Method for dyeing keratinous materials comprising using an organosilicon compound, a colored effect pigment, and a film-forming polymer II

Abstract

The present invention relates to a method for dyeing keratinous materials, in particular human hair, comprising the following steps: applying to the keratinous materials an agent (a) comprising at least one organosilicon compound, and applying to the keratinous materials an agent (b) comprising at least one coloring compound (b1) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), and at least one film-forming polymer (b2), wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments. The present invention also relates to a multi-component packaging unit comprising the two agents (a) and (b) in two separately packaged containers.

Description

[Technical Field]

[0001] The subject of the present invention is a method for dyeing keratinous materials, in particular human hair, which comprises the application of two different agents (a) and (b): Agent (a) contains at least one organosilicon compound; Agent (b) contains at least one coloring compound (b2) comprising at least one selected effect pigment.

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

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

[0004] When using direct dyes, the already prepared dye diffuses from the colorant into the hair fiber. Compared to oxidative dyes, dyes obtained with direct dyes have a shorter color retention time and are more quickly washable. Direct dye stains typically remain on the hair for 5 to 20 washes.

[0005] 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 understood to be insoluble coloring substances. They exist in the dye composition as small particles without dissolving and are exclusively attached externally to the surface of the hair fiber and / or skin. Therefore, color pigments 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 "hair mascara."

[0006] Until now, consumers have had no choice but to use oxidative dyes, especially if they want long-lasting hair coloring. However, despite numerous optimization attempts, oxidative dyes cannot completely avoid the unpleasant odor of ammonia or amines. In addition, the hair damage associated with the use of oxidative dyes can also have a negative impact on the user's hair. Therefore, the search for alternative, high-performance dyeing methods is an ongoing challenge.

[0007] EP 2168633 B1 deals with a method for producing long-lasting pigmented hair color, and teaches that by applying a combination of pigment, organosilicon compound, hydrophobic polymer and solvent to the hair, a color that is particularly resistant to shampooing can be obtained.

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

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

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

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

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

[0013] Surprisingly, it has been found that this problem can be successfully solved by coloring keratinous materials (especially human hair) by applying at least two agents (a) and (b) to the keratinous material (hair), where agent (a) contains at least one organosilicon compound and agent (b) contains at least one selected pigment (b1) and a film-forming polymer (b2).

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

[0015] A first object of the present invention is to provide a method for producing a process comprising the steps of: - applying an agent (a) comprising at least one organosilicon compound to keratinous materials, and - applying to the keratin material an agent (b) comprising at least one coloring compound (b1) comprising at least one effect pigment, and at least one film-forming polymer (b2), comprising a substrate platelet α) and a coating β). 1. A method for coloring keratinous materials, in particular human hair, comprising: (i) a coating having at least one layer of a metal oxide and / or metal oxide hydrate, and (ii) a coloring compound from the group of pigments.

[0016] Depending on the structure of the effect pigment according to the coloring compound (ii) from the group of pigments used, different shades can be obtained in the dyed keratin hair, for example metallic or glossy colorings. DETAILED DESCRIPTION OF THE INVENTION

[0017] Keratin substances Keratinous materials include hair, skin, nails (e.g., fingernails and / or toenails). Wool, fur, and feathers are also included within the definition of keratinous materials.

[0018] Preferably, keratinous materials are understood to be human hair, human skin and human nails (in particular fingernails and toenails). Keratinous materials are understood to be human hair.

[0019] Agents (a) and (b) In the method of the present invention, agents (a) and (b) are applied to keratinous materials, in particular human hair. The two measures (a) and (b) are different from each other.

[0020] Therefore, the following steps: - applying an agent (a) comprising at least one organosilicon compound to keratinous materials, and - applying to the keratin material an agent (b) comprising at least one coloring compound (b1) comprising at least one effect pigment, and at least one film-forming polymer (b2), comprising a substrate platelet α) and a coating β). A method for dyeing keratinous materials, in particular human hair, comprising the steps of: (i) applying a coating having at least one layer of a metal oxide and / or metal oxide hydrate and (ii) a coloring compound from the group of pigments; and (a) applying a coating having at least one layer of a metal oxide and / or metal oxide hydrate and a coloring compound from the group of pigments; and (b ...

[0021] Agent (a) Agent (a) is characterized in that it contains at least one organosilicon compound, in particular at least one organosilane. The organosilicon compounds or organosilanes contained in agent (a) are reactive compounds.

[0022] Composition (a) contains an organosilicon compound, particularly an organosilane, in a cosmetic carrier that can be water-containing, low-water-containing, or anhydrous.The cosmetic carrier can also be liquid, gel-like, creamy, paste, powder, or even solid (for example, in the form of a tablet or pressed product).Preferably, the cosmetic carrier of formulation (a) is an aqueous or aqueous alcoholic carrier.For hair dyes, such carriers are, for example, creams, emulsions, gels, or surfactant-containing foam liquids such as shampoos, foam aerosols, foam compositions, or other preparations suitable for application to hair.

[0023] The cosmetic carrier preferably contains water, meaning that the carrier contains at least 2% water by weight based on its weight. Preferably, the water content is greater than 5% by weight, more preferably greater than 10% by weight, and even more preferably greater than 15% by weight. The cosmetic carrier may be hydroalcoholic. Aqueous / alcoholic solutions herein are aqueous solutions containing 2-70% by weight of a C1-C4 alcohol, more specifically ethanol or isopropanol. The agent may further contain other organic solvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol, or 1,2-propylene glycol. All water-soluble organic solvents are preferred.

[0024] As used herein, the term "colorant" refers to a colorant for keratinous materials, particularly human hair, that is produced using pigments and / or direct dyes. During this coloring process, the coloring compounds are deposited on the surface of the keratinous material in a particularly homogeneous and smooth film or diffuse into the keratinous fibers. The film is formed in situ by oligomerization or polymerization of the organosilicon compound and by the interaction of the organosilicon compound with the coloring compound.

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

[0026] 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. Organosilicon compounds are preferably compounds containing 1 to 3 silicon atoms. Organosilicon compounds preferably contain 1 or 2 silicon atoms.

[0027] The agent (a) particularly preferably comprises at least one organosilicon compound (a1) selected from silanes having one, two or three silicon atoms.

[0028] According to the IUPAC method, the term "silane" is a compound 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 hydroxy groups.

[0029] In a particularly preferred embodiment, the method is characterized in that an agent (a) comprising at least one organosilicon compound selected from silanes containing one, two or three silicon atoms is applied to the keratinous material.

[0030] Agent (a) particularly preferably comprises at least one organosilicon compound selected from silanes containing one, two or three silicon atoms, which organosilicon compound further comprises one or more hydroxyl or hydrolyzable groups and one or more basic chemical functional groups per molecule.

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

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

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

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

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

[0036] In another very particularly preferred embodiment, the method comprises applying an agent (a) to keratinous materials or human hair, the agent (a) being a compound represented by formula (I) and / or (II): Formula (I): R1R2N-L-Si(OR3) a (R4) b (I) [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] Formula (II): TIFF0007739257000001.tif6134[In the formula, -R5, R 5' , R 5"each independently represents a hydrogen atom or a C1-C6 alkyl group; -R6, R 6' and R 6" each independently represents a C1-C6 alkyl group; -A, A', A", A"' and A"" are independently straight or branched chain divalent 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): -(A"")-Si(R6") d" (OR5") c" (III) represents a group represented by -c represents an integer from 1 to 3, -d represents the integer 3-c, -c' represents an integer 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, - at least one of e, f, g and h is different from 0] The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0037] Examples of substituents R1, R2, R3, R4, R5, R5', R5", R6, R6', R6", R7, R8, L, A, A', A", A'' and A"" in compounds of formula (I) and (II) are shown below.

[0038] Examples of C1-C6 alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl, and n-hexyl. Propyl, ethyl, and methyl are preferred alkyl groups. Examples of C2-C6 alkenyl groups are vinyl, allyl, but-2-enyl, but-3-enyl, and isobutenyl, with vinyl and allyl being preferred C2-C6 alkenyl groups. Preferred examples of hydroxy C1-C6 alkyl groups are hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, and 6-hydroxyhexyl groups; the 2-hydroxyethyl group is particularly preferred. Examples of amino C1-C6 alkyl groups are aminomethyl, 2-aminoethyl, and 3-aminopropyl groups. The 2-aminoethyl group is particularly preferred. Straight-chain divalent C1-C 20 Examples of alkylene groups include methylene (-CH-), ethylene (-CH-CH-), propylene (-CH-CH-CH-), and butylene (-CH-CH-CH-CH-). Propylene (-CH-CH-CH-) is particularly preferred. Divalent alkylene groups may be branched from a chain length of 3 C atoms. Branched divalent C-C 20 Examples of alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0039] Formula (I): R1R2N-L-Si(OR3) a (R4) b (I) In the organosilicon compound (a1) of the formula: the radicals R1 and R2 independently of one another represent a hydrogen atom or a C1-C6 alkyl group. Highly preferably, R1 and R2 both represent a hydrogen atom.

[0040] At the center of the organosilicon compound (a1) is a structural unit or linker -L-, which is a linear or branched divalent C-C 20 It means an alkylene group.

[0041] Preferably, -L- is a linear divalent C-C 20 It means an alkylene group. More preferably, -L- means a straight-chain divalent C1-C6 alkylene group. Particularly preferred -L- means a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-) or a butylene group (-CH2-CH2-CH2-CH2-). L means a propylene group (-CH2-CH2-CH2-).

[0042] Formula (I): R1R2N-L-Si(OR3) a (R4) b (I) The organosilicon compound (a1) represented by the formula (a1) has a silicon-containing group -Si(OR3) at one end. a (R4) b It has.

[0043] 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, and R3 and R4 each independently represent a methyl group or an ethyl group.

[0044] 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.

[0045] The most washfast dyeings were obtained when the agent (a) contained at least one organosilicon compound (a1) of formula (I) in which the radicals R3 and R4, independently of one another, represent a methyl or ethyl group.

[0046] Furthermore, dyeings with the best washing fastness properties were obtained when the agent (a) contained at least one organosilicon compound (a1) of formula (I) where a is the number 3, in which case the remaining b's are the number 0.

[0047] In another preferred embodiment, the agent (a) is characterized in that it comprises at least one organosilicon compound (a1) of formula (I) in which R3 and R4, independently of one another, represent a methyl or ethyl group, a represents the number 3, and b represents the number 0.

[0048] In another preferred embodiment, the method comprises the step of: R1R2N-L-Si(OR3) a (R4) b (I) [In the formula, -R1 and R2 both represent hydrogen atoms; -L represents a linear divalent C1-C6 alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or an ethylene group (-CH2-CH2-), -R3 represents a hydrogen atom, an ethyl group, or a methyl group; -R4 represents a methyl group or an ethyl group; -a represents the number 3, -b represents the number 0] The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0049] When b is 0, the group R4 is absent in the compound of formula (I).

[0050] Thus, in another preferred embodiment, the method comprises the step of: R1R2N-L-Si(OR3) a (R4) b (I) [In the formula, -R1 and R2 both represent hydrogen atoms; -L represents a linear divalent C1-C6 alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or an ethylene group (-CH2-CH2-), -R3 represents a hydrogen atom, an ethyl group, or a methyl group; -a represents the number 3, -b represents the number 0] The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0051] Organosilicon compounds (a1) of formula (I) that are particularly suitable for solving the problems of the present invention are -(3-aminopropyl)triethoxysilane TIFF0007739257000002.tif3473-(3-aminopropyl)trimethoxysilane TIFF0007739257000003.tif3465-1-(3-aminopropyl)silanetriol TIFF0007739257000004.tif2056-(2-aminoethyl)triethoxysilane TIFF0007739257000005.tif3464-(2-aminoethyl)trimethoxysilane TIFF0007739257000006.tif3455-1-(2-aminoethyl)silanetriol TIFF0007739257000007.tif2047-(3-Dimethylaminopropyl)triethoxysilane TIFF0007739257000008.tif3475-(3-Dimethylaminopropyl)trimethoxysilane TIFF0007739257000009.tif3466-1-(3-dimethylaminopropyl)silanetriol TIFF0007739257000010.tif2057-(2-Dimethylaminoethyl)triethoxysilane TIFF0007739257000011.tif3566-(2-dimethylaminoethyl)trimethoxysilane, and / or TIFF0007739257000012.tif3457-1-(2-dimethylaminoethyl)silanetriol The file is TIFF0007739257000013.tif2039.

[0052] In another preferred embodiment, the method comprises the step of: -(3-aminopropyl)triethoxysilane -(3-aminopropyl)trimethoxysilane -1-(3-aminopropyl)silanetriol -(2-aminoethyl)triethoxysilane -(2-aminoethyl)trimethoxysilane -1-(2-aminoethyl)silanetriol -(3-dimethylaminopropyl)triethoxysilane -(3-dimethylaminopropyl)trimethoxysilane -1-(3-dimethylaminopropyl)silanetriol -(2-dimethylaminoethyl)triethoxysilane -(2-dimethylaminoethyl)trimethoxysilane -1-(2-dimethylaminoethyl)silanetriol and -A mixture of them and characterized in that it comprises at least one organosilicon compound (a1) represented by formula (I).

[0053] The organosilicon compound (a1) of formula (I) is commercially available. (3-aminopropyl)trimethoxysilane can be purchased, for example, from Sigma-Aldrich. (3-aminopropyl)triethoxysilane is also commercially available from Sigma-Aldrich.

[0054] In another embodiment, agent (a) has formula (II): The composition comprises at least one organosilicon compound represented by TIFF0007739257000014.tif6134.

[0055] The organosilicon compound (a1) 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.

[0056] 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 e, f, g and h are each, independently of one another, the number 0 or 1, and at least one of e, f, g and h is different from 0. In other words, the organosilicon compound of formula (II) contains at least one atomic group selected from the group consisting of -(A)-, -[NR7-(A')]-, -[O-(A")]- and -[NR8-(A"')]-.

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

[0058] 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.

[0059] 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.

[0060] Dyeings with the best washing fastness were obtained when c and c' both represented the number 3. In this case, d and d' both represented the number 0.

[0061] In another preferred embodiment, the method comprises the step of: TIFF0007739257000015.tif6134[in the formula, -R5 and R5' independently represent a methyl group or an ethyl group; -c and c' together represent the number 3, -d and d' both represent the number 0] The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0062] When c and c' are both the number 3 and d and d' are both the number 0, the organosilicon compound has the formula (IIa): (RO)Si-(A) e -[NR7-(A')] f -[O-(A")] g -[NR8-(A"')] h -Si(OR5')3(IIa) is equivalent to

[0063] e, f, g and h may independently represent the numbers 0 or 1, and at least one of e, f, g and h is different from 0. Thus, the symbols e, f, g and h represent the atomic group -(A) e - and -[NR7-(A')] f -and-[O-(A")] g - and -[NR8-(A"')] h - is present in the central portion of the organosilicon compound represented by formula (II).

[0064] In the present invention, it has been found that the presence of certain atomic groups is particularly advantageous for improving washing fastness. Particularly good results have been obtained when at least two of e, f, g and h represent the number 1. Particularly preferably, e and f together represent the number 1. Furthermore, g and h together represent the number 0.

[0065] When e and f both represent the number 1 and g and h both represent the number 0, the organosilicon compound (a1) has the formula (IIb): (R5O) c (R6) d Si-(A)-[NR7-(A')]-Si(R6') d' (OR5') c' (IIb) is equivalent to

[0066] The groups A, A', A", A"' and A"" are independently straight or branched chain divalent C-C 20 Preferably, the groups A, A', A", A"' and A"" are each independently a linear divalent C-C alkylene group. 20 More preferably, the groups A, A', A", A"' and A"" independently represent a straight chain divalent C1-C6 alkylene group.

[0067] In particular, the groups A, A', A", A"' and A"" independently of one another represent a methylene group (-CH-), an ethylene group (-CH-CH-), a propylene group (-CH-CH-CH-) or a butylene group (-CH-CH-CH-CH-). Particularly preferably, the groups A, A', A", A"' and A"" represent a propylene group (-CH-CH-CH-).

[0068] When f represents the number 1, the organosilicon compound of formula (II) contains the structural group -[NR7-(A')]-.

[0069] When h represents the number 1, the organosilicon compound of formula (II) comprises the structural group -[NR8-(A"')]-.

[0070] In the formula, 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): -(A"")-Si(R6") d "(OR5") c " (III) represents a group represented by the following formula:

[0071] 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 atoms of formula (III).

[0072] When f represents the number 1 and 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 the atomic group of formula (III), the agent (a) contains an organosilicon compound having three reactive silane groups.

[0073] In another preferred embodiment, the method comprises the step of: TIFF0007739257000016.tif6134[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 present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0074] In another preferred embodiment, the method comprises the step of: - e and f together represent the number 1, - g and h together represent the number 0, -A and A' each independently represent a methylene group (-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 comprises at least one organosilicon compound (a1) represented by the following formula:

[0075] The organosilicon compound (a1) of formula (II) suitable for solving the problems of the present invention is -3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007739257000017.tif39113-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007739257000018.tif45130-N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007739257000019.tif39113-N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007739257000020.tif45130-2-[bis[3-(trimethoxysilyl)propyl]amino]ethanol TIFF0007739257000021.tif47113-2-[bis[3-(triethoxysilyl)propyl]amino]ethanol TIFF0007739257000022.tif53130-3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine TIFF0007739257000023.tif60113-3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine TIFF0007739257000024.tif63126-N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine TIFF0007739257000025.tif48113-N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine TIFF0007739257000026.tif54130-N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine TIFF0007739257000027.tif45113-N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The file is TIFF0007739257000028.tif51130.

[0076] The organosilicon compound (a1) of formula (II) is commercially available.

[0077] Bis(trimethoxysilylpropyl)amine, which has the CAS number 82985-35-1, can be purchased from Sigma-Aldrich.

[0078] Bis[3-(triethoxysilyl)propyl]amine, which has the CAS number 13497-18-2, can be purchased, for example, from Sigma-Aldrich.

[0079] N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine, also known as bis(3-trimethoxysilylpropyl)-N-methylamine, is commercially available from Sigma-Aldrich or Fluorochem.

[0080] 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.

[0081] In another preferred embodiment, agent (a) is -3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -N-methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -2-[bis[3-(trimethoxysilyl)propyl]amino]ethanol -2-[bis[3-(triethoxysilyl)propyl]amino]ethanol -3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine -N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine -N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine -N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine, and / or -N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine and characterized in that it comprises at least one organosilicon compound (a1) represented by formula (II).

[0082] In another dyeing test, the agent (a) applied to the keratin material in the method is a dye of formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) It has been found to be particularly advantageous if the composition contains at least one organosilicon compound (a1) of the formula

[0083] Formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The organosilicon compound (a1) represented by the formula (I) is also called an alkylalkoxysilane-type or alkylhydroxysilane-type silane.

[0084] In another preferred embodiment, the method comprises the step of: R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The present invention is characterized in that it comprises at least one organosilicon compound (a1) represented by the following formula:

[0085] In another preferred embodiment, the method comprises the step of: (a) comprising, in addition to one or more organosilicon compounds (a1) of formula (I), a compound of formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The present invention is characterized in that it comprises at least one further organosilicon compound (a1) represented by the following formula:

[0086] In another preferred embodiment, the method comprises the step of: (a) comprising, in addition to one or more organosilicon compounds (a1) of formula (II), a compound of formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The present invention is characterized in that it comprises at least one further organosilicon compound (a1) represented by the following formula:

[0087] In another preferred embodiment, the method comprises the step of: (a) comprising, in addition to one or more organosilicon compounds of formula (I) and / or (II), a compound of formula (IV): R9Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R9 is C1-C 18 represents an alkyl group, -R 10 represents a hydrogen atom or a C1-C6 alkyl group, -R 11 represents a C1-C6 alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k] The present invention is characterized in that it comprises at least one further organosilicon compound (a1) represented by the following formula:

[0088] In the organosilicon compound of formula (IV), the group R9 is C1-C 18 This C1-C alkyl group 18The alkyl group is saturated and may be straight or branched. Preferably, R is a straight chain C-C 18 R9 represents an alkyl group. Preferably, R9 represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, or an n-octadecyl group. Particularly preferably, R9 represents a methyl group, an ethyl group, an n-propyl group, an n-hexyl group, or an n-octyl group.

[0089] In the organosilicon compound (a1) represented by 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.

[0090] In the organosilicon compound (a1) represented by formula (IV), the group R 11 represents a C1-C6 alkyl group. 11 represents a methyl group or an ethyl group.

[0091] 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.

[0092] The dyeings with the best washing fastness properties were obtained when the process used an agent (a) comprising at least one organosilicon compound (a1) of formula (IV) in which k is the number 3. In this case, the remaining m's are the numbers 0.

[0093] Organosilicon compounds (a1) of formula (IV) that are particularly suitable for solving the problems of the present invention are -Methyltrimethoxysilane TIFF0007739257000029.tif3430-Methyltriethoxysilane TIFF0007739257000030.tif4139-Ethyltrimethoxysilane TIFF0007739257000031.tif3439-Ethyltriethoxysilane TIFF0007739257000032.tif4147-n-Hexyltrimethoxysilane TIFF0007739257000033.tif3475-n-Hexyltriethoxysilane TIFF0007739257000034.tif4184-n-Octyltrimethoxysilane TIFF0007739257000035.tif3494-n-Octyltriethoxysilane TIFF0007739257000036.tif41102-n-Dodecyltrimethoxysilane and / or TIFF0007739257000037.tif34130-n-Dodecyltriethoxysilane TIFF0007739257000038.tif43140n-octadecyltrimethoxysilane and / or n-octadecyltriethoxysilane.

[0094] In another preferred embodiment, the method comprises the step of: -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Propyltrimethoxysilane -Propyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -Dodecyltrimethoxysilane -Dodecyltriethoxysilane octadecyltrimethoxysilane and / or -Octadecyltriethoxysilane and characterized in that it comprises at least one organosilicon compound (a1) represented by formula (IV).

[0095] In the course of the investigations leading to the present invention, it was found that even when agent (a) contains two organosilicon compounds that are structurally different from one another, a particularly stable and uniform film is obtained on keratinous materials.

[0096] In another preferred embodiment, the method is characterized in that agent (a) comprises at least two structurally different organosilicon compounds.

[0097] In another preferred embodiment, the method is characterized in that an agent (a) comprising at least one organosilicon compound of formula (I) and at least one organosilicon compound of formula (IV) is applied to the keratinous material.

[0098] In another particularly preferred embodiment, the method comprises applying an agent (a) to keratinous materials, wherein the agent (a1) comprises at least one organosilicon compound of formula (I) selected from the group consisting of (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and further comprises at least one organosilicon compound of formula (IV) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.

[0099] The organosilicon compound is a reactive compound. In the present invention, it has been found that the agent (a) preferably contains one or more organosilicon compounds (a1) in a total amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 5.0 to 10% by weight, based on the total weight of the agent (a).

[0100] In this regard, it has been found to be particularly preferred if agent (a) contains one or more organosilicon compounds (a1) of formula (I) and / or (II) in a total amount of 0.1 to 20% by weight, preferably 0.2 to 15% by weight, particularly preferably 0.2 to 3% by weight, based on the total weight of agent (a).

[0101] It has been found particularly preferred that the agent (a) contains one or more organosilicon compounds (a1) of formula (IV) in a total amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 2 to 8% by weight, based on the total weight of the agent (a).

[0102] In the case of organosilicon compounds having at least one hydrolyzable group, hydrolysis occurs even when a small amount of water is added. Organosilicon compounds and / or hydrolyzates having at least one hydroxyl group can react with each other in a condensation reaction. Therefore, agent (a) can contain both an organosilicon compound having at least one hydrolyzable group and its hydrolyzate and / or condensate. When an organosilicon compound having at least one hydroxyl group is used, agent (a) can contain both an organosilicon compound having at least one hydroxyl group and its condensate.

[0103] Condensate is understood to be the product produced by the reaction of at least two organosilicon compounds, each of which has at least one hydroxyl group or hydrolyzable group per molecule, with the removal of water and / or alkanol.Condensate can be, for example, not only a dimer, but also a trimer or oligomer, and the condensate is in equilibrium with the monomer.Depending on the amount of water used or consumed in hydrolysis, the equilibrium shifts from the organosilicon compound of the monomer to the condensate.

[0104] Particularly good results have been obtained when using organosilicon compounds (a1) of formula (I) and / or (II) in the process. As mentioned above, hydrolysis / condensation begins even with a small amount of water, so hydrolysis products and / or condensation products of organosilicon compounds of formula (I) and / or (II) are also included in this embodiment.

[0105] Particularly durable colorations were obtained when an alkaline formulation of agent (a) was used. Preferably, agent (a) contains water and has a pH of 7 to 11.5, preferably 7.5 to 11, more preferably 8 to 10.5.

[0106] In another very particularly preferred embodiment, the method is characterized in that the agent (a) has a pH of 7 to 11.5, preferably 7.5 to 11, more preferably 8 to 10.5.

[0107] Agent (b) The agent (b) is characterized by the presence of at least one color-imparting compound (b1) and at least one film-forming polymer (b2). The coloring compound (b1) comprises at least one effect pigment comprising a substrate platelet α) and a coating β), the coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments.

[0108] The effect pigments are coloured by the presence in at least one layer of a coloured compound (ii) from the group of pigments.

[0109] Thus, with the aid of "colored" effect pigments, keratin fibers can be dyed in particularly intense and diverse shades.

[0110] The effect pigment comprises a substrate platelet.

[0111] The substrate wafer preferably has an average thickness of at most 150 nm, preferably less than 50 nm, more preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate platelet 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 wafer 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.

[0112] The substrate plate is preferably monolithic. In this specification, "monolithic" means that the substrate plate consists of a single, self-contained unit without cracks, layers, or inclusions, although microstructural variations may occur within the substrate platelet. The substrate platelet is preferably homogeneous in structure, i.e., there are no concentration gradients within the platelet. In particular, the substrate platelet does not have a layered structure and does not have particles or dispersed particles therein.

[0113] The dimensions of the substrate platelets can be adjusted depending on the specific application, for example the desired effect on keratinous materials. Typically, the substrate platelets have an average maximum diameter of about 2 to 200 μm, especially about 5 to 100 μm.

[0114] In a preferred embodiment, the shape factor (aspect ratio), which is the ratio of the average dimension to the average thickness, is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably greater than 750. The average dimension of the uncoated substrate platelet is the d50 value of the uncoated substrate platelet. Unless otherwise stated, the d50 value is measured by quixel wet dispersion using a Sympatec Helos instrument. To prepare the sample, the sample to be analyzed is pre-dispersed in isopropanol for 3 minutes.

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

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

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

[0118] Aluminum substrate plates can be produced, inter alia, by stamping from aluminum foil or by common milling and spraying techniques. For example, aluminum flakes are available from the Hall process, which is a wet milling process.

[0119] Other metal flakes, such as bronze flakes, can be obtained by dry milling processes such as the Hametag process.

[0120] The substrate platelets can have various shapes. For example, lamellar and lenticular metal platelets or so-called vacuum deposited pigments (VMP) can be used as substrate platelets. Lamellar substrate platelets are characterized by irregularly configured edges and are also called "cornflakes" because of their appearance. Lenticular substrate flakes have regularly rounded edges and are also called "dollar coins" because of their appearance.

[0121] The metal or metal alloy substrate plate can be passivated, for example, by anodizing (oxide layer) or chromating.

[0122] The coating can change the surface and / or optical properties of the effect pigment and increase the mechanical and chemical load-bearing capacity of the effect pigment. For example, only the upper and / or lower surface of the substrate wafer can be coated, with the side surfaces being recessed. Preferably, the entire surface of the substrate platelet, including the side surfaces, which may be passivated if desired, is covered by the layer. The substrate platelet is preferably completely covered by the coating.

[0123] The coating may be composed of one or more layers. In a preferred embodiment, the coating has only layer A. In an equally preferred embodiment, the coating has a total of at least two, preferably two or three layers. It may be preferred that the coating has two layers A and B, with layer B being different from layer A. Preferably, layer A is located between layer B and the surface of the substrate plate. In another preferred embodiment, the coating has three layers A, B, and C. In this embodiment, layer A is located between layer B and the surface of the substrate wafer, and layer C is located above layer B, which is different from the layer B below.

[0124] Suitable materials for layer A, and optionally layers B and C, are all substances that can be applied to the substrate platelet in the long term. Such materials should preferably be applied in the form of a film. Preferably, the entire surface of the substrate platelet, including the side surfaces and optionally passivated, is covered by layer A, or layers A and B, or layers A, B and C.

[0125] It is preferred that the metal oxide and / or metal oxide hydrate (i) is selected from the group consisting of silicon (dioxide), silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromium oxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide, zinc oxide and mixtures thereof.

[0126] Layer A preferably contains at least one low refractive index metal oxide and / or metal oxide hydrate. Preferably, Layer A contains at least 95% by weight of low refractive index metal oxide (hydrate). The low refractive index material has a refractive index of 1.8 or less, preferably 1.6 or less.

[0127] Suitable low refractive index metal oxides for Layer A include, for example, silicon dioxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, and mixtures thereof, with silicon dioxide being preferred. Layer A preferably has a thickness of 1 to 100 nm, particularly preferably 5 to 50 nm, and particularly preferably 5 to 20 nm.

[0128] If present, Layer B may comprise at least one high refractive index metal oxide (hydrate) different from Layer A. The high refractive index material has a refractive index of at least 1.9, preferably at least 2.0, more preferably at least 2.4. Preferably, Layer B comprises at least 95% by weight, more preferably at least 99% by weight, of the high refractive index metal oxide.

[0129] When Layer B comprises a (high refractive index) metal oxide, it preferably has a thickness of at least 50 nm. Preferably, the thickness of Layer B is 400 nm or less, more preferably 300 nm or less.

[0130] Suitable high refractive index metal oxides for layer B are, for example, selectively light-absorbing (i.e., colored) metal oxides such as iron(III) oxide (α- and γ-FeO, red), cobalt(II) oxide (blue), chromium(III) oxide (green), titanium(III) oxide (blue, usually mixed with titanium oxynitride and titanium nitride) and vanadium(V) oxide (orange), as well as mixtures thereof. Colorless high refractive index oxides such as titanium dioxide and / or zirconium oxide are also suitable.

[0131] In addition to the high-refractive-index metal oxide, Layer B can contain a selectively absorbing dye, preferably in an amount of 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight, in each case based on the total amount of Layer B. Suitable dyes are organic and inorganic dyes that can be stably incorporated into the metal oxide coating. Dyes within the meaning of the present invention have a solubility in water (760 mmHg) of more than 0.5 g / L at 25°C and are therefore not considered pigments.

[0132] Alternatively, for metal oxides, layer B may comprise a metal particle-carrying layer, with the metal particles deposited on the surface of this metal particle-only layer. 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 not covered by metal particles.

[0133] The metal particle support layer includes a metal layer and / or a metal oxide layer.

[0134] When the metal particle support layer includes a metal layer and a metal oxide layer, the arrangement of these layers is not limited.

[0135] 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).

[0136] The metal layer can be formed, for example, by adding an alkali to a metal salt solution containing the metal.

[0137] 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.

[0138] A metal particle support layer in the form of a metal oxide layer can be produced, for example, by hydrolysis of an alkoxide of the metal to form the metal of the metal oxide in a sol-gel process.

[0139] The thickness of the metal particle support layer is preferably 30 nm or less, and more preferably in the range of 0.1 to 10 nm.

[0140] 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).

[0141] 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.

[0142] Suitable methods for forming metal particles include vacuum deposition, sputtering, chemical vapor deposition (CVD), electroless plating, etc. Among these methods, electroless plating is particularly preferred.

[0143] In a preferred embodiment, the effect pigment has a further layer C comprising a metal oxide (hydrate) different from the underlying layer 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.

[0144] Layer C preferably has a thickness of 10 to 500 nm, more preferably 50 to 300 nm.

[0145] The coating of the effect pigments has at least one layer which, in addition to the metal oxide and / or metal oxide hydrate, further comprises a color-imparting compound from the group of the pigments.

[0146] The at least one layer comprising a coloring compound (ii) selected from the group consisting of metal oxides and / or metal oxide hydrates (i) and pigments can be layer A, B and / or C. If the coating has only one layer A, layer A also contains a coloring compound (ii) from the group of pigments.

[0147] If the coating of the effect pigment has two layers A and B, each containing a metal oxide, then both layers A and B or only one of these two layers may contain a color-imparting compound (ii) from the group of pigments. Preferably, layer A contains a coloring compound (ii) from the group of pigments.

[0148] If the coating has layers A, B, and C, each containing a metal oxide (hydrate), each of layers A, B, and C can contain a coloring compound (ii) selected from the group consisting of pigments. Alternatively, in this embodiment, two of the three layers can contain a coloring compound from the group consisting of pigments. Thus, coloring compound (ii) can come from the group of pigments in layers A and B, layers A and C, or layers B and C. Similarly, only one of the three layers can contain a coloring compound (ii) from the group consisting of pigments. Thus, coloring compound (ii) can come from the group of pigments in layers A, B, or C. In a particularly preferred embodiment of the effect pigment comprising a coating with layers A, B, and C, coloring compound (ii) comes from the group of pigments in layers A and / or C.

[0149] When the coating comprises layers A, B, and C, where layers A and C comprise metal oxides (hydrates) and layer B comprises a metal layer having metal particles deposited thereon, each of layers A and C may comprise a coloring compound (ii) selected from the group consisting of pigments. Alternatively, in this embodiment, only one of layers A and C may comprise a coloring compound (ii) from the group of pigments.

[0150] In a particularly preferred embodiment of the effect pigment comprising a coating with layers A, B and C, the colored compound (ii) comes from the group of the pigments in layers A and / or C.

[0151] It is particularly preferred that the effect pigment comprises an aluminum substrate platelet and a silica-containing layer A. If the substrate platelet-based effect pigment has a layer A and a layer C, it is preferred that the effect pigment has an aluminum substrate platelet and silica-containing layers A and C.

[0152] At least one layer of the effect pigment comprises a color-imparting compound (ii) from the group of pigments.

[0153] A pigment within the meaning of the present invention is a coloring compound having a solubility in water of less than 0.5 g / L, preferably less than 0.1 g / L, and more preferably less than 0.05 g / L at 25°C. Water solubility can be measured, for example, by the following method: 0.5 g of pigment is weighed into a beaker. A magnetic stirrer is added. 1 L of distilled water is then added. The mixture is heated at 25°C for 1 hour while stirring on a magnetic stirrer. If undissolved pigment components are visible in the mixture after this time, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be visually evaluated, perhaps due to the high strength of the finely dispersed pigment, the mixture is filtered. If undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0154] Suitable pigments may be of inorganic and / or organic origin.

[0155] In a preferred embodiment, the effect pigment comprises at least one color-imparting compound selected from the group consisting of inorganic and / or organic pigments.

[0156] Preferred pigments are selected from synthetic or natural inorganic pigments. Naturally occurring inorganic pigments can be prepared, for example, from chalk, ochre, umber, green earth, calcined Siena or graphite. Also usable inorganic pigments include black pigments such as black iron oxide, colored pigments such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments.

[0157] Particularly suitable are colored metal oxides, metal hydroxides and metal oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and / or molybdates. Particularly preferred pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, pigment blue 29), chromium oxide hydrate (CI 77289), Prussian blue (iron ferrocyanide, CI 77510) and / or carmine (cochineal).

[0158] Colored pearlescent pigments are also particularly preferred. They 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, sodalite, biotite, lepidolite, and margarite. To produce pearlescent pigments combined with metal oxides, mica, primarily muscovite or phlogopite, is coated with the metal oxide.

[0159] 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 the respective pigment can be changed.

[0160] A preferred mica-based pigment is a synthetic mica platelet based on synthetic fluorphlogopite (INCI) and coated with a metal oxide. The synthetic fluorphlogopite platelet is coated with, for example, tin oxide, iron oxide, and / or titanium dioxide. The metal oxide layer may further contain a pigment such as iron hexacyanoferrate (II / III) or carmine red. Such mica pigments are available, for example, from Eckart under the name SYNCRYSTAL.

[0161] Preferred effect pigments are therefore characterized in that they contain at least one coloring compound (ii) from the group of pigments selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or from colored mica or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0162] In another preferred embodiment, the effect pigment is characterized in that it contains at least one coloring compound from the group of pigments selected from mica or mica-based pigments reacted with one or more metal oxides selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron 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).

[0163] Other suitable pigments are based on borosilicate platelets coated with metal oxides, such as tin oxide, iron oxide, silicon dioxide, and / or titanium dioxide. Such borosilicate pigments are available, for example, from Eckart under the name Mirage or from BASF SE under the name Reflecks.

[0164] Examples of particularly suitable pigments are sold by Merck under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron®, by Sensient under the trade names Ariabel® and Unipure®, by Eckart Cosmetic Colors under the trade name Prestige®, by BASF SE under the trade names Flamenco®, Cellini®, Cloisonne®, Duocrome®, Gemtone®, Timica®, MultiReflections, Chione and by Sunstar under the trade name Sunshine®.

[0165] Particularly preferred pigments under the trade name Colorona® are, for example: Colorona Copper, Merck, Mica, CI 77491 (Iron Oxide) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxide), Alumina Colorona Patina Silver, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona RY, Merck, CI 77891 (Titanium Dioxide), Mica, CI 75470 (Carmine) Colorona Oriental Beige, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Dark Blue, Merck, Mica, Titanium Dioxide, Ferric Ferrocyanide Colorona Chameleon, Merck, CI 77491 (iron oxide), mica Colorona Aborigine Amber, Merck, Mica, CI 77499 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Blackstar Blue, Merck, CI 77499 (iron oxide), mica Colorona Patagonian Purple, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) Colorona Red Brown, Merck, Mica, CI 77491 (Iron Oxides), CI 77891 (Titanium Dioxide) Colorona Russet, Merck, CI 77491 (Titanium Dioxide), Mica, CI 77891 (Iron Oxides) Colorona Imperial Red, Merck, Mica, Titanium Dioxide (CI 77891), D&C Red No. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (Titanium Dioxide), Mica, CI 77288 (Chromium Oxide Green) Colorona Light Blue, Merck, Mica, Titanium Dioxide (CI 77891), Ferric Ferrocyanide (CI 77510) Colorona Red Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Gold Plus MP 25, Merck, Mica, Titanium Dioxide (CI 77891), Iron Oxide (CI 77491) Colorona Carmine Red, Merck, mica, titanium dioxide, carmine Colorona Blackstar Green, Merck, Mica, CI 77499 (Iron Oxides) Colorona Bordeaux, Merck, Mica, CI 77491 (Iron Oxides) Colorona Bronze, Merck, Mica, CI 77491 (Iron Oxide) Colorona Bronze Fine, Merck, Mica, CI 77491 (Iron Oxides) Colorona Fine Gold MP 20, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Sienna Fine, Merck, CI 77491 (iron oxide), mica Colorona Sienna, Merck, Mica, CI 77491 (Iron Oxides) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, CI 77491 (Iron Oxide), Tin Oxide Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxides, Mica, CI 77891, CI 77491 (EU) Colorona Mica Black, Merck, CI 77499 (Iron Oxides), Mica, CI 77891 (Titanium Dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Blackstar Gold, Merck, Mica, CI 77499 (Iron Oxides) Colorona SynCopper, Merck, Synthetic Fluorphlogopite and Iron Oxide Colorona SynBronze, Merck, Synthetic Fluorphlogopite and Iron Oxide

[0166] Particularly preferred pigments under the trade name Xirona® are, for example: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Le Rouge, Merck, iron oxide and silica

[0167] Particularly preferred pigments under the trade name Unipure (registered trademark) are, for example: Unipure Red LC 381 EM, Sensitive CI 77491 (iron oxide), silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxide), Silica

[0168] Particularly preferred pigments under the trade name Unipure (registered trademark) are, for example: Unipure Red LC 381 EM, Sensitive CI 77491 (iron oxide), silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxide), Silica

[0169] In another embodiment, the effect pigment may also comprise one or more color-imparting compounds (ii) selected from the group consisting of organic pigments.

[0170] Organic pigments are correspondingly insoluble organic dyes or colorants which may be selected, for example, from the group consisting of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine and / or triarylmethane compounds.

[0171] Examples of particularly suitable organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a color index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a color index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a color index of CI 61565, CI 61570, CI 74260, orange pigments with a color index of CI 11725, CI 15510, CI 45370, CI 71105, and orange pigments with a color index of CI 12085, CI 12120, CI 13000, CI 14000, CI 15000, CI 16000, CI 17000, CI 18000, CI 19140, CI 20040, CI 21100, CI 21108, CI 4 ...9140, CI 20040, CI 21100, CI 21108, CI 47000, CI 19140, CI 20040, CI 21100, 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.

[0172] In another particularly preferred embodiment, the effect pigment is selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with a Color Index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with a Color Index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with a Color Index of CI 61565, CI 61570, CI 74260, orange pigments with a Color Index of CI 11725, CI 15510, CI 45370, CI 71105, and tallow pigments with a Color Index of CI 12085, CI 13000, CI 14000, CI 15000. 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915, CI 75470 red pigments, and mixtures thereof.

[0173] The organic pigment may be a color paint. In the present invention, the term "color lacquer" is understood to mean a particle comprising a layer of absorbed dye, and the particle and dye unit are insoluble under the above conditions. The particle may be, for example, an inorganic material, such as aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or aluminum.

[0174] For example, alizarin color varnish can be used.

[0175] Suitable coloring compounds (ii) from the group of pigments are also inorganic and / or organic pigments modified with polymers, which can, for example, increase the affinity of the pigments for the respective materials of at least one layer.

[0176] The particle size of the coloring compound used depends on the layer in which the colorant layer is present. The color-imparting compound preferably has a particle size D smaller than the layer thickness of at least one layer. 90 More preferably, the particle size of the color-imparting compound is 95 is smaller than the layer thickness of at least one layer. Even more preferably, the particle size D of the coloring compound 99 is smaller than the layer thickness of at least one layer. Highly preferably, the particle size D of the coloring compound 100 is smaller than the layer thickness of at least one layer. The particle size of the coloring compound can be measured, for example, using dynamic light scattering (DLS) or static light scattering (SLS). 90 means that 90% of the particles of the coloring compound are smaller than the layer thickness of at least one layer. 95 means that 95% of the particles of the coloring compound are smaller than the layer thickness of at least one layer, and so on.

[0177] (i) metal oxides and / or metal oxide hydrates, and (ii) a coloring compound selected from the group consisting of pigments The amount of color-imparting compound (ii) from the group of pigments in at least one layer comprising is preferably up to 5% by weight, based on the total weight of the layer.

[0178] Layers A and C serve for corrosion protection and chemical and physical stabilization. Particularly preferably, layers A and C contain silicon dioxide or aluminum oxide applied by a sol-gel process.

[0179] Effect pigments based on coated substrate platelets preferably have a thickness of 70 to 500 nm, particularly preferably 100 to 400 nm, particularly preferably 150 to 320 nm, for example 180 to 290 nm. A small thickness of the coated substrate platelet is achieved by keeping the thickness of the uncoated substrate platelet small, but also by adjusting the thickness of coating A and, if present, coating C, to as small a value as possible.

[0180] The adhesion and abrasion resistance of effect pigments comprising a substrate platelet α) and a coating β) on keratinous materials, where the coating has at least one layer of metal oxides and / or metal oxide hydrates (i) and a coloring compound (ii) from the pigment group, can be significantly improved by further modifying the outermost 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, preferably metal oxide-containing, layer A, B, or C. The outermost layer refers to the layer spatially furthest from the substrate platelet. The organic compounds are preferably functional silane compounds capable of bonding to the metal oxide-containing layer A, B, or C. These may be monofunctional or bifunctional compounds.

[0181] 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( 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, or phenylallyldichlorosilane.

[0182] Further modification with monofunctional silanes, alkylsilanes, or arylsilanes can be carried out. This has only one functional group covalently bonded to the surface (i.e., the outermost, metal oxide-containing layer) of the effect pigment comprising the substrate platelet (α) and the coating (β), or to the metal surface if the coating is not fully coated. Here, the coating comprises at least one layer of a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the pigment group. The hydrocarbon group of the silane points away from the pigment. Depending on the type and nature of the hydrocarbon group 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 silica-coated aluminum substrate platelets surface-modified with monofunctional silanes. Octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane are particularly preferred. Due to the altered surface properties / hydrophobization, adhesion, abrasion resistance and conformability in application can be improved.

[0183] It has also been found that effect pigments with such surface modifications exhibit better compatibility with the organosilicon compounds and / or their condensates or polymers used.

[0184] Particularly good results have been obtained when agent (a) contains one or more effect pigments in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, and very preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0185] Agent (b) may, in addition to the effect pigment, comprise further coloring compounds selected from the group consisting of pigments and / or direct dyes.

[0186] The agent (b) is further characterized in that it comprises at least one film-forming polymer (b2).

[0187] Polymer is a macromolecule that has a molecular weight of at least 1000g / mol, preferably at least 2500g / mol, particularly preferably at least 5000g / mol, and is composed of identical repeating organic units.The polymer of the present invention can be a synthetic polymer that is produced by polymerizing one kind of monomer or by polymerizing multiple kinds of monomers that are structurally different from each other.When polymer is produced by polymerizing one kind of monomer, it is called homopolymer.When multiple kinds of structurally different monomers are used in polymerization, the resulting polymer is called copolymer.

[0188] The maximum molecular weight of the polymer depends on the degree of polymerization (number of polymerized monomers) and batch size, which is determined by the polymerization method. In the present invention, the maximum molecular weight of the film-forming polymer (b) is 10 7 g / mol or less, preferably 10 6 g / mol or less, particularly preferably 10 5 It is preferred that it is less than or equal to g / mol.

[0189] 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. The formation of a film can be demonstrated, for example, by microscopic observation of keratinous materials treated with the polymer.

[0190] The film-forming polymer (b2) in agent (b) may be hydrophilic or hydrophobic.

[0191] In a first embodiment, it may be preferable to use at least one hydrophobic film-forming polymer in agent (b).

[0192] A hydrophobic polymer is a polymer that has a solubility in water of less than 1% by weight at 25° C. (760 mmHg).

[0193] The solubility of a film-forming hydrophobic polymer in water can be measured, for example, as follows: Place 1 g of polymer in a beaker. Draw up to 100 g with water. Add a magnetic stir bar and heat the mixture to 25°C on a magnetic stirrer while stirring. Allow to stir for 60 minutes. The aqueous mixture is then visually assessed. If the polymer-water mixture cannot be visually assessed due to high turbidity of the mixture, filter the mixture. If undissolved polymer remains on the filter paper, the polymer solubility is less than 1% by weight.

[0194] These include acrylic acid type polymers, polyurethanes, polyesters, polyamides, polyureas, cellulose polymers, nitrocellulose polymers, silicone polymers, acrylamide type polymers and polyisoprene.

[0195] Particularly suitable film-forming hydrophobic polymers are, for example, polymers from the group consisting of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and / or polyamides.

[0196] In another preferred embodiment, the composition (b) is characterized in that it comprises at least one film-forming hydrophobic polymer (b2) selected from the group consisting of copolymers of acrylic acid, copolymers of methacrylic acid, homopolymers or copolymers of acrylic acid esters, homopolymers or copolymers of methacrylic acid esters, homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and / or polyamides.

[0197] It has been found that film-forming hydrophobic polymers selected from the group of synthetic polymers, polymers obtained by radical polymerization or natural polymers are particularly suitable for solving the problems in the present invention.

[0198] Other particularly suitable film-forming hydrophobic polymers are olefins, such as cycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinyl amides, at least one C-C 20 Alkyl group, aryl group or C2-C 10 It can be selected from homopolymers or copolymers of esters or amides of (meth)acrylic acid having hydroxyalkyl groups.

[0199] Other film-forming hydrophobic polymers may be selected from homopolymers or copolymers of isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, isopentyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and / or mixtures thereof.

[0200] Another film-forming hydrophobic polymer is (meth)acrylamide, N-alkyl (meth)acrylamide, C2-C 18 It can be selected from those having an alkyl group, such as homopolymers or copolymers of N-ethylacrylamide, N-tert-butylacrylamide, N-octylacrylamide, and N-di(C1-C4)alkyl(meth)acrylamide.

[0201] Other preferred anionic copolymers are, for example, copolymers of acrylic acid, methacrylic acid, or their C1-C6 alkyl esters, which are sold under the INCI name 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.

[0202] Very particularly preferred commercially available polymers are, for example, Aculyn® 22 (acrylates / steareth-20 methacrylate copolymer), Aculyn® 28 (acrylates / beheneth-25 methacrylate copolymer), Structure 2001® (acrylates / steareth-20 itaconate copolymer), Structure 3001® (acrylates / ceteth-20 itaconate copolymer), Structure Plus® (acrylates / aminoacrylate C10-30 alkyl PEG-20 itaconate copolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (acrylates / C10-30 alkyl acrylate crosspolymer), Synthalen W 2000® (acrylates / palmethylene-25 acrylate copolymer) or Rohme und The commercially available product is Soltex OPT (Acrylates / C12-22 Alkyl Methacrylate Copolymer) manufactured by Haas.

[0203] Suitable polymers based on vinyl monomers include, for example, homopolymers and copolymers of N-vinylpyrrolidone, vinylcaprolactam, vinyl-(C1-C6)alkyl-pyrrole, vinyloxazole, vinylthiazole, vinylpyrimidine or vinylimidazole.

[0204] Also particularly suitable are copolymers octylacrylamide / acrylates / butylaminoethyl methacrylate copolymers, such as those sold under the trade names AMPHOMER® or LOVOCRYL® 47 by NATIONAL STARCH, or the acrylates / octylacrylamide copolymers sold under the trade names DERMACRYL® LT and DERMACRYL® 79 by NATIONAL STARCH.

[0205] Suitable olefin-based polymers include homopolymers and copolymers of ethylene, propylene, butene, isoprene, and butadiene.

[0206] In another embodiment, the film-forming hydrophobic polymer may be a block copolymer containing at least one block of styrene or a styrene derivative. Such a block copolymer may be a copolymer containing one or more blocks in addition to the styrene block, such as styrene / ethylene, styrene / ethylene / butylene, styrene / butylene, styrene / isoprene, or styrene / butadiene. Such polymers are commercially available from BASF under the trade name "Luvitol HSB."

[0207] Surprisingly, it has been found that particularly intense and wash-fast colorations are obtained when agent (b) comprises at least one film-forming polymer (b2) selected from the group consisting of homopolymers and copolymers of acrylic acid, homopolymers and copolymers of methacrylic acid, homopolymers and copolymers of acrylic acid esters, homopolymers and copolymers of methacrylic acid esters, homopolymers and copolymers of acrylic acid amides, homopolymers and copolymers of methacrylic acid amides, homopolymers and copolymers of vinylpyrrolidone, homopolymers and copolymers of vinyl alcohol, homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of ethylene, homopolymers and copolymers of propylene, homopolymers and copolymers of styrene, polyurethanes, polyesters and polyamides.

[0208] In another preferred embodiment, the method is characterized in that the agent (b) comprises at least one film-forming polymer (b2) selected from the group consisting of homopolymers and copolymers of acrylic acid, homopolymers and copolymers of methacrylic acid, homopolymers and copolymers of acrylic acid esters, homopolymers and copolymers of methacrylic acid esters, homopolymers and copolymers of acrylic acid amides, homopolymers and copolymers of methacrylic acid amides, homopolymers and copolymers of vinylpyrrolidone, homopolymers and copolymers of vinyl alcohol, homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of ethylene, homopolymers and copolymers of propylene, homopolymers and copolymers of styrene, polyurethanes, polyesters and polyamides.

[0209] In another embodiment, it may be preferable to use at least one hydrophilic film-forming polymer (b2) in agent (b).

[0210] 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.

[0211] The solubility of a film-forming hydrophilic polymer in water can be measured, for example, as follows: Place 1 g of polymer in a beaker. Bring to 100 g with water. Add a magnetic stir bar and heat the mixture to 25°C on a magnetic stirrer while stirring. Allow to stir for 60 minutes. The aqueous mixture is then visually assessed. A completely dissolved polymer will appear homogeneous to the naked eye. If the polymer-water mixture cannot be visually assessed due to high turbidity of the mixture, filter the mixture. If no undissolved polymer remains on the filter paper, the solubility of the polymer is greater than 1% by weight.

[0212] Nonionic, anionic and cationic polymers can be used as film-forming hydrophilic polymers.

[0213] 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.

[0214] Furthermore, it is particularly preferred to use polyvinylpyrrolidone (PVP) and / or vinylpyrrolidone-containing copolymers as film-forming hydrophilic polymers.

[0215] In another very particularly preferred embodiment, the agent (b) is characterized in that it comprises at least one film-forming hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone (PVP) and copolymers of polyvinylpyrrolidone.

[0216] It is further preferred if the agent contains polyvinylpyrrolidone (PVP) as the film-forming hydrophilic polymer. Surprisingly, the washfastness of the dyes obtained with the PVP-containing agent (b) was also very good.

[0217] 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.

[0218] The polymer PVP K 30 sold by Ashland (ISP, POI Chemical) is another very suitable polyvinylpyrrolidone (PVP). PVP K 30 is a polyvinylpyrrolidone that is highly soluble in cold water and has the CAS number 9003-39-8. The molecular weight of PVP K 30 is approximately 40,000 g / mol.

[0219] Other particularly suitable polyvinylpyrrolidones are the substances known under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60, LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115, available from BASF.

[0220] The use of film-forming hydrophilic polymers (b2) from the group of the polyvinylpyrrolidone copolymers also leads to particularly good and wash-fast coloring results.

[0221] 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.

[0222] Among the vinylpyrrolidone-containing copolymers, styrene / VP copolymer and / or vinylpyrrolidone-vinyl acetate copolymer and / or VP / DMAPA acrylate copolymer and / or VP / vinylcaprolactam / DMAPA acrylate copolymer are particularly preferred in cosmetic compositions.

[0223] Vinylpyrrolidone-vinyl acetate copolymers are sold by BASF SE under the name Luviskol® VA. For example, VP / vinylcaprolactam / DMAPA acrylate copolymers are sold by Ashland Inc. under the trade name Aquaflex® SF-40. For example, VP / DMAPA acrylate copolymers are sold by Ashland under the name Styleze CC-10, which is a highly preferred vinylpyrrolidone-containing copolymer.

[0224] Other suitable copolymers of polyvinylpyrrolidone may also be obtained by reaction of N-vinylpyrrolidone with at least one further monomer from the group consisting of N-vinylformamide, vinyl acetate, ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactone and / or vinyl alcohol.

[0225] In another very particularly preferred embodiment, the agent (b) is characterized in that it comprises at least one film-forming hydrophilic polymer (b2) selected from the group consisting of polyvinylpyrrolidone (PVP), vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / styrene copolymer, vinylpyrrolidone / ethylene copolymer, vinylpyrrolidone / propylene copolymer, vinylpyrrolidone / vinylcaprolactam copolymer, vinylpyrrolidone / vinylformamide copolymer and / or vinylpyrrolidone / vinyl alcohol copolymer.

[0226] Another fussy copolymer of vinylpyrrolidone is the polymer known by the INCI name Maltodextrin / VP Copolymer.

[0227] It has also been possible to obtain intensely colored keratinous materials, especially hair, having particularly good washfastness properties when non-ionic film-forming hydrophilic polymers are used as film-forming hydrophilic polymers.

[0228] In another embodiment, agent (b) may comprise at least one non-ionic film-forming hydrophilic polymer (b2).

[0229] According to the present invention, nonionic polymers are understood to be polymers that, under standard conditions in protic solvents, such as water, do not have structural units with permanent cationic or anionic groups that must be compensated by counterions, and remain electrically neutral. Cationic groups include quaternized ammonium groups, but do not include protonated amines. Anionic groups include carboxylic and sulfonic acid groups.

[0230] the below described: Polyvinylpyrrolidone, N-vinylpyrrolidone and copolymers of vinyl esters of N-vinylpyrrolidone and vinyl acetate of carboxylic acids containing 2 to 18 carbon atoms, Copolymer of N-vinylpyrrolidone, N-vinylimidazole and methacrylamide, Copolymer of N-vinylpyrrolidone, N-vinylimidazole and acrylamide, Copolymer of N-vinylpyrrolidone and N,N-di(C1-C4)alkylamino-(C2-C4)alkylacrylamide Preferred are formulations which comprise as non-ionic film-forming hydrophilic polymers at least one polymer selected from the group consisting of:

[0231] 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, in particular 30:70 to 60:40. Suitable copolymers of vinylpyrrolidone and vinyl acetate are available, for example, from BASF SE under the trademarks Luviskol® VA 37, Luviskol® VA 55, Luviskol® VA 64 and Luviskol® VA 73.

[0232] Another particularly preferred polymer is selected from the INCI name VP / methacrylamide / vinylimidazole copolymer, which is available from BASF SE under the trade name Luviset Clear.

[0233] Another particularly preferred non-ionic film-forming hydrophilic polymer is the copolymer of N-vinylpyrrolidone and N,N-dimethylaminiopropylmethacrylamide, which is sold, for example, by ISP under the INCI name VP / DMAPA acrylate copolymer, e.g. under the trade name Styleze® CC 10.

[0234] The cationic polymer is a copolymer of N-vinylpyrrolidone, N-vinylcaprolactam, N-(3-dimethylaminopropyl) methacrylamide and 3-(methacryloylamino)propyl-lauryl-dimethylammonium chloride (INCI name: Polyquaternium-69), which is sold, for example, by ISP under the trade name AquaStyle® 300 (28-32% by weight of active substance in an ethanol-water mixture, molecular weight 350,000).

[0235] Other suitable film-forming hydrophilic polymers include: vinylpyrrolidone-vinylimidazolium methchloride copolymers, available under the names Luviquat® FC 370, FC 550 and INCI names Polyquaternium-16, as well as FC 905 and HM 552; vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers (which are commercially available, for example, under the name Aquaflex® SF 40, with acrylic esters and acrylic amides as third monomer components); Examples include:

[0236] Polyquaternium-11 is a reaction product of diethyl sulfate with a copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate. Suitable commercial products are available from BASF SE under the names Dehyquart® CC 11 and Luviquat® PQ 11 PN, or from Ashland Inc. under the names Gafquat 440, Gafquat 734, Gafquat 755, or Gafquat 755N.

[0237] Polyquaternium-46 is a reaction product of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulfate, and is available, for example, from BASF SE under the name Luviquat® Hold. Polyquaternium-46 is preferably used in an amount of 1 to 5 wt. % based on the total weight of the cosmetic composition. It is particularly preferred to use Polyquaternium-46 in combination with a cationic guar compound. It is even more highly preferred to use Polyquaternium-46 in combination with a cationic guar compound and Polyquaternium-11.

[0238] Suitable anionic film-forming hydrophilic polymers may be, for example, acrylic acid polymers, which may be in non-crosslinked or crosslinked form. Such products are sold by Lubrizol under the trade names Carbopol 980, 981, 954, 2984 and 5984, or by 3V Sigma (The Sun Chemicals, Inter-Harz) under the names Synthalen M and Synthalen K.

[0239] Examples of suitable film-forming hydrophilic polymers from the group of natural gums are xanthan gum, gellan gum, carob gum.

[0240] Examples of suitable film-forming hydrophilic polymers from the group of polysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose and carboxymethyl cellulose.

[0241] Suitable film-forming hydrophilic polymers from the acrylamide group are, for example, polymers prepared from (meth)acrylamido-C1-C4-alkylsulfonic acid or salt monomers. The corresponding polymers may be selected from the polymers of polyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid, polyacrylamidopropanesulfonic acid, poly2-acrylamido-2-methylpropanesulfonic acid, poly-2-methylacrylamido-2-methylpropanesulfonic acid and / or poly-2-methylacrylamido-n-butanesulfonic acid.

[0242] Preferred polymers of poly(meth)acrylamide-C1-C4-alkyl-sulfonic acid are crosslinked and at least 90% neutralized. These polymers may be crosslinked or non-crosslinked.

[0243] Crosslinked, fully or partially neutralized polymers of the poly-2-acrylamido-2-methylpropanesulfonic acid type are available under the INCI names "ammonium polyacrylamido-2-methyl-propanesulfonate" or "ammonium polyacryldimethyltauramide".

[0244] 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.

[0245] In another obviously very particularly preferred embodiment, the method is characterized in that the agent (b) comprises at least one anionic film-forming polymer (b2).

[0246] In this context, it is preferred that the agent (b) comprises at least one structural unit of formula (PI) and at least one structural unit of formula (P-II): TIFF0007739257000039.tif29168[In the formula, M is a hydrogen atom, ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium. The best results were obtained when the composition contained at least one film-forming polymer (b2) comprising:

[0247] In a further preferred embodiment, the method comprises the step of: the agent (b) comprises at least one structural unit of formula (PI) and at least one structural unit of formula (P-II): TIFF0007739257000040.tif29168[in the formula, M is a hydrogen atom, ammonium (NH4), sodium, potassium, 1 / 2 magnesium, or 1 / 2 calcium. The film-forming polymer (b2) is characterized in that it contains at least one film-forming polymer (b2) containing:

[0248] When M represents a hydrogen atom, the structural unit represented by formula (PI) is based on an acrylic acid unit.

[0249] When M represents an ammonium counterion, the structural unit of formula (PI) is based on the ammonium salt of acrylic acid.

[0250] When M represents a sodium counterion, the structural unit of formula (PI) is based on the sodium salt of acrylic acid.

[0251] When M represents a potassium counterion, the structural unit of formula (PI) is based on the potassium salt of acrylic acid.

[0252] When M represents half an equivalent of a magnesium counterion, the structural unit of formula (PI) is based on the magnesium salt of acrylic acid.

[0253] When M represents half an equivalent of a calcium counterion, the structural unit of formula (PI) is based on the calcium salt of acrylic acid.

[0254] The one or more film-forming polymers (b2) are preferably used in agent (b) in specific quantitative ranges. In this context, it has been found to be particularly advantageous for solving the problems of the present invention when agent (b) comprises one or more film-forming polymers (b2) in a total amount of 0.1 to 18% by weight, preferably 1 to 16% by weight, more preferably 5 to 14.5% by weight, and very particularly preferably 8 to 12% by weight, relative to the total weight of agent (b).

[0255] In a further preferred embodiment, the method is characterized in that the agent (b) comprises one or more film-forming polymers (b2) in a total amount of 0.1 to 18% by weight, preferably 1 to 16% by weight, more preferably 5 to 14.5% by weight, very particularly preferably 8 to 12% by weight, relative to the total weight of agent (b).

[0256] Other ingredients in formulations (a) and (b) Agents (a) and (b) may contain one or more optional ingredients.

[0257] It is particularly preferred that the agent (a) used in the dyeing process comprises at least one coloring compound (a2) selected from the group consisting of pigments and / or direct dyes.

[0258] In this regard, the use of pigments has been found to be particularly preferred.

[0259] In another very particularly preferred embodiment, the method is characterized in that the agent (a) comprises at least one coloring compound (a2) selected from the group consisting of pigments.

[0260] Pigments from the group of pigments which can be used as coloring compound (a2) correspond to those already described above as coloring compound (ii).

[0261] In a preferred embodiment, the agent is characterized in that the agent (a) comprises at least one color-imparting compound (a2) from the group consisting of inorganic and / or organic pigments.

[0262] In another preferred embodiment, the method is characterized in that the agent (a) comprises at least one coloring compound (a2) from the group of inorganic pigments selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or from colored mica or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0263] In another preferred embodiment, the method is characterized in that the agent (a) comprises at least one coloring compound (a2) from the group of pigments selected from mica or mica-based pigments reacted with one or more metal oxides selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron 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).

[0264] Other effect pigments, such as metallic luster pigments, can be used.

[0265] Effect pigments can include, for example, lamellar substrate platelet-based pigments, lenticular substrate platelet-based pigments, substrate platelet-based pigments, including vacuum deposited pigments (VMPs).

[0266] Suitable effect pigments include, for example, the pigments Alegrace® Marvelous, Alegrace® Gorgeous or Alegrace® Aurous from Schlenk Metallic Pigments.

[0267] Also suitable effect pigments are the aluminum-based pigments of the SILVERDREAM series and the VISIONAIRE series of pigments from Eckart, which are based on aluminum or copper / zinc-containing metal alloys.

[0268] Other suitable effect pigments are the aluminum-based pigments of the Cosmicolor® series manufactured by Toyal Europe. A particularly suitable effect pigment is the colored effect pigment Cosmicolor® Celeste.

[0269] Other suitable effect pigments are based on platelet-shaped borosilicates coated with metal oxides, such as tin oxide, iron oxide, silicon dioxide, and / or titanium dioxide. Such borosilicate-based pigments are available, for example, from Eckart under the name Mirage or from BASF SE under the name Reflecks.

[0270] Particularly good results have been obtained when agent (a) contains one or more pigments as coloring compounds (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, and very preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0271] In another embodiment of the method, the agent (a) may contain one or more coloring compounds (a2) from the group of the organic pigments.

[0272] In another particularly preferred embodiment, the method comprises the step of: providing composition (a) containing at least one of carmine, quinacridone, phthalocyanine, sorghum, blue pigments having a Color Index of CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments having a Color Index of CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments having a Color Index of CI 61565, CI 61570, CI 74260, orange pigments having a Color Index of CI 11725, CI 15510, CI 45370, CI 71105, red pigments having a Color Index of CI 12085, CI 13000, CI 14000, CI 15000, CI 16000, CI 17000, CI 18000, CI 19000, CI 20000, CI 21100, CI 21108, CI 21100, CI 21108, CI 47000, CI 47005, 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.

[0273] The use of such pigments in agent (a) is particularly preferred due to their excellent stability to light and temperature. It is also preferred that the pigments used have a specific particle size. This particle size, on the one hand, ensures a uniform distribution of the pigment in the polymer film formed, and, on the other hand, avoids rough hair or skin feel after application of the cosmetic product. Therefore, in the present invention, at least one pigment has an average particle size D of 1 to 50 μm, preferably 5 to 45 μm, preferably 10 to 40 μm, and 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).

[0274] The agent (a) used in the method as the coloring compound (a2) may contain one or more direct dyes. Direct-acting dyes are dyes that act directly on hair and do not require an oxidation step to form color. Direct dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0275] Direct 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, direct dyes within the meaning of the present invention have a solubility in water (760 mmHg) at 25°C of greater than 1 g / L.

[0276] Direct dyes can be classified into anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

[0277] In another preferred embodiment, the method is characterized in that the agent (a) further contains at least one anionic direct dye, cationic direct dye and / or non-ionic direct dye as coloring compound (a2).

[0278] In another preferred embodiment, the method is characterized in that the agent (a) further comprises at least one coloring compound (a2) selected from the group consisting of anionic direct dyes, nonionic direct dyes and / or cationic direct dyes.

[0279] 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.

[0280] 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.

[0281] During the course of investigations leading to the present invention, it was found that dyed goods of particularly high color strength can be produced by using agent (a) containing at least one anionic direct dye.

[0282] Therefore, in a very particularly preferred embodiment, the method is characterized in that the agent (a) further comprises, as coloring compound (a2), at least one anionic direct dye.

[0283] Anionic direct dyes are also called acid dyes. Acid dyes are direct dyes that have at least one carboxylic acid group (-COOH) and / or at least one sulfonic acid group (-SO3H). Depending on the pH value, the protonated forms of the carboxylic acid or sulfonic acid groups (-COOH, -SO3H) can be converted to their deprotonated forms (-OO - , -SO3 - The proportion of the protonated form increases with decreasing pH. When direct dyes are used as their salts, the carboxylic or sulfonic acid groups are present in deprotonated form and are neutralized with the corresponding stoichiometrically equivalent cation to maintain electrical neutrality. Acid dyes can also be used in the form of their sodium and / or potassium salts.

[0284] 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.

[0285] Alkaline earth salts (e.g., calcium and magnesium salts) or aluminum salts of acid dyes often have lower solubilities than the corresponding alkali salts. If the solubility of these salts is less than 0.5 g / L (25°C, 760 mmHg), they are not included in the definition of direct dyes.

[0286] 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, such as those found in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthan dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.

[0287] In one embodiment, a method for dyeing keratin materials is preferred, characterized in that the composition (a) further comprises, as coloring compound (a2), at least one anionic direct dye selected from the group consisting of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthan dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes, each of which has at least one carboxylic acid group (-COOH), sodium carboxylate group (-COONa), potassium carboxylate group (-COOK), sulfonic acid group (-SOH), sodium sulfonate group (-SONa) and / or potassium sulfonate group (-SOK).

[0288] For example, one or more compounds from the following groups may be selected as particularly suitable acid dyes: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA no. B001), Acid Yellow 3 (COLIPA no. 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 no. 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 no. 015), Acid Orange 10 (CI 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1; CI 20170; KATSU 201; sodium salt-free; Brown No. 201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D&C Brown No. 1), Acid Red 14 (CI 14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red 27(E 123, CI 16185, C-Rot 46, Real red D, FD&C Red Nr.2、Food Red 9、Naphthol red S)、Acid Red 33(Red 33、Fuchsia Red、D&C Red 33、CI 17200)、Acid Red 35(CI C.I.18065)、Acid Red 51(CI 45430、Pyrosin B、Tetraiodfluorescein、Eosin J、Iodeosin)、Acid Red 52(CI 45100、Food Red 106、Solar Rhodamine B、Acid Rhodamine B、Red n°106 Pontacyl Brilliant Pink)、Acid Red 73(CI 27290)、Acid Red 87(Eosin、CI 45380)、Acid Red 92(COLIPA n℃53、CI 45410)、Acid Red 95(CI 45425、Erythtosine,Simacid Erythrosine Y)、Acid Red 184(CI 15685)、Acid Red 195、Acid Violet 43(Jarocol Violet 43、Ext. D&C Violet n°2、C.I. 60730、COLIPA n°063)、Acid Violet 49(CI 42640)、Acid Violet 50(CI 50325)、Acid Blue 1(Patent Blue、CI 42045)、Acid Blue 3(Patent Blue V、CI 42051)、Acid Blue 7(CI 42080)、Acid Blue 104(CI 42735)、Acid Blue 9(E 133、Patent blue AE、Amido blue AE、Erioglaucin A、CI 42090、C.I. Food Blue 2)、Acid Blue 62(CI 62045)、Acid Blue 74(E 132、CI 73015)、Acid Blue 80(CI 61585)、Acid Green 3(CI 42085、Foodgreen1)、Acid Green 5(CI 42095)、Acid Green 9(C.I.42100)、Acid Green 22(C.I.42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brilliant Acid Green BS, CI 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n°401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n°B15), Acid Black 52(CI 15711), Food Yellow 8(CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and / or D&C Brown 1. .

[0289] For example, the water solubility of an anionic direct dye can be measured as follows: 0.1 g of anionic direct dye is introduced into a beaker. A magnetic stir bar is added. 100 mL of water is then added. The mixture is heated to 25°C while stirring on a magnetic stirrer. Stir for 60 minutes. The aqueous mixture is then visually evaluated. If undissolved residues are still present, increase the amount of water, for example, in 10 mL increments. Add water until the amount of dye used is completely dissolved. If the dye strength is too high to visually evaluate the dye-water mixture, filter the mixture. If undissolved dye remains on the filter paper, repeat the solubility test with more water. If 0.1 g of anionic direct dye dissolves in 100 mL of water at 25°C, the solubility of the dye is 1 g / L.

[0290] 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).

[0291] Therefore, a particularly preferred method is such that the agent (a) is Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 27, acid red 33, acid red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 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.

[0292] The direct dyes, especially anionic direct dyes, can be used in various amounts in the medium (a) depending on the desired color intensity. Particularly good results are obtained when the agent (a) contains one or more direct dyes (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, and very particularly preferably 0.5 to 4.5% by weight, based on the total weight of the agent (a).

[0293] In another preferred embodiment, the method is characterized in that agent (a) further contains one or more direct dyes as coloring compounds (a2) in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, and very particularly preferably 0.5 to 4.5% by weight, based on the total weight of agent (a).

[0294] The formulation may contain one or more surfactants. The term "surfactant" refers to a surface-active substance. Surfactants are classified into anionic surfactants, which consist of a hydrophobic group and a negatively charged hydrophilic head group; amphoteric surfactants, which have both a negative charge and a countervailing positive charge; cationic surfactants, which have a hydrophobic group and a positively charged hydrophilic group; and nonionic surfactants, which have no charge but have a strong dipole moment and are highly hydrated in aqueous solution.

[0295] 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.

[0296] Amphoteric surfactants are those with a C8-C 24 These surfactants are surface-active compounds that contain at least one free amino group and at least one -COOH or -SOH group in addition to an alkyl or acyl group and are capable of forming an intramolecular salt. Examples of suitable amphoteric surfactants include N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids, and alkylaminoacetic acids, each having approximately 8 to 24 carbon atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines, and sulfobetaines.

[0297] Particularly preferred amphoteric surfactants are N-cocos alkylaminopropionate, cocos acylaminoethylaminopropionate and C 12 -C 18 -acyl sarcosine.

[0298] The formulation may also contain at least one additional nonionic surfactant. Suitable nonionic surfactants are alkyl polyglycosides and alkylene oxide addition products to fatty alcohols and fatty acids, with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with good properties are also obtained when the formulation contains, as a nonionic surfactant, a fatty acid ester of ethoxylated glycerol reacted with at least 2 moles of ethylene oxide.

[0299] The formulation may also contain at least one cationic surfactant. Cationic surfactants are surfactants, i.e., surface-active compounds, each of which has one or more positive charges. Cationic surfactants contain only positive charges. Typically, such surfactants are composed of a hydrophobic portion and a hydrophilic head group, where the hydrophobic portion is usually composed of a hydrocarbon backbone (e.g., consisting of one or two straight or branched alkyl chains), and the positive charge resides in the hydrophilic head group. Examples of cationic surfactants 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 is.

[0300] Furthermore, the cationic charge can also be part of a heterocycle (e.g., an imidazolium or pyridinium ring) in the form of an onium structure. In addition to the functional unit with a cationic charge, the cationic surfactant may also contain other uncharged functional groups, as in the case of esterquats. 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.

[0301] Furthermore, the agent may also contain at least one anionic surfactant. Anionic surfactants are surface active agents that exclusively have an anionic charge (neutralized by the corresponding counter cation). Examples of anionic surfactants are fatty acids, alkyl sulfates, alkyl ether sulfates and ether carboxylic acids, with 12 to 20 carbon atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

[0302] The anionic surfactant is used in a total amount of 0.1 to 45% by weight, preferably 1 to 30% by weight, and most preferably 1 to 15% by weight, based on the total weight of each agent.

[0303] To adjust the desired pH value, the agents (a) and (b) may contain at least one alkalizing and / or acidifying agent. For the purposes of the present invention, the pH value is the pH value measured at a temperature of 22°C.

[0304] As alkalizing agents, agents (a) and (b) may contain, for example, ammonia, alkanolamines and / or basic amino acids.

[0305] The alkanolamine that can be used in the composition is preferably selected from the primary amine that has the C2-C6 alkyl group with at least one hydroxyl group.Preferred alkanolamine is selected from the group consisting of 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol.

[0306] Particularly preferred alkanolamines are selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol.Accordingly, a particularly preferred embodiment is characterized in that agent (a) and / or agent (b) comprise an alkanolamine selected from 2-aminoethan-1-ol and / or 2-amino-2-methylpropan-1-ol as alkalizing agent.

[0307] For the purposes of the present invention, an amino acid is an organic compound whose structure contains at least one protic amino group and at least one -COOH or at least one -SOH group. Preferred amino acids are aminocarboxylic acids, in particular α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0308] According to the present invention, a basic amino acid is an amino acid with an isoelectric point pI greater than 7.

[0309] The basic α-aminocarboxylic acid contains at least one asymmetric carbon atom. In the present invention, both enantiomers can be used equally well as specific compounds or mixtures thereof, especially as racemates. However, it is particularly preferred to use the naturally preferred isomeric form, usually in the L configuration.

[0310] The basic amino acid is preferably selected from the group consisting of arginine, lysine, ornithine and histidine, particularly preferably arginine and lysine.Accordingly, in another particularly preferred embodiment, the agent is characterized in that the alkalizing agent is a basic amino acid selected from the group consisting of arginine, lysine, ornithine and / or histidine.

[0311] Agent (a) and / or agent (b) may also contain other alkalizing agents, in particular inorganic alkalizing agents. Applicable inorganic alkalizing agents are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

[0312] 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.

[0313] Acidifying agents known to those skilled in the art are, for example, organic acids such as citric acid, acetic acid, maleic acid, lactic acid, malic acid or tartaric acid, and dilute mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.

[0314] Agent (a) and / or agent (b) may further comprise a matting agent. Suitable matting agents include, for example, (modified) starch, wax, talc, and / or (modified) silica. The amount of the matting agent is preferably 0.1 to 10% by weight, based on the total amount of agent (a) or agent (b). Preferably, agent (b) comprises a matting agent.

[0315] Agent (a) and / or agent (b) may also contain other active ingredients, auxiliaries and additives, such as solvents; fatty components, such as C8-C 30Fatty acid triglycerides, C8-C 30 Fatty acid monoglycerides, C8-C 30 fatty acid diglycerides and / or hydrocarbons; polymers; structurants, such as glucose or sodium chloride, hair conditioning compounds, such as phospholipids, for example lecithin and cephalin; perfume oils, dimethyl isosorbide and cyclodextrin; fibre structure improving active ingredients, in particular mono-, di- and oligosaccharides, for example glucose, galactose, fructose, fructose and lactose; dyes for colouring the product; anti-dandruff active ingredients, for example piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides; protein hydrolysates of animal and / or plant origin and fatty acid condensates or optionally in the form of anionic or cationically modified derivatives; vegetable oils; light stabilizers and UV blockers; active ingredients, for example panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acid and its salts, bisabolol, They may also contain boroles; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes, such as fatty alcohols, beeswax, montan wax and kerosene; swelling and penetrating agents, such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidine, urea, primary, secondary and tertiary phosphates; opacifying agents, such as latex, styrene / PVP and styrene / acrylamide copolymers; pearlizing agents, such as ethylene glycol mono- and distearate and PEG-3-distearate; and blowing agents, such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0316] The selection of these other substances is made by those skilled in the art according to the desired properties of the agent. Other optional ingredients and the amounts of such ingredients to be used are clearly stated in the relevant manuals known to those skilled in the art. The additional active ingredients and auxiliary agents are preferably used in agent (a) and / or agent (b) in an amount of 0.0001 to 25% by weight and 0.0005 to 15% by weight, respectively, based on the total weight of each agent.

[0317] Method for dyeing keratinous materials The method involves applying agents (a) and (b) to keratinous materials, particularly human hair. Agents (a) and (b) are therefore ready-to-use agents. Agents (a) and (b) are different.

[0318] In principle, agents (a) and (b) can be applied simultaneously or successively, although successive application is preferred.

[0319] The best results were obtained when agent (a) was applied to the keratinous material as a pre-treatment agent and then agent (b) was applied as a colorant.

[0320] Thus, the following: - in a first step, an agent (a) comprising at least one organosilicon compound (a1) is applied to the keratinous materials, and - in a second step, applying to the keratin material an agent (b) comprising at least one coloring compound (b1) comprising at least one effect pigment and at least one film-forming polymer (b2), comprising a substrate platelet α) and a coating β); Particularly preferred is a method for dyeing keratinous materials, in particular human hair, which comprises in this order: (i) a metal oxide and / or metal oxide hydrate; and (ii) a coloring compound from the group of pigments.

[0321] Furthermore, in order to impart a high resistance to washing out to the dyed keratinous material over a long period of time, it is particularly preferred to apply agents (a) and (b) within the same dyeing process, which means that there is a time of at most a few hours between the application of agents (a) and (b).

[0322] In another preferred embodiment, the method is characterized in that agent (a) is applied first, followed by agent (b), and the time between application of agents (a) and (b) is at most 24 hours, preferably at most 12 hours, particularly preferably at most 6 hours.

[0323] The method involves first treating keratinous materials, in particular human hair, with agent (a), followed by applying the actual coloring agent (b), which contains coloring compounds, to the keratinous materials.

[0324] The pretreatment agent (a) is characterized by the inclusion of at least one reactive organosilicon compound. The one or more reactive organosilicon compounds (a) functionalize the hair surface upon contact. Thus, a first film is formed. In the second step of the method, a colorant (b) is then applied to the hair. Upon application of the colorant (b), the colorant interacts with the film formed by the organosilicon compound and thus binds to the keratinous material.

[0325] In another embodiment, the method comprises the steps of: (1) applying agent (a) to keratinous materials; (2) a step of allowing the agent (a) to act for 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes; (3) optionally rinsing the keratinous material with water; (4) applying agent (b) to keratinous materials; (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 In particular, a procedure comprising in this order:

[0326] Rinsing the keratinous material with water in steps (3) and (6) of the method means, in the present invention, that in this rinsing step, only water is used, without using any other agent other than agents (a) and (b).

[0327] In step (1), agent (a) is first applied to keratinous materials, in particular human hair.

[0328] After application, agent (a) is left on the keratinous substance to act. In this regard, an exposure time of 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, and most preferably 30 seconds to 2 minutes to the keratinous substance, or human hair, has been found to be particularly advantageous. In a preferred embodiment of the method, agent (a) can then be rinsed off from the keratinous substance before applying agent (b) to the hair in the next step.

[0329] When agent (b) was applied to keratinous materials still exposed to agent (a), similarly washfast dyeings were obtained.

[0330] In step (4), agent (b) is applied to the keratinous material, after which agent (b) is allowed to act on the hair.

[0331] Even with short contact times of agent (b), this process allows the production of dyeings having particularly good strength and washing fastness. It has been found to be particularly advantageous for contact times on keratinous materials, on hair, to be between 10 seconds and 10 minutes, preferably between 20 seconds and 5 minutes, and most preferably between 30 seconds and 3 minutes.

[0332] In step (6), agent (b) (and agent (a) if still present) is rinsed from the keratinous material with water.

[0333] Multi-component packaging unit (kit) In the method, agents (a) and (b) are applied to the keratinous material, i.e., the two agents (a) and (b) are each ready-to-use agents.

[0334] To enhance the user's comfort, it is preferable to provide the user with all the necessary resources in the form of a multi-component packaged unit (kit).

[0335] Therefore, a second object of the present invention is to provide a comprehensive set of individually packaged a first container containing agent (a), and a second container containing agent (b); A multi-component packaging unit (kit) for coloring keratinous materials, comprising: agent (a) comprises at least one organosilicon compound (a1), agent (b) comprises at least one coloring compound (b1) comprising a substrate platelet α) and a coating β), and at least one film-forming agent (b2), The coating is a multi-component packaging unit having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments.

[0336] The organosilicon compound contained in agent (a) of the kit corresponds to the organosilicon compound used in agent (a) of the above method.

[0337] and the coloring compound comprised in means (b) of the kit is selected from the group consisting of effect pigments comprising a substrate platelet α) and a coating β) (wherein the coating comprises at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments), and the coloring compound comprised in means (b) of the kit is selected from the group consisting of effect pigments comprising a substrate platelet α) and a coating β) (wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments), and corresponds to the color-imparting compound used in means (b) of the method.

[0338] Agent (a) contains one or more organosilicon compounds and, as described above, reactive compounds that can be hydrolyzed and / or oligomerized and / or polymerized in the presence of water. As a result of the high reactivity of the organosilicon compounds, the organosilicon compounds form a film on keratinous materials.

[0339] It may be preferable to prepare the ready-to-use agent (a) only immediately prior to use, in order to avoid premature hydrolysis, oligomerization and / or polymerization.

[0340] In another embodiment, a multi-component packaging unit (kit) for coloring keratinous materials is preferably packaged separately from each other, the first container contains an agent (a'), which agent (a') comprises at least one organosilicon compound; the second container contains an agent (a"), which agent (a") comprises water, a third container comprises an agent (b), which comprises at least one coloring compound (b1) comprising at least one effect pigment comprising a substrate platelet α) and a coating β) (wherein the coating has at least one layer which is a metal oxide and / or metal oxide hydrate (i), and a coloring compound (ii) from the group of pigments), and at least one film-forming polymer (b2).

[0341] In order to be able to provide a composition that is as stable as possible during storage, the agent (a') itself preferably has a low water content or is formulated to be free of water.

[0342] In a preferred embodiment, the multi-component packaging unit (kit) is characterized in that the agent (a') has a water content of less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, even more preferably less than 0.1% by weight, and very particularly preferably less than 0.01% by weight, based on the total weight of the agent (a').

[0343] The agent (a") comprises water. In a preferred embodiment, the multicomponent packaging unit (kit) is characterized in that the agent (a") has a water content of 15 to 100% by weight, preferably 35 to 100% by weight, more preferably 55 to 100% by weight, even more preferably 65 to 100% by weight and very particularly preferably 75 to 100% by weight, based on the total weight of the agent (a").

[0344] In this embodiment, the ready-to-use agent (a) is prepared by mixing agents (a') and (a").

[0345] For example, the user may first stir or shake agent (a') containing one or more organosilicon compounds with the water-containing agent (a"). The user can then apply this mixture of (a') and (a") to the keratinous material immediately after preparation or after a short reaction time of 10 seconds to 20 minutes. The user can then apply agent (b) as described above.

[0346] In this embodiment of the multi-component packaging unit, it may be preferable for the agent (a") to further comprise at least one color-imparting compound (a2), which is preferably selected from the group consisting of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments, and / or from the group consisting of colored mica or mica-based pigments coated with at least one metal oxide and / or metal oxychloride.

[0347] Alternatively, the multi-component packaging unit may further comprise an agent (a") containing at least one coloring compound (a2). Preferably, agent (a") further comprises a silicone polymer.

[0348] In this embodiment, the ready-to-use agent (a) is prepared by mixing agents (a'), (a") and (a"').

[0349] For further preferred embodiments of the multi-component packaging unit, what has already been said regarding the method applies. Preferred aspects of the present invention include the following. [1] The following process: - applying an agent (a) comprising at least one organosilicon compound (a1) to keratinous materials, and - applying to the keratin material an agent (b) comprising at least one coloring compound (b1) comprising at least one effect pigment, and at least one film-forming polymer (b2), comprising a substrate platelet α) and a coating β). 1. A method for dyeing keratinous materials, in particular human hair, comprising: (i) a coating having at least one layer of a metal oxide and / or metal oxide hydrate, and (ii) a coloring compound from the group of pigments. [2] The method of [1], wherein agent (a) contains at least one organosilicon compound selected from silanes having one, two, or three silicon atoms, and the organosilicon compound preferably contains one or more basic chemical functional groups and one or more hydroxyl or hydrolyzable groups per molecule. [3] The agent (a) is represented by formula (I) and / or (II): Formula (I): R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b (I) [In the formula, -R 1 、R 2 are independently 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 is a hydrogen atom or C 1 -C 6 is an alkyl group, -R 4 is C 1 -C 6 represents an alkyl group, -a represents an integer from 1 to 3, -b represents the integer 3-a] Formula (II): TIFF0007739257000041.tif6134 [In the formula, -R 5 、R 5' 、R 5" are independently a hydrogen atom or C 1 -C 16 represents an alkyl group, -R 6 、R 6' and R 6" independently, C 1 -C 16 represents an alkyl group, -A, A', A", A"' and A"" are independently straight or branched chain divalent C 1 -C 20 represents an alkylene group, -R 7 and R 8 are independently hydrogen atoms, C 1 -C 6 Alkyl group, hydroxy C 1 -C 6 Alkyl group, C 2 -C 6 Alkenyl group, amino C 1 -C 6 An alkyl group or a group of formula (III): -(A"")-Si(R 6 ") d" (OR 5 ") c" (III) represents a group represented by -c represents an integer from 1 to 3, -d represents the integer 3-c, -c' represents an integer 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, - at least one of e, f, g and h is different from 0] The method according to [1] or [2], characterized in that it comprises at least one organosilicon compound represented by the following formula: [4] The agent (a) is represented by the formula (I): R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b (I) [In the formula, -R 1 、R 2 Both represent 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 represents a hydrogen atom, an ethyl group, or a methyl group; -R 4 represents a methyl group or an ethyl group, -a represents the number 3, -b represents the number 0] The method according to any one of [1] to [3], characterized in that the organic silicon compound contains at least one organosilicon compound represented by the following formula: [5] Agent (a) is -(3-aminopropyl)triethoxysilane -(3-aminopropyl)trimethoxysilane -1-(3-aminopropyl)silanetriol -(2-aminoethyl)triethoxysilane -(2-aminoethyl)trimethoxysilane -1-(2-aminoethyl)silanetriol -(3-dimethylaminopropyl)triethoxysilane -(3-dimethylaminopropyl)trimethoxysilane -1-(3-dimethylaminopropyl)silanetriol -(2-dimethylaminoethyl)triethoxysilane -(2-dimethylaminoethyl)trimethoxysilane -1-(2-dimethylaminoethyl)silanetriol, and -A mixture of them The method according to any one of [1] to [4], characterized in that the method comprises at least one organosilicon compound represented by formula (I) selected from the group consisting of: [6] The agent (a) is represented by the formula (II): TIFF0007739257000042.tif6134 [In the formula, - e and f together represent the number 1, - g and h together represent the number 0, -A and A' are independently a linear divalent C 1 -C 6 represents an alkylene group, -R 7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group, or a group represented by formula (III). The method according to any one of [1] to [5], characterized in that the organic silicon compound contains at least one organosilicon compound represented by the following formula: [7] Agent (a) is -3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -N-methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -2-[bis[3-(trimethoxysilyl)propyl]amino]ethanol -2-[bis[3-(triethoxysilyl)propyl]amino]ethanol -3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine -N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine -N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine -N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine, -N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine, and -A mixture of them The method according to any one of [1] to [6], characterized in that the method comprises at least one organosilicon compound represented by formula (II) selected from the group consisting of: [8] The agent (a) is represented by the formula (IV): R 9 Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R 9 is C 1 -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 [7], characterized in that the organic silicon compound contains at least one organosilicon compound represented by the following formula: [9] Agent (a) is -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -Propyltrimethoxysilane -Propyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -Dodecyltrimethoxysilane -Dodecyltriethoxysilane -Octadecyltrimethoxysilane -octadecyltriethoxysilane and -A mixture of them The method according to any one of [1] to [8], characterized in that the method comprises at least one organosilicon compound represented by formula (IV) selected from the group consisting of:

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

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

[10] , wherein is smaller than the layer thickness of at least one layer.

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

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

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

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

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

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

[15] Separately packaged, a first container containing an agent (a) comprising at least one organosilicon compound, and a second container containing at least one coloring compound (b1) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), and an agent (b) comprising at least one film-forming polymer (b2); 1. A kit for dyeing keratinous materials, comprising: a coating having at least one layer which is a metal oxide and / or metal oxide hydrate (i) and a coloring compound (ii) from the group of pigments. [Example]

[0350] 1. Composition The following compositions were prepared (all numbers are in weight percent unless otherwise stated): TIFF0007739257000043.tif34153

[0351] The silane was mixed with some water and the mixture was left for 30 minutes. Citric acid / ammonia was then added to adjust the pH to the desired value. Water was then added to make up to 100g.

[0352] TIFF0007739257000044.tif45153

[0353] 2. Application A lock of hair (Kerling, Euronatural hair white) was immersed in the medium (a) and left therein for 1 minute. Excess formulation (a) was then wiped off each lock. Each lock was briefly rinsed with water. Excess water was squeezed off each lock. Each hair tress was then immersed in agent (b) and left therein for 1 minute. Excess agent (b) was then wiped off each hair tress. Each hair tress was briefly rinsed with water. Excess water was then squeezed off each hair tress. The tresses were then visually evaluated.

Claims

1. The following steps: - applying an agent (a) comprising at least one organosilicon compound (a1) to keratinous materials, and - applying to the keratin material an agent (b) comprising at least one coloring compound (b1) comprising at least one effect pigment, and at least one film-forming polymer (b2), comprising a substrate platelet α) and a coating β).

1. A method for dyeing keratinous materials, comprising: (i) a coating having at least one layer of a metal oxide and / or metal oxide hydrate, and (ii) a coloring compound from the group of pigments; and (a) a dye of formula (IV): R 9 Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R 9 is C 1 -C 18 represents an alkyl group, -R 10 is a hydrogen atom or C 1 -C 6 represents an alkyl group, -R 11 is C 1 -C 6 represents an alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k. wherein the keratinous material is one or more selected from the group consisting of hair, nails, wool, fur and feathers.

2. The agent (a) is represented by formula (I) and / or (II): Formula (I): R 1 R 2 N-L-Si(OR 3 ) a (R 4 ) b (I) [In the formula, -R 1 , R 2 are independently 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 is a hydrogen atom or C 1 -C 6 is an alkyl group, -R 4 is C 1 -C 6 represents an alkyl group, -a represents an integer from 1 to 3, -b represents the integer 3-a] Formula (II): [In the formula, -R 5 , R 5' , R 5" are independently a hydrogen atom or C 1 -C 16 represents an alkyl group, -R 6 , R 6' and R 6" independently, C 1 -C 16 represents an alkyl group, - A, A', A", A"' and A"" are independently straight or branched chain divalent C 1 -C 20 represents an alkylene group, -R 7 and R 8 are independently hydrogen atoms, C 1 -C 6 Alkyl group, hydroxy C 1 -C 6 Alkyl group, C 2 -C 6 Alkenyl group, amino C 1 -C 6 An alkyl group or a group of formula (III): -(A"")-Si(R 6 ") d" (OR 5 ") c" (III) represents a group represented by -c represents an integer from 1 to 3, -d represents the integer 3-c; -c' represents an integer from 1 to 3, -d' represents the integer 3-c'; -c" represents an integer from 1 to 3, -d" represents the integer 3-c"; -e represents 0 or 1, -f represents 0 or 1, -g represents 0 or 1; -h represents 0 or 1; - at least one of e, f, g and h is different from 0] 2. The method of claim 1, comprising at least one organosilicon compound represented by the formula:

3. The agent (a) has the formula (I): R 1 R 2 N-L-Si(OR 3 ) a (R 4 ) b (I) [In the formula, -R 1 , R 2 Both represent hydrogen atoms, -L is a linear divalent C 1 -C 6 represents an alkylene group, -R 3 represents a hydrogen atom, an ethyl group, or a methyl group; -R 4 represents a methyl group or an ethyl group, -a represents the number 3, -b represents the number 0] 3. The method according to claim 1, wherein the organic silicon compound is at least one of the following:

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 - 1-(2-dimethylaminoethyl)silanetriol, and - their mixtures 4. The method according to claim 2, comprising at least one organosilicon compound of formula (I) selected from the group consisting of:

5. The agent (a) has the formula (II): [In the formula, -e and f together represent the number 1, - g and h together represent the number 0, -R 5 , R 5' , R 5" are independently a hydrogen atom or C 1 -C 16 represents an alkyl group, -R 6 , R 6' and R 6" independently, C 1 -C 16 represents an alkyl group, - A and A' are independently a linear divalent C 1 -C 6 represents an alkylene group, - A", A"' and A"" are independently straight or branched chain divalent C 1 -C 20 represents an alkylene group, -R 7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group, or a group of formula (III): -(A"")-Si(R 6 ") d" (OR 5 ") c" (III) represents a group represented by -R 8 is a hydrogen atom, C 1 -C 6 Alkyl group, hydroxy C 1 -C 6 Alkyl group, C 2 -C 6 Alkenyl group, amino C 1 -C 6 represents an alkyl group or a group represented by formula (III), -c represents an integer from 1 to 3, -d represents the integer 3-c; -c' represents an integer from 1 to 3, -d' represents the integer 3-c'; -c" represents an integer from 1 to 3, -d" represents the integer 3-c"] 5. The method according to claim 1, further comprising the step of:

6. Agent (a) is -3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -N-methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -2-[bis[3-(trimethoxysilyl)propyl]amino]ethanol -2-[bis[3-(triethoxysilyl)propyl]amino]ethanol -3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine -3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine -N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine -N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine -N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine, N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine, and - their mixtures 6. The method according to claim 2 or 5, characterized in that it comprises at least one organosilicon compound of formula (II) selected from the group consisting of:

7. Agent (a) is -Methyltrimethoxysilane -Methyltriethoxysilane -Ethyltrimethoxysilane -Ethyltriethoxysilane -propyltrimethoxysilane -propyltriethoxysilane -Hexyltrimethoxysilane -Hexyltriethoxysilane -Octyltrimethoxysilane -Octyltriethoxysilane -Dodecyltrimethoxysilane -Dodecyltriethoxysilane -Octadecyltrimethoxysilane -octadecyltriethoxysilane and - their mixtures 7. The method according to claim 1, comprising at least one organosilicon compound of formula (IV) selected from the group consisting of:

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

9. Particle size D of coloring compound (ii) 90 The method according to any one of claims 1 to 8, characterized in that is smaller than the layer thickness of at least one layer.

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

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

12. 12. The method according to claim 1, wherein the agent (a) further comprises at least one coloring compound (a2).

13. Separately packaged, a first container containing an agent (a) comprising at least one organosilicon compound, and a second container containing at least one coloring compound (b1) comprising at least one effect pigment comprising a substrate platelet α) and a coating β), and an agent (b) comprising at least one film-forming polymer (b2); 1. A kit for dyeing keratinous materials, comprising: a coating having at least one layer of metal oxides and / or metal oxide hydrates (i) and a coloring compound (ii) from the group of pigments, and the agent (a) is a compound of formula (IV): R 9 Si(OR 10 ) k (R 11 ) m (IV) [In the formula, -R 9 is C 1 -C 18 represents an alkyl group, -R 10 is a hydrogen atom or C 1 -C 6 represents an alkyl group, -R 11 is C 1 -C 6 represents an alkyl group, -k is an integer from 1 to 3, -m represents the integer 3-k. wherein the keratinous material is one or more selected from the group consisting of hair, nails, wool, fur, and feathers.

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