an ammonium counterion, the structural unit represented by formula (PI) is based on the ammonium salt of acrylic acid. When M represents a sodium counterion, the structural unit of formula (PI) is based on the sodium salt of acrylic acid. When M represents a potassium counterion, the structural unit represented by formula (PI) is based on the potassium salt of acrylic acid.

[0287] When M represents 1 / 2 equivalent of a magnesium counter ion, the structural unit represented by formula (PI) is based on the magnesium salt of acrylic acid. When M represents 1 / 2 equivalent of calcium counter ions, the structural unit represented by formula (PI) is based on the calcium salt of acrylic acid.

[0288] The film-forming polymer or polymers (b1) are preferably used in agent (b) in amounts within certain ranges. Herein, it has proven particularly advantageous for solving the problem according to the invention if agent (b) comprises one or more film-forming polymers as sealing agent (b1) in a total amount of 0.1 to 18% by weight, preferably 1 to 16% by weight, more preferably 5 to 14.5% by weight, and very particularly preferably 8 to 12% by weight, based on the total weight of agent (b).

[0289] In a further preferred embodiment, the method is characterized in that agent (b) comprises one or more film-forming polymers as sealing agent (b1) in a total amount of 0.1 to 18% by weight, preferably 1 to 16% by weight, more preferably 5 to 14.5% by weight, very particularly preferably 8 to 12% by weight, based on the total weight of agent (b).

[0290] The application of agent (b), which contains a film-forming polymer as a sealant (b1), is intended to seal and / or fix the colored film initially formed by the application of agent (a). By applying the second agent (b), which also contains a film-forming polymer as a sealant (b1), the film-forming polymer (b1) is deposited in the form of an additional film on the colored film formed in the first layer. The multilayer film system thus produced exhibits improved resistance to external influences.

[0291] Here, the film produced by the agent (b) containing a film-forming polymer as the sealing agent (b1) is preferably not colored itself.In this way, it can be ensured that a certain degree of wear of the second film formed by the agent (b) does not cause any color change in the entire film system.Therefore, it is particularly preferred that the agent (b) does not contain or contains only a very small amount of colorant compounds.

[0292] In an alternative embodiment, the sealing agent (b1) comprises an alkalizing agent.

[0293] Particularly preferably, the alkalizing agent is selected from the group consisting of ammonia, C2-C6 alkanolamines, basic amino acids, alkali metal hydroxides and alkaline earth metal hydroxides.

[0294] In another particularly preferred embodiment, the method is characterized in that the sealing agent (b1) comprises at least one alkalizing agent selected from the group consisting of ammonia, C2-C6 alkanolamines, basic amino acids, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal silicates, alkali metal metasilicates, alkaline earth metal silicates, alkaline earth metal metasilicates, alkali metal carbonates and alkaline earth metal carbonates.

[0295] Aftertreatment with an agent (b) containing ammonia has been found to have a particularly positive effect on improving the washfastness and rubfastness of the dyeings obtained in this process.

[0296] In the context of a further very particularly preferred embodiment, the method is characterized in that the agent (b) comprises ammonia as sealing agent (b1).

[0297] Good results were also obtained when agent (b) contained at least one C2-C6 alkanolamine as sealing agent (b1).

[0298] The alkanolamine that can be used in agent (b) can be selected from the group of primary amines having a C2-C6 alkyl group with 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.

[0299] In a further preferred embodiment, the method according to the invention is characterized in that the agent (b) contains as sealing agent (b1) at least one alkalizing agent from the group consisting of alkanolamines, preferably selected from the group consisting of 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol and 2-amino-2-methylpropane-1,3-diol.

[0300] Good results were also obtained when agent (b) contained at least one basic amino acid as sealing agent (b1).

[0301] For the purposes of the present invention, an amino acid is an organic compound containing at least one protic amino group and at least one -COOH or one -SOH group in its structure. Preferred amino acids are aminocarboxylic acids, in particular α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, whereby α-aminocarboxylic acids are particularly preferred.

[0302] According to the present invention, a basic amino acid is an amino acid with an isoelectric point pI greater than 7.0.

[0303] 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 their mixtures, especially as racemates. However, it is particularly advantageous to use the originally preferred isomer, usually the L-configuration.

[0304] The basic amino acid is preferably selected from the group formed by arginine, lysine, ornithine and histidine, particularly preferably arginine and lysine. Thus, in a further particularly preferred embodiment, the method is characterized in that the sealing agent (b1) is an alkalizing agent comprising a basic amino acid selected from the group consisting of arginine, lysine, ornithine and / or histidine.

[0305] In a further preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one alkalizing agent selected from the group of basic amino acids, preferably selected from the group of arginine, lysine, ornithine and histidine.

[0306] Good results have also been obtained when agent (b) contains at least one alkali metal hydroxide as sealing agent (b1). Examples of suitable alkali metal hydroxides are sodium hydroxide and potassium hydroxide.

[0307] Good results have also been obtained when agent (b) contains, as sealing agent (b1), an alkalizing agent containing at least one alkaline earth metal hydroxide. Suitable alkaline earth metal hydroxides include magnesium hydroxide, calcium hydroxide and barium hydroxide.

[0308] Good results have also been obtained when agent (b) contains at least one alkali metal silicate and / or alkali metal metasilicate as sealing agent (b1). Suitable alkali metal silicates include sodium silicate and potassium silicate. Suitable alkali metal metasilicates include sodium metasilicate and potassium metasilicate.

[0309] Good results have also been obtained when agent (b) contains at least one alkali metal carbonate and / or alkaline earth metal carbonate as sealing agent (b1). Suitable alkali metal carbonates include sodium carbonate and potassium carbonate. Suitable alkaline earth metal carbonates include magnesium carbonate and calcium carbonate.

[0310] Among the group of said sealing agents (b1) in the form of alkalizing agents, ammonia, C2-C6 alkanolamines, basic amino acids and alkali metal hydroxides have proven particularly suitable.

[0311] In the context of a further particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one alkalizing agent selected from the group consisting of ammonia, C2-C6 alkanolamines, basic amino acids and alkali metal hydroxides.

[0312] In another particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one alkalizing agent selected from the group consisting of ammonia, 2-aminoethan-1-ol, 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide and potassium hydroxide.

[0313] Agent (b) comprises an alkalizing agent as a sealing agent (b1) in a cosmetic carrier, preferably an aqueous cosmetic carrier.

[0314] In this regard, it has been found to be advantageous if agent (b) comprises 5.0 to 99.0% by weight, preferably 15.0 to 97.0% by weight, more preferably 25.0 to 97.0% by weight, even more preferably 35.0 to 97.0% by weight, and very particularly preferably 45.0 to 97.0% by weight, of water, based on the total weight of agent (b).

[0315] In the context of a further embodiment, the method is characterized in that agent (b) comprises 5.0 to 99.0% by weight, preferably 15.0 to 97.0% by weight, more preferably 25.0 to 97.0% by weight, even more preferably 35.0 to 97.0% by weight, and very particularly preferably 45.0 to 97.0% by weight of water, based on the total weight of agent (b).

[0316] The alkalizing agent contained in agent (b) influences the pH value of agent (b). It has been found that particularly specific alkaline pH values have a beneficial effect on the dyeing performance and fastness properties of the dyed products achievable in the present method.

[0317] Therefore, the agent (b) containing an alkalizing agent as the sealing agent (b1) preferably has a pH of 7.0 to 12.0, preferably 7.5 to 11.5, more preferably 8.0 to 11.0, and most preferably 8.5 to 9.5.

[0318] The pH value can be measured using conventional methods known in the art, such as measuring the pH using a glass electrode via a combination electrode, or measuring the pH using pH test paper.

[0319] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises an alkalizing agent as sealing agent (b1) and has a pH of 7.0 to 12.0, preferably 7.5 to 11.5, more preferably 8.0 to 11.0, most preferably 8.5 to 9.5.

[0320] For the purposes of the present invention, pH values are those measured at a temperature of 22°C.

[0321] In yet another embodiment, the sealing agent (b1) comprises an acidifying agent.

[0322] Particularly preferably, the acidifying agent is selected from the group consisting of inorganic acids, organic acids, and mixtures thereof.

[0323] Good results have been obtained when agent (b) comprises at least one inorganic acid as sealing agent (b1). Suitable inorganic acids are, for example, phosphoric acid, sulfuric acid and / or hydrochloric acid, with sulfuric acid being particularly preferred.

[0324] In a further preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one acidifying agent selected from the group consisting of inorganic acids, preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid and mixtures thereof.

[0325] In a further, even more preferred embodiment, the method is characterized in that the agent (b) comprises sulfuric acid as sealing agent (b1).

[0326] Good results were also obtained when agent (b) contained at least one organic acid as sealing agent (b1), such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, toluoic acid, hydratropic acid, atropic acid, cinnamic acid, isonicotin ... The acid is preferably selected from the group consisting of carboxylic acid, nicotinic acid, bicarbamic acid, 4,4'-dicyano-6,6'-vinicotinic acid, 8-carbamoyloctanoic acid, 1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1,2,4,6,7-naphthalenepentaacetic acid, malonaldehyde acid, 4-hydroxyphthalic acid, 1-pyrazolecarboxylic acid, gallic acid or propanetricarboxylic acid, glycolic acid, gluconic acid, lactic acid, maleic acid, ascorbic acid, malic acid, tartaric acid, citric acid and mixtures thereof.

[0327] In a further preferred embodiment, the method comprises the step of: agent (b) comprising, as sealing agent (b1), at least one acidifying agent selected from the group consisting of organic acids, wherein the organic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, glyceric acid, glyoxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid, elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid, camphoric acid, benzoic acid, o, m, p-phthalic acid, naphthoic acid, thiazolinone ... and is preferably selected from the group consisting of benzoic acid, ...

[0328] In a further, even more preferred embodiment, the method is characterized in that the agent (b) comprises acetic acid as sealing agent (b1).

[0329] Suitable acidifying agents also include methanesulfonic acid and / or 1-hydroxyethane-1,1-diphosphonic acid.

[0330] Among the group of said sealing agents (b1) in the form of acidifying agents, sulfuric acid and / or acetic acid have proven particularly suitable.

[0331] In the context of a further particularly preferred embodiment, the method is characterized in that the agent (b) comprises as sealing agent (b1) at least one acidifying agent selected from the group consisting of sulfuric acid, acetic acid and mixtures thereof.

[0332] Agent (b) comprises an acidifying agent as sealing agent (b1) in a cosmetic carrier, preferably an aqueous cosmetic carrier.

[0333] The acidifying agent contained in agent (b) influences the pH of agent (b), and it has been found that an acidic pH value has a beneficial effect on the dyeing performance and fastness properties of the dyeings achievable in the process.

[0334] For this reason, the agent (b) containing an acidifying agent as the sealing agent (b1) preferably has a pH of 2.0 to 6.5, preferably 3.0 to 6.0, more preferably 4.0 to 6.0, and most preferably 4.5 to 5.5.

[0335] The pH value can be measured using conventional methods known in the art, such as measuring the pH using a glass electrode via a combination electrode, or measuring the pH using pH test paper.

[0336] In another very particularly preferred embodiment, the method is characterized in that the agent (b) comprises an acidifying agent as sealing agent (b1) and has a pH of 2.0 to 6.5, preferably 3.0 to 6.0, more preferably 4.0 to 6.0, most preferably 4.5 to 5.5.

[0337] For the purposes of the present invention, pH values are those measured at a temperature of 22°C.

[0338] <Other ingredients in agents (a) and (b)> The above agents (a) and (b) may further contain one or more optional ingredients.

[0339] Agents (a) and / or (b) may further comprise one or more surfactants. The term surfactant refers to a surface-active substance. They are classified into anionic surfactants, which consist of a hydrophobic group and a negatively charged hydrophilic head group; zwitterionic surfactants, which have both a negative charge and a compensating positive charge; cationic surfactants, which have a hydrophobic group and a positively charged hydrophilic group; and nonionic surfactants, which have no charge but have a strong dipole moment in aqueous solution and are strongly hydrated.

[0340] 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 having 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-hydroxyethylimidazolines, each having 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is a fatty acid amide derivative known by the INCI name cocamidopropyl betaine.

[0341] Zwitterionic surfactants are those with C8-C 24These 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 -SO3H group and are capable of forming inner salts. Examples of suitable zwitterionic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylimidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids, and alkylaminoacetic acids, each containing 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.

[0342] Particularly preferred zwitterionic surfactants are N-cocosalklylaminopropionate, cocosacylaminoethylaminopropionate and C 12 -C 18 -acyl sarcosine.

[0343] The formulation may further comprise at least one nonionic surfactant. Suitable nonionic surfactants are alkyl polyglycosides and alkylene oxide addition products to fatty alcohols and fatty acids with 2 to 30 mol of ethylene oxide per mol of fatty alcohol or fatty acid. Furthermore, formulations with good properties can be obtained when the nonionic surfactant comprises a fatty acid ester of ethoxylated glycerol reacted with at least 2 mol of ethylene oxide.

[0344] Furthermore, the agent may contain at least one cationic surfactant. Cationic surfactants are surfactants, i.e., surface-active compounds, each of which has one or more positive charges. Cationic surfactants contain only positive charges. Usually, these surfactants consist of a hydrophobic part and a hydrophilic head group, and the hydrophobic part usually consists of a hydrocarbon structure (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 include: quaternary ammonium compounds which may have one or two alkyl chains with a chain length of 8 to 28 carbon atoms as hydrophobic groups, - a quaternary phosphonium salt substituted with one or more alkyl chains having a chain length of 8 to 28 carbon atoms, or - Tertiary sulfonium salts Examples include:

[0345] Furthermore, the cationic charge can also be part of a heterocycle in the form of an onium structure (e.g., an imidazolium ring or a pyridinium ring). In addition to the functional unit with a cationic charge, the cationic surfactant may also contain other uncharged functional groups, such as in the case of ester groups. 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 each agent.

[0346] The agent may further comprise 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.

[0347] The anionic surfactants are used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight, and most preferably 1 to 15% by weight, based on the total weight of each agent.

[0348] Agent (a) and / or agent (b) may further comprise a matting agent. Suitable matting agents include, for example, (modified) starch, wax, talc, and / or (modified) silicone. The amount of the matting agent is preferably between 0.1 and 10% by weight, based on the total amount of agent (a) or agent (b). Preferably, agent (a) comprises a matting agent.

[0349] Agent (a) and / or agent (b) may further comprise a thickening agent.

[0350] When using agent (a) and / or agent (b), they must not be so diluted that they drip off the keratinous materials, and for this reason it may be preferable for agent (a) and / or (b) to contain a thickener.

[0351] Therefore, in the context of one embodiment, the method for dyeing keratinous materials is preferably characterized in that agent (a) and / or agent (b) further comprises a thickener.

[0352] Suitable thickeners include, for example, chemically modified celluloses such as propyl cellulose, methyl ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, sulfoethyl cellulose, carboxymethyl sulfoethyl cellulose, hydroxypropyl sulfoethyl cellulose, hydroxyethyl sulfoethyl cellulose, methyl ethyl hydroxyethyl cellulose, methyl sulfoethyl cellulose and / or ethyl sulfoethyl cellulose.

[0353] In a preferred embodiment, the method for dyeing keratin materials is characterized in that agent (a) and / or agent (b) further comprise a thickener selected from the group consisting of propyl cellulose, methyl ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, sulfoethyl cellulose, carboxymethyl sulfoethyl cellulose, hydroxypropyl sulfoethyl cellulose, hydroxyethyl sulfoethyl cellulose, methyl ethyl hydroxyethyl cellulose, methyl sulfoethyl cellulose, ethyl sulfoethyl cellulose and mixtures thereof.

[0354] Particularly suitable thickening agents are selected from hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, and mixtures thereof.

[0355] In a particularly preferred embodiment, the method for dyeing keratinous materials is characterized in that agent (a) and / or agent (b) further comprise a thickener selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose and mixtures thereof.

[0356] Other suitable thickening agents include galactomannans. Preferred galactomannans include: Examples include galactomannans having the INCI name Cyamopsis tetragonoloba gum (guar gum), galactomannans having the INCI name Ceratonia siliqua (carob) gum (locust bean gum), galactomannans having the INCI name Cassia gum, and galactomannans having the INCI name Caesalpinia spinosa gum (tara gum).

[0357] Therefore, it is particularly preferred that the method for dyeing keratinous materials further comprises at least one galactomannan selected from the group consisting of a galactomannan having the INCI name Cyamopsis tetragonoloba gum (guar gum), a galactomannan having the INCI name Ceratonia siliqua (carob) gum (locust bean gum), a galactomannan having the INCI name Cassia gum, and a galactomannan having the INCI name Caesalpinia spinosa gum (tara gum). In a particularly preferred embodiment, the galactomannan comprises a galactomannan having the INCI name Caesalpinia spinosa gum (tara gum).

[0358] The amount of thickener is preferably 0.1 to 10% by weight, based in each case on the total amount of agent (a) and / or agent (b).

[0359] The agent may also contain other active ingredients, auxiliaries and additives, such as solvents; C8-C 30 Fatty acid triglycerides, C8-C 30 Fatty acid monoglycerides, C8-C 30fatty components such as fatty acid diglycerides and / or hydrocarbons; structurants, such as glucose, maleic acid and lactic acid, hair conditioning compounds, such as phospholipids, for example lecithin and kephaline; perfume oils, dimethyl isosorbide and cyclodextrin; fibre structure improving active ingredients, in particular mono-, di- and oligosaccharides, for example glucose, galactose, fructose, lactose; dyes for colouring the formulations; 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 their fatty acid condensates or optionally in the form of anionic or cationically modified derivatives; vegetable oils; light stabilizers and UV blockers; active ingredients, for example panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acid and the like. and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarin, hydroxybenzoic acids, catechins, tannins, leukoanthocyanidins, 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 paraffin; 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.

[0360] The selection of these other substances is made by the expert depending on the desired properties of the agent. For other optional ingredients and the amounts of these ingredients to be used, refer to the relevant manuals known to the expert. The additional active ingredients and auxiliary substances are preferably used in the formulation according to the present invention in an amount of 0.0001 to 25% by weight, in particular 0.0005 to 15% by weight, based on the total weight of each agent.

[0361] <Method for dyeing keratinous materials> In the procedure according to the invention, agents (a) and (b) are applied to keratinous materials, in particular human hair. Agents (a) and (b) are therefore ready-to-use agents. Agents (a) and (b) are different.

[0362] In principle, agents (a) and (b) can be applied simultaneously or successively, whereby successive application is preferred.

[0363] The best results were obtained when agent (a) was first applied to the keratinous material in a first step, and agent (b) was then applied in a second step.

[0364] Thus, very particular preference is given to a method for treating keratinous materials, in particular for colouring keratinous materials, in particular human hair, which method comprises the following steps in the indicated order: In a first step, an agent (a) is applied to the keratin material, the agent (a): (a1) at least one organosilicon compound selected from the group consisting of silanes containing one, two or three silicon atoms; (a2) a first colorant compound comprising at least one lenticular substrate platelet-based pigment; and (a3) Second Colorant Compound including, In a second step, an agent (b) is applied to the keratin material, the agent (b): (b1) at least one sealant Includes:

[0365] Furthermore, in order to impart high resistance to leaching to the dyed keratinous materials over a longer period of time, agents (a) and (b) are particularly preferably applied within one and the same dyeing process, which means that there is a period of up to several hours between the application of agents (a) and (b).

[0366] In a further preferred embodiment, the method comprises first applying agent (a) and then applying agent (b), and the time between the application of agent (a) and the application of agent (b) is at most 24 hours, preferably at most 12 hours, particularly preferably at most 6 hours.

[0367] A distinctive feature of agent (a) is that it contains at least one reactive organosilicon compound (a1). The reactive organosilicon compound (a1) undergoes an oligomerization or polymerization reaction, thereby functionalizing the hair surface upon contact with the hair. A first film is thus formed. The colorant compounds (a2) and (a3) are incorporated into this film. In the second step of the method, a second agent (b) is then applied to the hair. During application of agent (b), which contains at least one film-forming polymer as a sealant (b1), the latter interacts with the silane film, thereby bonding to the keratinous materials. During application of agent (b), which contains at least one alkalizing or acidifying agent as a sealant (b1), the formation of the silane film is favorably affected. The desired coloring of the keratinous materials is achieved using the colorant compound in agent (a).

[0368] In the context of a further embodiment, the following steps, in the order given: (1) applying agent (a) to a keratinous material; (2) a step of applying the agent (a) for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (3) optionally rinsing the keratinous material with water; (4) applying agent (b) onto the keratinous material; (5) a step of allowing the agent (b) to act for 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (6) Rinse the keratinous material with water Very particularly preferred is a method comprising:

[0369] In steps (3) and (6), rinsing the keratinous materials with water is understood according to the present invention to mean that only water is used in the rinsing step, and no other agents are used other than agents (a) and (b).

[0370] In step (1), the agent (a) is first applied to keratinous materials, particularly human hair.

[0371] After application, agent (a) is left to act on the keratinous materials. In this regard, application times to the hair of 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, particularly preferably 30 seconds to 2 minutes, have proven particularly beneficial.

[0372] In a preferred embodiment of the method, agent (a) can now be rinsed from the keratinous materials before agent (b) is applied to the hair in a subsequent step.

[0373] When agent (b) was applied to keratinous materials still exposed to agent (a), colorations with similarly good washfastness were obtained.

[0374] In step (4), agent (b) is then applied to the keratinous material. After application, agent (b) is allowed to act on the hair.

[0375] Even if the contact time of agent (b) is short, the process can produce dyeings with particularly good strength and washfastness. Application times to the hair of from 10 seconds to 10 minutes, preferably from 20 seconds to 5 minutes, and most preferably from 30 seconds to 3 minutes, have proven particularly beneficial.

[0376] In step (6), agent (b) (and optionally any agent (a) still present) is now rinsed from the keratinous materials with water.

[0377] In this embodiment, the steps (1) to (6) are preferably carried out within 24 hours.

[0378] Agent (a) includes a class of highly reactive compounds that, together with organosilicon compounds, can undergo hydrolysis or oligomerization and / or polymerization during use. As a result of their high reactivity, these organosilicon compounds form a film on keratinous materials.

[0379] It is of considerable advantage to the user to prepare the ready-to-use formulation (a) immediately before application to avoid premature oligomerization or polymerization.

[0380] In yet another embodiment, preferred is a method comprising the following steps in the order presented: (1) preparing agent (a) by mixing a first agent (a') and a second agent (a''); where the first agent (a') comprises at least one organosilicon compound (a1) from the group of silanes containing 1, 2 or 3 silicon atoms, and The second agent (a'') comprises a first colorant compound comprising at least one lenticular substrate platelet-based pigment (a2) and a second colorant compound (a3); (2) applying agent (a) onto the keratinous material; (3) a step of allowing the agent (a) to act for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) optionally rinsing the keratinous material with water; (5) applying agent (b) onto the keratinous material; (6) a step of allowing the agent (b) to act for 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratin material with water.

[0381] In order to provide a formulation that is as stable as possible during storage, the agent (a') itself is preferably prepared to have low moisture content or to be free of water.

[0382] In a preferred embodiment, the method is characterized in that the agent (a') contains a water content of 0.001 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight, and very particularly preferably 1.5 to 7% by weight, based on the total weight of the agent (a').

[0383] The agent (a'') may contain water.

[0384] Agent (a″) may further comprise a thickening agent. Within this embodiment, agent (a″) preferably comprises a thickening agent selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, and mixtures thereof.

[0385] Within this embodiment, the ready-to-use agent (a) is prepared by mixing agent (a') and agent (a'').

[0386] For example, a user can first stir or shake agent (a') containing organosilicon compound (a1) with agent (a''). The user can then apply this mixture of (a') and (a'') to keratinous materials either immediately after preparation or after a short reaction time of 10 seconds to 30 minutes. Thereafter, the user can apply agent (b) as described above.

[0387] It may be preferred that the method further comprises an agent (a''') comprising water and a second colorant compound (a3).

[0388] Therefore, in the context of a further embodiment, particularly preferred is a method comprising the following steps in the order given: (1) preparing agent (a) by mixing a first agent (a'), a second agent (a''), and a third agent (a'''); where: the first agent (a') comprises at least one organosilicon compound (a1) from the group of silanes containing 1, 2 or 3 silicon atoms; the second agent (a″) comprises a first colorant compound (a2) comprising a pigment based on at least one lenticular substrate platelet, and the third agent (a''') comprises a second coloring compound (a3) and at least 10% by weight of water, based on the total weight of agent (a'''); (2) applying agent (a) onto the keratinous material; (3) a step of allowing the agent (a) to act for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (4) optionally rinsing the keratinous material with water; (5) applying agent (b) onto the keratinous material; (6) a step of allowing the agent (b) to act for 30 seconds to 30 minutes, preferably 30 seconds to 10 minutes; (7) Rinse the keratin material with water.

[0389] Within this embodiment, the ready-to-use agent (a) is prepared by mixing agent (a'), agent (a'') and agent (a''').

[0390] For example, the user may first stir or shake agent (a") and agent (a'"), and then stir or shake the resulting mixture with agent (a') containing organosilicon compound (a1). The user can then apply this mixture of (a'), (a"), and (a'") to keratinous materials immediately after its preparation, or after a short reaction time of 10 seconds to 20 minutes. The user can then apply agent (b) as described above.

[0391] <Multi-component packaging unit (component kit)> For user convenience, the user is preferably provided with all necessary agents in a multi-component packaged unit (kit of parts).

[0392] Therefore, another subject of the present invention is a method for manufacturing a pharmaceutical composition comprising the following, prepared separately: - a first container containing an agent (a'), where the agent is (a'): (a1) at least one organosilicon compound selected from the group consisting of silanes having 1, 2, or 3 silicon atoms; and - a second container containing an agent (a''), where the agent (a''): (a2) a first colorant compound comprising at least one lenticular substrate platelet-based pigment; and (a3) a second colorant compound; - a third container containing agent (b), where agent (b): (b1) comprising at least one sealing agent; A multi-component packaged unit (kit of parts) for dyeing keratinous materials, comprising: wherein components (a1), (a2), (a3) and (b1) are disclosed in detail above.

[0393] The organosilicon compounds (a1) from the group of silanes containing one, two or three silicon atoms contained in the agent (a') of the kit correspond to the organosilicon compounds (a1) also used in the agent (a) of the method described above.

[0394] The first colorant compound comprising at least one lenticular substrate platelet-based pigment (a2) contained in agent (a'') of the kit corresponds to the first colorant compound comprising at least one lenticular substrate platelet-based pigment (a2) also used in agent (a) of the method described above.

[0395] The second colorant compound (a2) contained in the agent (a'') of the kit corresponds to the second colorant compound (a3) also used in the agent (a) of the method described above.

[0396] The sealant (b1) contained in the agent (b) of the kit is the same as the sealant (b1) used in the agent (b) of the method described above.

[0397] A second object of the present invention is to provide a method for manufacturing a medicament for the treatment of ... - a first container containing an agent (a'), where the agent is (a'): at least one organosilicon compound (a1) from the group consisting of silanes containing 1, 2 or 3 silicon atoms; - a second container containing an agent (a''), where the agent (a''): (a2) a first colorant compound comprising at least one lenticular substrate platelet pigment; - a third container containing an agent (a'''), wherein said agent is (a'''): (a3) a second colorant compound, and - a fourth container containing agent (b), where agent (b): (b1) comprising at least one sealing agent; A multi-component packaged unit (kit of parts) for dyeing keratinous materials, comprising: wherein components (a1), (a2), (a3) and (b1) are disclosed in detail above.

[0398] In the context of a further embodiment, a multi-component packaging unit (kit of parts) for coloring keratinous materials preferably comprises the following packaged separately from each other: - a first container containing an agent (a'), where the agent is (a'): at least one organosilicon compound (a1) from the group of silanes containing 1, 2 or 3 silicon atoms, and - a second container containing an agent (a''), the agent (a''): (a2) a first colorant compound comprising at least one lenticular substrate platelet-based pigment; - a third container containing an agent (a'''), said agent comprising (a'''): (a3) a second colorant compound selected from the group consisting of organic pigments and at least 10 wt. % water, based on the total weight of agent (a'''); - a fourth container containing an agent (b), wherein the agent is (b): (b1) comprises at least one sealing agent. wherein components (a1), (a2), (a3) and (b1) are disclosed in detail above.

[0399] In these embodiments, it may be preferred that agents (a''') and / or (b) further comprise a thickening agent.

[0400] According to this embodiment, a multi-component packaging unit (kit of parts) is preferred, in which agent (a''') comprises a thickener selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose and mixtures thereof.

[0401] Further preferred is a kit of parts wherein agent (b) comprises a thickening agent selected from the group consisting of ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and mixtures thereof.

[0402] Also preferred are multi-component kits in which agent (a''') and agent (b) each comprise a thickening agent selected from the group consisting of ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and mixtures thereof.

[0403] With regard to further preferred embodiments of the multi-component packaging unit, what has been said regarding the method applies mutatis mutandis.

[0404] Surprisingly, it has been shown that the presence of pigments based on lenticular substrate platelets in agent (a) results in dyeings with optimal grey coverage, in contrast to the use of pigments based on non-lenticular substrate platelets.

[0405] Therefore, a third subject of the present application is a method for producing a medicament for the treatment of a cancer, comprising the steps of: - applying an agent (a) to the keratinous material, wherein the agent (a) (a1) at least one organosilicon compound from the group of silanes containing one, two or three silicon atoms; (a2) a first colorant compound, and (a3) a second colorant compound; including, - applying an agent (b) to the keratinous material, wherein the agent (b) (b1) comprising at least one sealant; Including, The use of a first colorant compound (a2) comprising at least one pigment based on lenticular substrate platelets in a method for coloring keratinous materials, in particular human hair, to obtain a coloration with optimal gray coverage. [Example]

[0406] The following formulations were made (all values are in weight % unless otherwise stated):

[0407] [Table 1]

[0408] [Table 2]

[0409] [Table 3]

[0410] 5 g of agent (a'), 5 g of agent (a''), and 10 g of agent (a''') were mixed to prepare ready-to-use agent (a). Thereafter, agent (a) was left to stand for about 5 minutes.

[0411] [Table 4]

[0412] Agent (a) was massaged into one strand of hair (Kerling, Euronatural hair white) at a time and left to act for 1 minute, after which agent (a) was rinsed with water.

[0413] Thereafter, agent (b) was applied to the hair tresses and left to act for 5 minutes, after which it was also rinsed with water. Preferred embodiments of the present specification include at least the following. [1] A method for dyeing keratinous materials, in particular human hair, comprising the steps of: applying an agent (a) to the keratinous material, wherein the agent (a) (a1) at least one organosilicon compound selected from the group consisting of silanes containing one, two or three silicon atoms; (a2) a first colorant compound comprising at least one lenticular substrate platelet-based pigment; and (a3) a second colorant compound; including, applying an agent (b) to the keratinous material, wherein the agent (b) (b1) at least one sealing agent; A method comprising: [2] The agent (a) is represented by formula (I) and / or (II): TIFF0007719088000061.tif10161 [In the formula, -R 1 、R 2 are independently hydrogen atoms or C 1 -C 6 represents an alkyl group, -L is a linear or branched divalent C 1 -C 20 is an alkylene group, -R 3 、R 4 are C independently of each other. 1 -C 6 represents an alkyl group, -a represents an integer from 1 to 3, -b represents the integer 3-a] Formula (II): TIFF0007719088000062.tif10161 In the organosilicon compound represented by the formula: [- R 5 、R 5’ 、R 5'' 、R 6 、R 6' and R 6'' independently, C 1 -C 6 represents an alkyl group, A, A', A'', A''', and A'''' are independently straight or branched chain divalent C 1 -C 20 represents an alkylene group, - R 7 and R 8 are independently 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 An alkyl group or a group of formula (III): TIFF0007719088000063.tif10161 [In the formula, -c represents an integer from 1 to 3, -d represents the integer 3-c, -c' represents an integer of 1 to 3, -d' represents the integer 3-c', -c'' represents an integer from 1 to 3, -d'' represents the integer 3-c''; -e represents 0 or 1, -f represents 0 or 1, -g represents 0 or 1, -h represents 0 or 1, provided that at least one of the groups e, f, g and h is different from 0. represents a group represented by the formula: The method according to [1], characterized in that it contains at least one organosilicon compound (a1) represented by the following formula: [3] The agent (a) is represented by the formula (I): TIFF0007719088000064.tif10161 [In the formula, - R 1 、R 2 Both represent hydrogen atoms, - L is a linear, divalent C 1 -C 6 Alkylene groups, preferably propylene groups (-CH 2 -CH 2 -CH 2 -) or ethylene group (-CH 2 -CH 2 -) and - R 3 、R 4 each independently represents a methyl group or an ethyl group; - a represents the number 3, - b represents the number 0] The method according to [1] or [2], characterized in that it contains at least one organosilicon compound (a1) represented by the following formula: [4] Agent (a) is - (3-aminopropyl)triethoxysilane - (3-aminopropyl)trimethoxysilane - 1-(3-aminopropyl)silanetriol - (2-aminoethyl)triethoxysilane - (2-aminoethyl)trimethoxysilane - 1-(2-aminoethyl)silanetriol - (3-Dimethylaminopropyl)triethoxysilane - (3-Dimethylaminopropyl)trimethoxysilane - 1-(3-dimethylaminopropyl)silanetriol - (2-Dimethylaminoethyl)triethoxysilane (2-dimethylaminoethyl)trimethoxysilane and / or - 1-(2-dimethylaminoethyl)silanetriol The method according to any one of [1] to [3], characterized in that the method comprises at least one organosilicon compound (a1) represented by formula (I) selected from the group consisting of: [5] The agent (a) is represented by the formula (II): TIFF0007719088000065.tif10161 [In the formula, - e and f together represent the number 1, - g and h together represent the number 0, A and A' are independently a linear, divalent C 1 -C 6 represents an alkylene group, - R 7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group, or a group represented by formula (III). The method according to any one of [1] to [4], characterized in that the method comprises at least one organosilicon compound (a1) represented by the following formula: [6] The agent (a) is represented by the formula (IV): TIFF0007719088000066.tif10161 [In the formula, -R 9 is C 1 -C 18 represents an alkyl group, -R 10 is a hydrogen atom or C 1 -C 6 represents an alkyl group, -R 11 is C 1 -C 6 represents an alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The method according to any one of [1] to [5], characterized in that the method comprises at least one organosilicon compound (a1) represented by the following formula: [7] Agent (a) is - Methyltrimethoxysilane - Methyltriethoxysilane - Ethyltrimethoxysilane - Ethyltriethoxysilane - Propyltrimethoxysilane - Propyltriethoxysilane - Hexyltrimethoxysilane - Hexyltriethoxysilane - Octyltrimethoxysilane - Octyltriethoxysilane - Dodecyltrimethoxysilane - Dodecyltriethoxysilane - Octadecyltrimethoxysilane - octadecyltriethoxysilane and - A mixture of these The method according to any one of [1] to [6], characterized in that the method comprises at least one organosilicon compound (a1) represented by formula (IV) selected from the group consisting of: [8] The method according to any one of [1] to [7], wherein the agent (a) contains at least two structurally different organosilicon compounds (a1). [9] The method according to any one of [1] to [8], wherein the sealant contains a compound selected from the group consisting of a film-forming polymer, an alkalizing agent, an acidifying agent, and a mixture thereof.

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

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

[10] , wherein the substrate platelet comprises brass.

[12] Agent (a) is Carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a color index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a color index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a color index of CI 61565, CI 61570, CI 74260, orange pigments with a color index of CI 11725, CI 15510, CI 45370, CI 71105, and orange pigments with a color index of CI 12085, CI 12120, CI

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

[11] , further comprising the step of: (a) comprising a second colorant compound (a3) selected from the group consisting of organic pigments consisting of red pigments of 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.

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

[12] , characterized in that the agent (a) comprises a second colorant compound (a3) from the group of inorganic pigments selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or colored mica-based or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[14] The process of: - applying an agent (a) to the keratinous material, wherein the agent (a) (a1) at least one organosilicon compound from the group of silanes containing one, two or three silicon atoms; (a2) a first colorant compound, and (a3) a second colorant compound; including, - applying an agent (b) to the keratinous material, wherein the agent (b) is (b1) comprising at least one sealant; 1. The use of a first colorant compound (a2) comprising at least one pigment based on lenticular substrate platelets in a method for coloring keratinous materials, in particular human hair, to obtain a coloration with optimal gray coverage.

[15] Separately packaged: - a first container containing an agent (a'), where the agent is (a'): (a1) at least one organosilicon compound selected from the group consisting of silanes having 1, 2 or 3 silicon atoms; - a second container containing an agent (a''), where the agent (a''): (a2) a first colorant compound comprising at least one lenticular substrate platelet-based pigment; - a third container containing an agent (a'''), wherein said agent is (a'''): (a3) a second colorant compound; and - a fourth container containing agent (b), where agent (b): (b1) comprises at least one sealing agent A kit of components for dyeing keratinous materials, comprising:

Claims

1. 1. A method for dyeing keratinous materials, comprising the steps of: applying an agent (a) to the keratinous material, wherein the agent (a) is (a1) at least one organosilicon compound selected from the group consisting of silanes containing one, two or three silicon atoms; wherein (a1) is a compound of formula (I): [In the formula, - R 1 and R 2 independently represent a hydrogen atom or a C 1 -C 6 alkyl group; -L is a linear or branched divalent C 1 -C 20 alkylene group; R 3 and R 4 each independently represent a C 1 -C 6 alkyl group; -a represents an integer of 1 to 3; -b represents the integer 3-a. and at least one organosilicon compound represented by Formula (IV): [In the formula, -R 9 represents a C 1 -C 18 alkyl group; -R 10 represents a hydrogen atom or a C 1 -C 6 alkyl group; -R 11 represents a C 1 -C 6 alkyl group; -k is an integer from 1 to 3, -m represents an integer 3-k. At least one organosilicon compound represented by Including, (a2) a first colorant compound comprising at least one lenticular substrate platelet based pigment, where a lenticular substrate platelet is a lens-shaped substrate platelet; and (a3) a second colorant compound; Including, applying an agent (b) to the keratinous material, wherein the agent (b) is (b1) at least one sealing agent; A method comprising:

2. (a1) is a compound represented by formula (II): [In the formula, -R ５ , R ５’ , R ５'' , R ６ , R ６' and R ６'' is independent, C １ -C ６ represents an alkyl group, A, A', A'', A''', and A'''' are independently linear or branched divalent C １ -C ２０ represents an alkylene group, -R ７ and R ８ are independently a hydrogen atom, C １ -C ６ Alkyl group, hydroxy C １ -C ６ Alkyl group, C ２ -C ６ Alkenyl group, amino C １ -C ６ An alkyl group or a group of formula (III): represents a group represented by -c represents an integer of 1 to 3; -d represents the integer 3-c; -c' represents an integer of 1 to 3, -d' represents the integer 3-c'; -c'' represents an integer of 1 to 3; -d'' represents the integer 3-c''; -e represents 0 or 1; -f represents 0 or 1; -g represents 0 or 1; -h represents 0 or 1; provided that at least one of groups e, f, g and h is different from 0.

10. The method of claim 1, further comprising the step of:

3. (a1) is a compound of formula (I): [In the formula, -R １ , R ２ Both represent hydrogen atoms, - L is a linear, divalent C １ -C ６ represents an alkylene group, -R ３ , R ４ each independently represents a methyl group or an ethyl group; - a represents the number 3, - b represents the number 0] 3. The method according to claim 1, further comprising the step of:

4. (a1) is - (3-aminopropyl)triethoxysilane - (3-aminopropyl)trimethoxysilane - 1-(3-aminopropyl)silanetriol - (2-aminoethyl)triethoxysilane - (2-aminoethyl)trimethoxysilane - 1-(2-aminoethyl)silanetriol - (3-dimethylaminopropyl)triethoxysilane - (3-dimethylaminopropyl)trimethoxysilane - 1-(3-dimethylaminopropyl)silanetriol - (2-dimethylaminoethyl)triethoxysilane (2-dimethylaminoethyl)trimethoxysilane and / or - 1-(2-dimethylaminoethyl)silanetriol 4. The method according to claim 1, further comprising the step of:

5. (a1) is a compound represented by formula (II): [In the formula, e and f together represent the number 1, g and h together represent the number 0, A and A' are independently a linear, divalent C １ -C ６ represents an alkylene group, -R ７ represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group, or a group represented by formula (III).

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

6. (a1) is - Methyltrimethoxysilane - Methyltriethoxysilane - Ethyltrimethoxysilane - Ethyltriethoxysilane - Propyltrimethoxysilane - Propyltriethoxysilane - Hexyltrimethoxysilane - Hexyltriethoxysilane - Octyltrimethoxysilane - Octyltriethoxysilane - Dodecyltrimethoxysilane - Dodecyltriethoxysilane - Octadecyltrimethoxysilane - Octadecyltriethoxysilane and - Mixtures of these The method according to any one of claims 1 to 5, characterized in that it comprises at least one organosilicon compound represented by formula (IV) selected from the group consisting of:

7. The method according to any one of claims 1 to 6, characterized in that the sealing agent comprises a compound selected from the group consisting of a film-forming polymer, an alkalizing agent, an acidifying agent, and mixtures thereof.

8. The method according to any one of claims 1 to 7, characterized in that the substrate platelet comprises aluminum.

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

10. The agent (a) is Carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a color index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a color index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a color index of CI 61565, CI 61570, CI 74260, orange pigments with a color index of CI 11725, CI 15510, CI 45370, CI 71105, and orange pigments with a color index of CI 12085, CI 12120, CI 10. The method of claim 1, comprising a second colorant compound (a3) selected from the group of organic pigments consisting of red pigments of 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.

11. 11. The method according to claim 1, wherein the agent (a) comprises a second colorant compound (a3) from the group of inorganic pigments selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or colored mica-based or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

12. The following steps: applying an agent (a) to the keratinous materials, wherein the agent (a) is (a1) at least one organosilicon compound from the group of silanes containing one, two or three silicon atoms; wherein (a1) is a compound of formula (I): [In the formula, - R 1 and R 2 independently represent a hydrogen atom or a C 1 -C 6 alkyl group; -L is a linear or branched divalent C 1 -C 20 alkylene group; R 3 and R 4 each independently represent a C 1 -C 6 alkyl group; -a represents an integer of 1 to 3; -b represents the integer 3-a. and at least one organosilicon compound represented by Formula (IV): [In the formula, -R 9 represents a C 1 -C 18 alkyl group; -R 10 represents a hydrogen atom or a C 1 -C 6 alkyl group; -R 11 represents a C 1 -C 6 alkyl group; -k is an integer from 1 to 3, -m represents an integer 3-k. At least one organosilicon compound represented by Including, (a2) a first colorant compound, and (a3) a second colorant compound; Including, applying an agent (b) to the keratinous materials, wherein the agent (b) is (b1) at least one sealing agent; 1. A method for coloring keratinous materials, comprising: at least one pigment based on lenticular substrate platelets to obtain a coloration with optimal gray coverage, wherein the lenticular substrate platelets are lens-shaped substrate platelets; Including, Use of a first colorant compound (a2).

13. Separately packaged: a first container containing an agent (a'), where the agent is (a'): (a1) at least one organosilicon compound selected from the group consisting of silanes having 1, 2 or 3 silicon atoms; wherein (a1) is a compound of formula (I): [In the formula, - R 1 and R 2 independently represent a hydrogen atom or a C 1 -C 6 alkyl group; -L is a linear or branched divalent C 1 -C 20 alkylene group; R 3 and R 4 each independently represent a C 1 -C 6 alkyl group; -a represents an integer of 1 to 3; -b represents the integer 3-a. and at least one organosilicon compound represented by Formula (IV): [In the formula, -R 9 represents a C 1 -C 18 alkyl group; -R 10 represents a hydrogen atom or a C 1 -C 6 alkyl group; -R 11 represents a C 1 -C 6 alkyl group; -k is an integer from 1 to 3, -m represents an integer 3-k. At least one organosilicon compound represented by Including, a second container containing an agent (a″), where the agent is (a″): (a2) a first colorant compound comprising at least one lenticular substrate platelet based pigment, where a lenticular substrate platelet is a lens-shaped substrate platelet; a third container containing an agent (a'''), wherein said agent is (a'''): (a3) a second colorant compound; and a fourth container containing agent (b), where agent (b): (b1) comprises at least one sealing agent A kit of components for dyeing keratinous materials, comprising:

Images