Method for dyeing keratinous materials, particularly human hair

Abstract

The present invention relates to a method for dyeing keratinous materials, in particular human hair, comprising the following steps: (1) applying an agent (a) to a keratin material, said agent (a) comprising (a1) less than 10% by weight of water, (a2) at least one organosilicon compound from the group of silanes having one, two or three silicon atoms, and (a3) ​​at least one color-forming compound, based on the total weight of the agent (a); (2) applying an agent (b) to the keratinous material having the agent (a) attached thereto, wherein the agent (b) contains (b1) water; (3) applying agents (a) and (b) to the keratinous material; and (4) Rinse off both agents (a) and (b). in a given order.

Description

[Technical field]

[0001] The subject of the present application is a method for coloring keratinous materials, in particular human hair, which comprises the application of two agents (a) and (b). Agent (a) is characterized in that it has a low water content or is anhydrous and contains at least one organosilicon compound and a color-forming compound. Agent (a) is first applied to the keratinous material or hair. Agent (b), which contains water, is then added to the keratinous material or hair to which agent (a) is attached, whereby the water contained in agent (b) brings about hydrolysis of the silicon compound in question upon contact with agent (a). After the action of the two agents (a) and (b), they are both washed off. [Background technology]

[0002] Changing the shape and color of keratin fibers, especially hair, is an important area of ​​cosmetics today. To change hair color, the skilled person is familiar with various dyeing systems depending on the dyeing requirements. Oxidative dyes are usually used for permanent and strong dyeing with good fastness and good gray-hiding effect. Such dyes usually contain a precursor of the oxidative dye and a color-developing component known as a developer, which together form the actual dye under the influence of an oxidizing agent, for example hydrogen peroxide. Oxidative dyes are characterized by a very long-lasting colored finish.

[0003] When using direct dyes, the already fully formed dye diffuses from the hair dye into the hair fiber. Compared to oxidative hair colorants, the color obtained with direct dyes is less durable and washes out faster. The color from direct dyes usually remains on the hair for 5 to 20 washes.

[0004] The use of color pigments is known to change the color of hair and / or skin in the short term. Color pigments are generally understood to mean insoluble dyeing substances. They are present in the dye preparation in the form of small particles and are only deposited externally on the hair fiber and / or skin surface. They can therefore usually be removed again without residue by washing several times with a surfactant-containing cleanser. Various products of this type are available on the market under the name hair mascara.

[0005] If the user wishes to achieve a particularly long-lasting coloration, the use of oxidative hair dyes has been the only option up to now. However, despite numerous optimization attempts, the unpleasant ammonia and amine odors cannot be completely avoided with oxidative hair dyes. The hair damage associated with the use of oxidative dyes also has a negative impact on the user's hair. The search for alternative high-performance dyes and dyeing methods is therefore an ongoing task. Particular focus has been placed on coloring systems in which the color-forming compounds are integrated into a film, which adheres to the surface of the hair fiber and can be removed again on the user's request, without any residue and without changing the original hair color.

[0006] EP 2168633 B1 addresses the problem of using pigments to produce hair dyes with long-lasting color. The document teaches that a combination of pigments, organosilicon compounds, film developer polymers, and solvents can be applied to hair to produce dyes that are particularly resistant to rubbing and shampooing.

[0007] A great advantage of the alkoxysilanes used in EP 2168633 B1 is that the high reactivity of this compound class allows for very fast coating. Therefore, very good dyeing results can be obtained even with very short application times of just a few minutes. However, in addition to these advantages, the high reactivity of alkoxysilanes also entails some disadvantages.

[0008] The organosilicon compounds used in the dyes are highly reactive compounds that undergo hydrolysis or oligomerization and / or polymerization in the presence of water. It is important to control the rate of oligomerization or polymerization so that the colorant can be applied within an acceptable time for the user.

[0009] Due to their high reactivity, organic alkoxysilanes cannot be prepared with large amounts of water, since this immediately initiates hydrolysis and subsequent polymerization. The polymerization that occurs during storage of alkoxysilanes in aqueous media is manifested as thickening or gelling of the aqueous formulation. As a result, the formulation becomes highly viscous, gel-like, or gelatinous, and can no longer be applied uniformly to keratinous materials. Furthermore, if alkoxysilanes are stored in the presence of large amounts of water, they lose their reactivity and can no longer form a resistant, uniform film on keratinous materials. However, the formation of a uniform film is particularly important, especially for dyeing processes.

[0010] For these reasons, organoalkoxysilanes should be stored in anhydrous or low water environments and the corresponding preparations should be prepared in separate containers. Low water content preparations containing alkoxysilanes may also be referred to as "silane blends."

[0011] To apply to keratinous materials, the user must transfer the silane blend to a ready-to-use mixture and initiate the formation of a coating. In the work leading to the present invention, silane blends were mixed in different formulations and the performance properties of these blends were tested. In a test series, application mixtures with high water content were prepared from a carrier formulation containing the silane blend and water and were applied to hair strands. In this application method, oligomerization or polymerization of the silanes began directly upon contact with the water in the application mixture that had not yet been applied to the hair. It was found that the coloring results were highly dependent on the skill of the user and the speed at which the application mixture was applied to the hair. As a result, the hair was dyed very unevenly or only insufficiently in certain areas, especially when application was slow, when the user was inexperienced and was a first-time user, or when the area to be dyed was large.

[0012] Therefore, optimally adapting the polymerization rate, i.e. the rate at which the film is formed on the keratinous materials, to the conditions of use remains a major challenge. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] European Patent No. 2168633 Summary of the Invention [Problem to be solved by the invention]

[0014] The problem of the present application was to find a method for treating keratinous materials, which allows the polymerization rate of the organoalkoxysilanes to be adapted to the conditions of use, in particular the conditions prevailing during use on the human head, in other words a method was required which allows the reproducible formation of a uniform colored film suitable for dyeing, so that the entire head of the user is uniformly colored. [Means for solving the problem]

[0015] Surprisingly, it has been found that this object can be fully achieved by treating the keratinous material or hair in a manner that involves successive application of two agents (a) and (b). Agent (a) is a low-water preparation that contains one or more alkoxysilanes and also at least one color-forming compound. Due to the low water content, oligomerization or polymerization of the alkoxysilanes of agent (a) does not occur or only occurs to a very limited extent. This agent (a) with low water content and containing a dye is applied to the keratinous material.

[0016] In a subsequent step, agent (b) is applied to the keratinous material at the location where agent (a) is attached. Agent (b) contains a specified amount of water as an essential component. Application of agent (b) to the keratinous material causes the two agents (a) and (b) to mix with each other, which can be supported, for example, by vigorously rubbing or kneading the keratinous material to which the two agents are attached. Since application of agent (b) brings the alkoxysilanes present in agent (a) into contact with a specified amount of water, oligomerization / polymerization of the silanes begins only when the silanes are already located at the location on the keratinous material or hair where the colored film is to be formed.

[0017] A first subject of the invention is a method for dyeing keratinous materials, in particular human hair, comprising the following steps: (1) applying an agent (a) to a keratinous material, said agent (a) being present in an amount, relative to the total weight of agent (a), of: (a1) less than 10% by weight of water; (a2) at least one organosilicon compound from the group of silanes containing one, two or three silicon atoms, and (a3) at least one chromogenic compound; Including, (2) applying an agent (b) to the keratinous material having the agent (a) attached thereto, wherein the agent (b) is (b1) water Including, (3) applying agents (a) and (b) to the keratinous material; and (4) Rinse off both agents (a) and (b). in a predetermined order.

[0018] It has been shown that when this novel method is used on human hair, it is possible to obtain reproducible and uniform coloring results, also characterized by intense color development and very good fastness properties, where, what is particularly advantageous, the coloring result is independent of the time taken by the user to color the hair. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] <Keratin substances> Keratinous materials are understood to mean hair, skin, nails (e.g. fingernails and / or toenails). Furthermore, wool, fur and feathers are included in the definition of keratinous materials.

[0020] Keratinous materials are preferably understood to mean human hair, human skin, human nails, in particular fingernails and toenails. Keratinous materials are particularly preferably understood to mean human hair.

[0021] <Dyeing keratinous materials> In the context of the present invention, the term "coloring process" refers to all coloring processes which produce a colored coating on keratinous materials, which is cosmetically suitable for deposition on the surface of the keratinous materials and can be produced by all chromogenic compounds which can be incorporated into the coating. Such chromogenic compounds are, for example, pigments and direct dyes, particularly preferably pigments.

[0022] Within the scope of the described method, agents (a) and (b) are applied sequentially to keratinous material, in particular human hair. Agents (a) and (b) are each ready-to-use agents. The two agents (a) and (b) are different from each other.

[0023] <Step (1), applying agent (a) to keratinous material> In step (1) of the method of the invention, agent (a) is applied to keratinous materials, in particular human hair.

[0024] Here, application of agent (a) is carried out by distributing, or distributing and massaging, agent (a) onto the keratinous material (or hair), for example with gloved hands, a brush, an applicator bottle, or an applicator, at which point the keratinous material or hair is preferably towel-dried or otherwise dry.

[0025] Dry keratin material, in particular dry hair, is material that has not been subjected to any direct additional treatment prior to the coloring process (i.e. up to 3 hours prior to the coloring process) and that has not been moistened with water or water / shampoo.

[0026] Towel-dried keratinous material, in particular towel-dried hair, is defined as material / hair that has been wetted with water or washed within a maximum of 30 minutes, preferably within 15 minutes, prior to the start of the coloring process and then rubbed dry with a towel for approximately 30 seconds.

[0027] Example: A user thoroughly wets hair under a tap by completely saturating the hair with running water heated to approximately 35° C. The user then dries the hair with a dry towel for 30 seconds.

[0028] Towel-dried hair is characterized by no longer being dripping wet, i.e. no longer having a large portion of moisture on the surface of the hair. Nevertheless, the hair still has residual moisture due to water molecules present in the hair fiber, which causes the hair fiber to swell. It is very particularly preferred to apply agent (a) to towel-dried keratinous materials, especially towel-dried hair. The small amount of moisture present in towel-dried hair facilitates the application and distribution of agent (a) without initiating significant oligomerization or polymerization due to too much moisture.

[0029] In a further embodiment, the method according to the invention is characterized in that in step (1) the agent (a) is applied to towel-dried or dried keratinous material, very particularly preferably to towel-dried keratinous material.

[0030] In a further embodiment, the method according to the invention is characterized in that in step (1) the agent (a) is applied to towel-dried or dry human hair, very particularly preferably to towel-dried human hair.

[0031] After application to the keratinous materials or hair, agent (a) may be massaged in. Massaging can be achieved, for example, by mechanically massaging or rubbing the hair with gloved hands.

[0032] <Agent (a)> The agent (a) is a ready-to-use agent, characterized in that it contains less than 10% by weight of water (a1), based on the total weight of the agent (a), at least one organosilicon compound (a2) from the group of silanes having one, two or three silicon atoms, and at least one chromogenic compound (a3).

[0033] Agent (a) may be in the form of a liquid, gel or cream. Thus, agent (a) may be, for example, in the form of a cream, emulsion, gel, or surfactant-containing foaming solution, which contain less than 10% by weight of water.

[0034] <Water content in agent (a) (a1)> The water content is less than 10% by weight, based on the total weight of agent (a). This ensures that agent (a) is stable over the entire application time and premature undesirable oligomerization or polymerization of the silanes is avoided to a sufficient extent. Even if the stability of the agent is already ensured with a water content of up to 10% by weight, it has been found to be preferable to adjust the water content of agent (a) to values ​​below 10% by weight in order to further optimize stability and color strength. In this way, particularly good results have been obtained when the water content in agent (a) is 0-7.5% by weight, preferably 0.0-5.0% by weight, more preferably 0.0-4.0% by weight, very particularly preferably 0-2.5% by weight, based on the total weight of agent (a).

[0035] In a further very particularly preferred embodiment, the method according to the invention is characterized in that the agent (a) contains 0 to 7.5% by weight, preferably 0.0 to 5.0% by weight, even more preferably 0.0 to 4.0% by weight and very particularly preferably 0 to 2.5% by weight of water (a1), relative to the total weight of agent (a).

[0036] The range of 0 to 2.5% by weight of water means that the agent contains as little water as possible or else the amount of water possibly introduced into agent (a) by further components contained in agent (a) does not exceed 2.5% by weight.

[0037] <Organosilicon compound (a2) from the group of silanes in agent (a)>

[0038] As a second component (a2) essential to the invention, the agent (a) contains at least one organosilicon compound from the group of the silanes containing one, two or three silicon atoms.

[0039] Particularly preferably, the agent (a) comprises at least one organosilicon compound (a1) selected from silanes having one, two or three silicon atoms, which organosilicon compound contains one or more hydroxyl and / or hydrolyzable groups per molecule.

[0040] These organosilicon compounds (a1) or organosilanes contained in agent (a) are reactive compounds.

[0041] Organosilicon compounds, also called organosilicon compounds, are compounds that have a direct silicon-carbon (Si-C) bond or carbon is bonded to a silicon atom via an oxygen, nitrogen or sulfur atom. The organosilicon compounds according to the present invention are compounds that contain 1 to 3 silicon atoms. The organosilicon compounds particularly preferably contain 1 or 2 silicon atoms.

[0042] According to IUPAC rules, the name "silane" denotes a substance family of chemical compounds based on a silicon skeleton and hydrogen. In organosilanes, the hydrogen atoms are fully or partially replaced by organic groups such as (substituted) alkyl and / or alkoxy groups. In organosilanes, some of the hydrogen atoms can also be replaced by hydroxyl groups.

[0043] In a particularly preferred embodiment, the method is characterized in that an agent (a) containing at least one organosilicon compound (a1) selected from silanes having one, two or three silicon atoms and further comprising one or more hydroxyl or hydrolyzable groups per molecule is used on the keratinous material.

[0044] In a very particularly preferred embodiment, the method of the invention is characterized in that an agent (a) is used on the keratin materials which contains at least one first organosilicon compound (a1) selected from silanes having one, two or three silicon atoms and which further comprises one or more basic chemical functional groups per molecule and hydroxyl or hydrolyzable groups.

[0045] The basic group or basic chemical functionality may be, for example, an amino group, an alkylamino group, a dialkylamino group or a trialkylamino group, and is preferably attached 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.

[0046] 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 R', R'' and R''' functional groups represent the remaining three free valences of the silicon atom.

[0047] A very particularly preferred process according to the invention is characterized in that the agent (a) comprises at least one organosilicon compound selected from silanes having one, two or three silicon atoms, where said organosilicon compound preferably comprises one or more basic chemical functional groups and one or more hydroxyl or hydrolyzable groups per molecule.

[0048] It has been possible to obtain very good results when the agent (a) comprises at least one organosilicon compound (a1) of formula (I) and / or formula (II).

[0049] The compounds of formulas (I) and (II) are organosilicon compounds selected from silanes having one, two or three silicon atoms, which contain one or more hydroxyl and / or hydrolyzable groups per molecule.

[0050] In another very particularly preferred embodiment, the method further comprises the step of: (a) a compound represented by the formula (I) and / or the formula (II): Formula (I): TIFF2024531458000001.tif7151 [In the formula, R1 and R2 are each independently a hydrogen atom or a C1-C6 alkyl group; L is a linear or branched divalent C1-C 20 represents an alkylene group, R3 and R4 are each independently a C1-C6 alkyl group; a represents an integer from 1 to 3, b is an integer equal to 3-a Formula (II): TIFF2024531458000002.tif7151 [In the formula, R5, R5', R5'', R6, R6' and R6'', independently of one another, represent a C1-C6 alkyl group; A, A', A'', A''' and A'''' are, independently of one another, linear or branched divalent C1-C 20 represents an alkylene group, R7 and R8 are each independently a hydrogen atom, a C1-C6 alkyl group, a hydroxy-C2-C6 alkyl group, a C1-C6 alkenyl group, an amino-C1-C6 alkyl group or a group of formula (III): TIFF2024531458000003.tif7151(·c represents an integer between 1 and 3, d represents an integer equal to 3-c, c' represents an integer from 1 to 3, d' represents an integer equal to 3-c', c'' represents an integer from 1 to 3, d'' represents an integer equal to 3-c'', e represents 0 or 1, f represents 0 or 1, g represents 0 or 1, h represents 0 or 1, However, at least one of e, f, g, and h is different from 0. represents The composition is characterized in that it contains at least one organosilicon compound (a2) represented by the following formula:

[0051] The substituents R1, R2, R3, R4, R5, R5', R5'', R6, R6', R6'', R7, R8, L, A, A', A'', A''' and A'''' in the compounds represented by formulae (I) and (II) are illustrated below by way of example.

[0052] Examples of C1-C6 alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl and n-hexyl groups. 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 preferred C2-C6 alkenyl groups being vinyl and allyl. Preferred examples of hydroxy-C1-C6 alkyl groups are hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyhexyl groups, with the 2-hydroxyethyl group being 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 are, for example, methylene (-CH-), ethylene (-CH-CH-), propylene (-CH-CH-CH-), and butylene (-CH-CH-CH-CH-). The propylene group (-CH-CH-CH-) is particularly preferred. Beyond a chain length of three C atoms, the divalent alkylene group may also be branched. Branched C-C 20 Examples of divalent alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0053] Formula (I): In the organosilicon compound of TIFF2024531458000004.tif7151, the functional groups R1 and R2, independently of one another, represent a hydrogen atom or a C1-C6 alkyl group. Very particularly preferably, the groups R1 and R2 represent a hydrogen atom.

[0054] The central part of the organosilicon compound is a linear or branched divalent C1-C 20 A structural unit representing an alkylene group or a linker -L-.

[0055] Divalent C1-C 20 The alkylene group may alternatively be a divalent or double-bonded C-C 20They may also be referred to as alkylene groups, which means that each group L may participate in two bonds: one bond from the amino group R1R2N to the linker L, and the second bond between the linker L and the silicon atom.

[0056] Preferably, -L- is a linear divalent C-C 20 It is more preferred that -L- represents a linear divalent C1-C6 alkylene group. Particularly preferred is that -L- represents a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-) or a butylene group (-CH2-CH2-CH2-CH2-). Very particularly preferred is that L represents a propylene group (-CH2-CH2-CH2-).

[0057] The linear propylene group (-CH2-CH2-CH2-) may alternatively be referred to as a propane-1,3-diyl group.

[0058] Formula (I): The organosilicon compounds in TIFF2024531458000005.tif7151 are silicon-containing groups -Si(OR3) a (R4) b at one end.

[0059] Terminal structural unit -Si(OR3) a (R4) b In the formula (I), the functional group R3 represents a hydrogen atom or a C1-C6 alkyl group, and the functional group R4 represents a C1-C6 alkyl group. Particularly preferably, the functional groups R3 and R4 each independently represent a methyl group or an ethyl group.

[0060] In this case, a represents an integer between 1 and 3, and b represents an integer 3-a. When a represents the number 3, b is 0. When a represents the number 2, b is 1. When a represents the number 1, b is 2.

[0061] Particularly resistant coatings can be obtained when the agent (a) comprises at least one organosilicon compound (a2) of formula (I) in which the functional groups R3, R4, independently of one another, represent a methyl or ethyl group.

[0062] When a method for coloring human hair is used, it has been possible to obtain colorations with the best washing fastness when the agent (a) comprises at least one organosilicon compound (a2) of formula (I) in which the functional groups R3, R4, independently of one another, represent a methyl or ethyl group.

[0063] Furthermore, colorations with the best washing fastness can be obtained when agent (a) comprises at least one organosilicon compound of formula (I) in which the functional group a represents the number 3. In this case, the group b represents the number 0.

[0064] In another preferred embodiment, the agent (a) is of the formula R3 and R4 each independently represent a methyl group or an ethyl group; a represents the number 3, · b represents the number 0, It is characterized by containing at least one organosilicon compound (a2) represented by formula (I).

[0065] In another preferred embodiment, the method of the present invention comprises the step of: TIFF2024531458000006.tif7151 [In the formula, R1 and R2 each represent a hydrogen atom. 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, a methyl group or an ethyl group; R4 represents a methyl group or an ethyl group; a represents the number 3, ·b represents the number 0 The composition is characterized in that it contains at least one first organosilicon compound (a2) represented by the formula:

[0066] Organosilicon compounds of formula (I) which are particularly well suited for solving the problem according to the invention are: (3-Aminopropyl)triethoxysilane TIFF2024531458000007.tif3473·(3-aminopropyl)trimethoxysilane TIFF2024531458000008.tif3464·1-(3-aminopropyl)silanetriol TIFF2024531458000009.tif2161·(2-aminoethyl)triethoxysilane TIFF2024531458000010.tif3464·(2-Aminoethyl)trimethoxysilane TIFF2024531458000011.tif3455·1-(2-aminoethyl)silanetriol TIFF2024531458000012.tif2151·(3-Dimethylaminopropyl)triethoxysilane TIFF2024531458000013.tif3475·(3-Dimethylaminopropyl)trimethoxysilane TIFF2024531458000014.tif3466·1-(3-Dimethylaminopropyl)silanetriol TIFF2024531458000015.tif2262·(2-Dimethylaminoethyl)triethoxysilane TIFF2024531458000016.tif3566·(2-Dimethylaminoethyl)trimethoxysilane, and / or TIFF2024531458000017.tif3457·1-(2-Dimethylaminoethyl)silanetriol TIFF2024531458000018.tif2753

[0067] In a further preferred embodiment, the method of the invention comprises the step of: (3-Aminopropyl)triethoxysilane (3-Aminopropyl)trimethoxysilane 1-(3-aminopropyl)silanetriol (2-Aminoethyl)triethoxysilane (2-Aminoethyl)trimethoxysilane 1-(2-aminoethyl)silanetriol (3-Dimethylaminopropyl)triethoxysilane (3-Dimethylaminopropyl)trimethoxysilane 1-(3-Dimethylaminopropyl)silanetriol (2-Dimethylaminoethyl)triethoxysilane (2-Dimethylaminoethyl)trimethoxysilane, and / or 1-(2-Dimethylaminoethyl)silanetriol The composition is characterized in that it contains at least one organosilicon compound (a2) selected from the group consisting of:

[0068] Organosilicon compounds of formula (I) above are commercially available.

[0069] For example, (3-aminopropyl)trimethoxysilane can be purchased from Sigma-Aldrich. (3-aminopropyl)triethoxysilane is also commercially available from Sigma-Aldrich.

[0070] In another embodiment, the agent has formula (II): It contains at least one organosilicon compound (a2) represented by TIFF2024531458000019.tif7151.

[0071] The organosilicon compounds of formula (II) each contain a silicon-containing group (RO) c (R6) d Si- and -Si(R6') d’ (OR5') c’ at both ends of them.

[0072] Located in the central portion of the molecule of formula (II) is the group -(A) e- and -[NR7-(A')] f - and -[O-(A'')] g - and -[NR8-(A'')] h -, where each of the functional groups e, f, g and h, independently of one another, represents the number 0 or 1, provided that at least one of the functional groups e, f, g and h is different from 0. In other words, the organosilicon compound of formula (II) contains at least one group from the group consisting of -(A)-, -[NR7-(A')]-, -[O-(A'')]- and -[NR8-(A''')]-.

[0073] Two terminal structural units (RO) c (R6) d Si- and Si(R6') d’ (OR5') c’ In the formula, the functional groups R5, R5', and R5" each independently represent a hydrogen atom or a C1-C6 alkyl group. The functional groups R6, R6', and R6" each independently represent a C1-C6 alkyl group.

[0074] Here, c is an integer between 1 and 3, and d is an integer between 3 and 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.

[0075] Similarly, c' represents an integer between 1 and 3, and d' represents an integer between 3 and 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.

[0076] The most stable coatings or dyeings with the best washing fastness have been obtained when the groups c and c' both represent the number 3. In this case, d and d' both represent the number 0.

[0077] In a further preferred embodiment, the method further comprises the step of: TIFF2024531458000020.tif7151 [In the formula, R5 and R5' are each independently a methyl or ethyl group; c and c' each represent the number 3, ·d and d' both represent the number 0. The composition is characterized in that it contains at least one organosilicon compound (a2) represented by the following formula:

[0078] When c and c' are both the number 3 and d and d' are both the number 0, the organosilicon compound of the present invention has the formula (IIa): Equivalent to TIFF2024531458000021.tif7151.

[0079] The functional groups e, f, g and h may each independently represent the number 0 or 1. At least one of the functional groups e, f, g and h is different from 0. Thus, the abbreviations e, f, g and h are used to denote -(A) e -, -[NR7-(A')] f -,-[O-(A'')] g - and -[NR8-(A'')] h - which group is present in the central portion of the organosilicon compound of formula (II).

[0080] In this context, the presence of certain groups has been found to be particularly advantageous in terms of increasing the washing fastness. Particularly good results can be obtained when at least two of the functional groups e, f, g and h represent the number 1. Very particularly preferably, e and f both represent the number 1. Furthermore, very particularly preferably, g and h both represent the number 0.

[0081] When e and f both represent the number 1, and g and h both represent the number 0, the organosilicon compound in the present invention has the formula (IIb): Equivalent to TIFF2024531458000022.tif7151.

[0082] The functional groups A, A', A'', A''' and A'''' are, independently of one another, linear or branched divalent C1-C 20Preferably, the functional groups A, A', A'', A''' and A'''' are each independently a linear or branched divalent C-C alkylene group. 20 It represents an alkylene group. More preferably, the functional groups A, A', A'', A''' and A'''' independently of one another represent a linear divalent C1-C6 alkylene group. Particularly preferably, the functional groups A, A', A'', A''' and A'''' independently of one another represent a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-) or a butylene group (-CH2-CH2-CH2-CH2-). Very particularly preferably, the functional groups A, A', A'', A''' and A'''' represent a propylene group (-CH2-CH2-CH2-).

[0083] Divalent C1-C 20 The alkylene group may alternatively be a divalent or double-bonded C-C 20 Also referred to as an alkylene group, this means that each group A, A', A'', A''' and A'''' can participate in two bonds.

[0084] The linear propylene group (-CH2-CH2-CH2-) may alternatively be referred to as a propane-1,3-diyl group.

[0085] When the group f represents the number 1, the organosilicon compound of formula (II) comprises the structural group --[NR7--(A')]--.

[0086] When the functional group h represents the number 1, the organosilicon compound of formula (II) comprises the structural group -[NR8-(A''')]-.

[0087] In this regard, R7 and R8 are each independently hydrogen, 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): Represents the base of TIFF2024531458000023.tif7151.

[0088] Most preferably, the functional groups R7 and R8 independently of each other represent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III).

[0089] When the functional group f represents the number 1 and the functional group h represents the number 0, the organosilicon compound according to the invention comprises the group [NR7-(A')] but does not comprise the group -[NR8-(A''')]. When the group R7 represents a group of formula (III), the agent (a) comprises an organosilicon compound having three reactive silane groups.

[0090] In a further preferred embodiment, the method further comprises the step of: TIFF2024531458000024.tif7151 [in the formula, e and f together represent the number 1, g and h together represent the number 0, A and A' are each independently a linear divalent C1-C6 alkylene group; R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III). The composition is characterized in that it contains at least one organosilicon compound (a2) represented by the following formula:

[0091] In another preferred embodiment, the method further comprises the step of: e and f together represent the number 1, g and h together represent the number 0, A and A' are each independently a methylene group (-CH2-), an ethylene group (-CH2-CH2-) or a propylene group (-CH2-CH2-CH2), They contain at least one organosilicon compound (a2) of formula (II), in which R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III).

[0092] Organosilicon compounds of formula (II) suitable for solving the problems according to the present invention are as follows: 3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF2024531458000025.tif40113·3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF2024531458000026.tif45129·N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine TIFF2024531458000027.tif40113·N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine TIFF2024531458000028.tif45129·2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol TIFF2024531458000029.tif47113·2-[bis[3-(triethoxysilyl)propyl]amino]ethanol TIFF2024531458000030.tif53129·3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine TIFF2024531458000031.tif60113·3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine TIFF2024531458000032.tif63127·N1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine TIFF2024531458000033.tif48113·N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine TIFF2024531458000034.tif54129·N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine TIFF2024531458000035.tif45113·N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine TIFF2024531458000036.tif51129

[0093] Organosilicon compounds of formula (II) above are commercially available.

[0094] Bis(trimethoxysilylpropyl)amine, having the CAS number 82985-35-1, can be purchased, for example, from Sigma-Aldrich.

[0095] Bis[3-(triethoxysilyl)propyl]amine, having the CAS number 13497-18-2, can be purchased, for example, from Sigma-Aldrich.

[0096] N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine, also known as bis(3-trimethoxysilylpropyl)-N-methylamine, can be purchased, for example, from Sigma-Aldrich or Fluorochem.

[0097] 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine, having the CAS number 18784-74-2, can be purchased, for example, from Fluorochem or Sigma-Aldrich.

[0098] In another preferred embodiment, the method further comprises the step of: 3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine, 3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine, N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine, N-methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine, 2-[bis[3-(trimethoxysilyl)propyl]amino]-ethanol, 2-[bis[3-(triethoxysilyl)propyl]amino]ethanol, 3-(trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine, 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine, N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine, N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine, and / or N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine The composition is characterized by comprising at least one organosilicon compound (a2) selected from the group consisting of:

[0099] In a further dyeing test, the agent (a) applied to the keratin material in the method has the formula (IV): It has also been found to be very advantageous if the composition comprises at least one organosilicon compound (a2) of the type shown in TIFF2024531458000037.tif7151.

[0100] The compound of formula (IV) is an organosilicon compound selected from silanes having one, two or three silicon atoms, which organosilicon compound contains one or more hydroxyl and / or hydrolyzable groups per molecule.

[0101] Formula (IV): TIFF2024531458000038.tif7151 [In the formula, ·R9 is C1-C 18 represents an alkyl group, ·R 10 represents a hydrogen atom or a C1-C6 alkyl group, ·R11 represents a C1-C6 alkyl group, k represents an integer from 1 to 3, m represents an integer between 3 and k. The organosilicon compounds represented by the formula: are also sometimes called alkylalkoxysilane-type or alkylhydroxysilane-type silanes.

[0102] In a further embodiment, the method of the present invention relates to a compound according to the present invention, wherein the agent (a) is a compound of formula (IV): TIFF2024531458000039.tif7151 [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 represents an integer from 1 to 3, m represents an integer between 3 and k. The composition is characterized in that it contains at least one first organosilicon compound (a2) represented by the following formula:

[0103] In a further very particularly preferred embodiment, the method according to the invention comprises the agent (a) comprising, in addition to said organosilicon compound, a compound of formula (IV): TIFF2024531458000040.tif7151 [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 represents an integer from 1 to 3, m represents an integer between 3 and k. The composition is characterized in that it comprises at least one first further organosilicon compound represented by the formula:

[0104] In a further preferred embodiment, the method comprises the step of: (a) comprising, in addition to the organosilicon compound of formula (II), a compound of formula (IV): TIFF2024531458000041.tif7151 [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 represents an integer from 1 to 3, m represents an integer between 3 and k. The present invention is characterized in that it contains at least one further organosilicon compound represented by the formula:

[0105] In another preferred embodiment, the method further comprises the step of: (a) comprising, in addition to the organosilicon compounds of formula (I) and / or formula (II), a compound of formula (IV): TIFF2024531458000042.tif7151 [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 represents an integer from 1 to 3, m represents an integer between 3 and k. The present invention is characterized in that it contains at least one further organosilicon compound represented by the formula:

[0106] In the organosilicon compound of formula (IV), the functional group R9 is C1-C 18 This C1-C alkyl group. 18 The alkyl group is saturated and may be linear or branched. Preferably, R is a linear C-C 18 R9 represents an alkyl group. Preferably, R9 represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group or an n-octadecyl group. Particularly preferably, R9 represents a methyl group, an ethyl group, an n-hexyl group or an n-octyl group.

[0107] In the organosilicon compound represented by formula (IV), the functional group R 10 represents a hydrogen atom or a C1-C6 alkyl group. 10 represents a methyl group or an ethyl group.

[0108] In the organosilicon compound represented by formula (IV), the functional group R 11 represents a C1-C6 alkyl group. Particularly preferably, R 11 represents a methyl group or an ethyl group.

[0109] Furthermore, k represents an integer from 1 to 3, and m represents an integer from 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.

[0110] Particularly stable coatings, i.e. dyeings with good washing fastness, have been obtained when an agent (a) containing at least one organosilicon compound (a1) of formula (IV) in which the functional group k represents the number 3 is used in the process. In this case, the functional group m represents the number 0.

[0111] Organosilicon compounds of the formula (IV) which are particularly well suited to solving the problems according to the invention are: Methyltrimethoxysilane TIFF2024531458000043.tif3429·Methyltriethoxysilane TIFF2024531458000044.tif4139·Ethyltrimethoxysilane TIFF2024531458000045.tif3439·Ethyltriethoxysilane TIFF2024531458000046.tif4147·n-Hexyltrimethoxysilane TIFF2024531458000047.tif3475·n-Hexyltriethoxysilane TIFF2024531458000048.tif4184·n-Octyltrimethoxysilane TIFF2024531458000049.tif3493·n-Octyltrimethoxysilane TIFF2024531458000050.tif41103·n-dodecyltrimethoxysilane, and / or TIFF2024531458000051.tif34130·n-Dodecyltriethoxysilane TIFF2024531458000052.tif43140 n-Octadecyltrimethoxysilane, and / or n-Octadecyltriethoxysilane

[0112] In a further preferred embodiment, the method of the invention comprises the step of: Methyltrimethoxysilane Methyltriethoxysilane Ethyltrimethoxysilane Ethyltriethoxysilane Propyltrimethoxysilane Propyltriethoxysilane Hexyltrimethoxysilane Hexyltriethoxysilane Octyltrimethoxysilane Octyltriethoxysilane Dodecyltrimethoxysilane, Dodecyltriethoxysilane, Octadecyltrimethoxysilane, and / or Octadecyltriethoxysilane The composition is characterized by comprising at least one organosilicon compound (a2) represented by formula (IV) selected from the group consisting of:

[0113] The above-mentioned organosilicon compounds are reactive compounds. In this respect, it has been found to be advantageous if the agent (a) comprises one or more organosilicon compounds (a2) in a total amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 8% by weight, based on the total weight of the agent (a).

[0114] In a further preferred embodiment, the method is characterized in that the agent (a) comprises one or more organosilicon compounds (a2) in a total amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 8% by weight, based on the total weight of agent (a).

[0115] In order to obtain particularly good dyeing results, it is particularly advantageous to use the organosilicon compounds of formula (I) and / or (II) in the agent (a) in a specific range of amounts. Particularly preferably, the agent (a) comprises one or more organosilicon compounds (a2) of formula (I) and / or (II) in a total amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the total weight of the agent (a).

[0116] In a further preferred embodiment, the method is characterized in that the agent (a) comprises one or more organosilicon compounds (a2) of the formulae (I) and / or (II) in a total amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, particularly preferably 0.5 to 3% by weight, based on the total weight of agent (a).

[0117] Furthermore, it has been found to be very particularly preferred that the organosilicon compounds of formula (IV) are present in the agent (a) in a specific range of amounts.Particularly preferably, the agent (a) comprises one or more organosilicon compounds (a2) of formula (IV) in a total amount of 0.1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 4 to 9% by weight, based on the total weight of the agent (a).

[0118] In another preferred embodiment, the method is characterized in that the agent (a) contains one or more organosilicon compounds (a2) of formula (IV) in a total amount of 0.1 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 3.2 to 10% by weight, based on the total weight of agent (a).

[0119] In the course of the research which led to the present invention, it was found that particularly stable and uniform coatings are obtained on keratinous materials when agent (a) comprises two organosilicon compounds which are structurally different from one another.

[0120] In a further preferred embodiment, the method according to the invention is characterized in that the agent (a) comprises at least two organosilicon compounds (a2) which are structurally different from one another.

[0121] In a preferred embodiment, the method is characterized in that an agent (a) comprising at least one organosilicon compound of formula (I) and at least one organosilicon compound of formula (IV) is applied to the keratinous material.

[0122] In an explicitly very particularly preferred embodiment, the method is characterized in that the agent (a) 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, to the keratinous material.

[0123] In a further preferred embodiment, the method is characterized in that the agent (a) comprises, relative to the total weight of agent (a): 0.5 to 5% by weight of at least one first organosilicon compound (a2) selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane and (2-dimethylaminoethyl)triethoxysilane, 3.2 to 10 wt. % of at least one second organosilicon compound (a2) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, and octadecyltriethoxysilane.

[0124] In this embodiment, the agent (a) contains one or more organosilicon compounds of the first group in a total amount of 0.5 to 3% by weight, which are selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane (2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane and / or (2-dimethylaminoethyl)triethoxysilane.

[0125] In this embodiment, the agent (a) contains one or more organosilicon compounds of the second group in a total amount of 3.2 to 10% by weight. The organosilicon compounds of the second group are selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane.

[0126] <Oligomer and / or condensation product of organosilicon compound (a2)>

[0127] In the above-mentioned organosilicon compounds (a2) from the group consisting of silanes with one, two or three silicon atoms, even the addition of small amounts of water leads to hydrolysis, or oligomerization and / or polymerization. The degree of oligomerization or polymerization here depends on the amount of water that comes into contact with the silane or silane (a2). The aim of the method according to the invention is that the formation of a coloured film, i.e. the final polymerization from the silane (a2) in step (2) of the method, only occurs if the agent (a) is already located on the keratinous material. Nevertheless, due to the high reactivity of the silane (a2), oligomerization or precondensation has already taken place before the application of the agent (a), and the silane (a2) may already be oligomerized in the agent (a) or already polymerized to a small extent.

[0128] Thus, both silanes (a2) having 1, 2 or 3 silicon atoms and their oligomers and / or condensation products can be contained in the agent (a).Accordingly, according to the invention, the term "silanes (a2) having 1, 2 or 3 silicon atoms" also includes their hydrolysis products, oligomers and / or condensation products.

[0129] The corresponding oligomers and / or condensation products of hydrolysis are, for example, the following compounds: ##STR1## In this case, the condensation products represent the largest oligomeric compounds, but are not polymeric.

[0130] Hydrolysis of C1-C6 alkoxysilanes of formula (SI) with water (reaction scheme using the example of 3-aminopropyltriethoxysilane): TIFF2024531458000053.tif20155

[0131] Depending on the amount of water used, the hydrolysis reaction can be carried out multiple times for each C1-C6 alkoxysilane used: TIFF2024531458000054.tif20156 or TIFF2024531458000055.tif20156

[0132] Hydrolysis of C1-C6 alkoxysilanes of formula (S-IV) with water (reaction scheme using the example of methyltrimethoxysilane): TIFF2024531458000056.tif21120

[0133] Depending on the amount of water used, the hydrolysis reaction can be carried out multiple times for each C1-C6 alkoxysilane used: TIFF2024531458000057.tif21125 or TIFF2024531458000058.tif21125

[0134] A possible condensation reaction is, for example, the following (shown based on a mixture of (3-aminopropyl)triethoxysilane and methyltrimethoxysilane): TIFF2024531458000059.tif33156 and / or TIFF2024531458000060.tif33154 and / or TIFF2024531458000061.tif33156 and / or TIFF2024531458000062.tif33144 and / or TIFF2024531458000063.tif33142 and / or TIFF2024531458000064.tif33143 and / or TIFF2024531458000065.tif22143

[0135] Although the exemplary reaction schemes above each show condensation to form a dimer, further condensation to oligomers having several silane atoms is also possible and preferred.

[0136] Condensation products are understood to mean products formed by the reaction of at least two organosilicon compounds having at least one hydroxyl or hydrolyzable group in one molecule, with the elimination of water and / or the elimination of alkanol. The condensation products can be, for example, dimers, but also trimers and oligomers, and the condensation products are in equilibrium with the monomers. Depending on the amount of water used or consumed in the hydrolysis, the equilibrium between the monomeric organosilicon compounds and the condensation products changes.

[0137] Very particularly good results can be obtained when using organosilicon compounds of formula (I) and / or (II) and / or (IV) in this method.As already mentioned above, hydrolysis / condensation already occurs in the presence of small amounts of moisture, so the hydrolysis and / or condensation products of organosilicon compounds (I) and / or (II) and / or (IV) of this embodiment are also included.

[0138] <Color-forming compound (a3) ​​in agent (a)> The agent (a) comprises at least one chromogenic compound as a third component essential to the invention. In the formation of the film produced by polymerization of the silane (a2), the chromogenic compound is retained and thus fixed on the keratin surface. Such chromogenic compounds are very particularly preferably pigments and / or direct dyes, very particularly preferably pigments.

[0139] In a further particularly preferred embodiment, the method according to the invention is characterized in that the agent (a) comprises at least one chromophoric compound (a3) ​​from the group of the pigments and / or direct dyes.

[0140] In a further particularly preferred embodiment, the method according to the invention is characterized in that the agent (a) comprises at least one pigment (a3).

[0141] Pigments in the sense of the present invention are understood to mean chromogenic compounds whose solubility in water at 25° C. is less than 0.5 g / L, preferably less than 0.1 g / L, and even more preferably less than 0.05 g / L. The solubility in water can be measured, for example, by the following method: 0.5 g of pigment are weighed out in a beaker. A stirring bar is added. Then 1 liter of distilled water is added. The mixture is heated at 25° C. for 1 hour while stirring with a magnetic stirrer. If after this time undissolved components of the pigment are still visible in the mixture, the solubility of the pigment is less than 0.5 g / L. If the pigment-water mixture cannot be evaluated visually due to the high intensity of the pigment present finely dispersed, the mixture is filtered. If some undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g / L.

[0142] Suitable pigments may be of inorganic and / or organic origin.

[0143] In a preferred embodiment, the process is characterized in that it comprises at least one chromophoric compound (a3) ​​from the group of inorganic and / or organic pigments.

[0144] Preferred pigments are selected from synthetic or natural inorganic pigments.Naturally occurring inorganic pigments can be produced, for example, from chalk, ocher, umber, green earth, burnt sienna or graphite.Furthermore, black pigments, such as black iron oxide, colored pigments, such as ultramarine or red iron oxide, and fluorescent or phosphorescent pigments can be used as inorganic color pigments.

[0145] 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 dye pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), Prussian blue (ferric ferrocyanide, CI 77510) and / or carmine (cochineal).

[0146] Likewise, particularly preferred pigments are colored pearlescent pigments. These are usually mica-based and may be coated with one or more metal oxides. Micas are layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce pearlescent pigments in combination with metal oxides, mica, mainly muscovite or phlogopite, is coated with metal oxide.

[0147] A preferred method is therefore characterized in that the agent (a) comprises at least one inorganic pigment (a3), preferably selected from coloured metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or mica-based colour pigments coated with at least one metal oxide and / or metal oxychloride.

[0148] A suitable pigment based on synthetic mica is for example Timiron® SynWhite Satin from Merck.

[0149] In a further preferred embodiment, the method is characterized in that the agent (a) and / or the agent (b) comprises at least one chromogenic compound from the group of pigments selected from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or Prussian blue (ferric ferrocyanide, CI 77510).

[0150] Other suitable pigments are based on platelet-shaped borosilicates coated with metal oxides. These are, for example, coated with tin oxide, iron oxide, silicon dioxide and / or titanium dioxide. Such borosilicate pigments are available, for example, under the names MIRAGE from Eckart and Reflecks from BASF SE.

[0151] Examples of particularly suitable pigments are commercially available, for example under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® or SynCrystal from Eckart Cosmetic Colors, Flamenco®, Cellini®, Cloisonne®, Duocrome®, Gemtone®, Timica®, MultiReflections, Chione from BASF SE, and Sunshine® from Sunstar.

[0152] Very particularly preferred colour pigments having the trade name Colorona® are, for example: Colorona Copper, Merck, Mica, CI 77491 (Iron Oxide) Colorona Copper Fine, 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 Oxides (CI 77491) Colorona Carmine Red, Merck, Mica, Titanium Dioxide, Carmine Colorona Blackstar Green, Merck, Mica, CI 77499 (Iron Oxides) Colorona Bordeaux, Merck, Mica, CI 77491 (Iron Oxide) Colorona Bronze, Merck, Mica, CI 77491 (Iron Oxide) Colorona Bronze Fine, Merck, Mica, CI 77491 (Iron Oxides) Colorona Fine Gold MP 20, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Sienna Fine, Merck, CI 77491 (iron oxide), mica Colorona Sienna, Merck, Mica, CI 77491 (Iron Oxide) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, CI 77491 (Iron Oxides), Tin Oxide Colorona Sun Gold Sparkle MP 29, Merck, Mica, Titanium Dioxide, Iron Oxide, Mica, CI 77891, CI 77491(EU) Colorona Mica Black, Merck, CI 77499 (iron oxides), mica, CI 77891 (titanium dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium Dioxide), CI 77491 (Iron Oxides) Colorona Blackstar Gold, Merck, Mica, CI 77499 (Iron Oxides) Colorona® SynCopper, Merck, synthetic fluorphlogopite (and) iron oxide Colorona® SynBronze, Merck, a synthetic fluorophlogopite (and) iron oxide.

[0153] Other particularly preferred pigments under the trade name Xirona® are, for example: Xirona® Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona® Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona® Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona® Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona® Le Rouge, Merck, iron oxide (and) silica.

[0154] In addition, particularly preferred pigments under the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI 77491 (iron oxide), silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxide), Silica Unipure Yellow LC 182 EM,Sensient,CI 77492(Iron Oxide),Silica.

[0155] Very particularly preferred dye pigments also having the trade name Flamenco® are, for example: Flamenco® Summit Turquoise T30D, BASF, titanium dioxide (and) mica Flamenco® Super Violet 530Z, BASF, mica (and) titanium dioxide.

[0156] In another embodiment, in the method, agent (a) and / or agent (b) may comprise one or more chromogenic compounds from the group of organic pigments.

[0157] The organic pigments in the present invention are correspondingly insoluble organic dyes or colour varnishes which may be selected, for example, from the group of nitroso, nitro, azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine and / or triarylmethane compounds.

[0158] Examples of particularly suitable organic pigments are e.g. 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, orange pigments with a color index of CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470 red pigments.

[0159] In another particularly preferred embodiment, the method of the present invention is characterized in that the agent (a) is preferably 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 red pigments with a Color Index of CI 15700. 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915, CI 75470 red pigments.

[0160] The organic pigment may also be a color varnish. The term color varnish in the sense of the present invention means a particle comprising a layer of absorbed dye, the unit consisting of particle and dye being insoluble under the above conditions. The particles may be, for example, inorganic substances, which may be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate or aluminum.

[0161] For example, Alizarin color varnish can be used as the color varnish.

[0162] For dyeing keratinous materials, pigments of a particular shape can also be used. For example, pigments based on small substrate plates, lamellar and / or lenticular, can be used. Furthermore, dyeing based on small substrate plates containing vacuum metallized pigments is also possible.

[0163] In another embodiment, the method according to the invention can be characterized in that the agent (a) also comprises one or more chromogenic compounds (a3) ​​from the group of pigments based on lamellar substrate plates, pigments based on lenticular substrate plates and vacuum metallized pigments.

[0164] Substrate plates of this type have an average thickness of at most 50 nm, preferably less than 30 nm, particularly preferably at most 25 nm, for example at most 20 nm. The average thickness of the substrate plate is at least 1 nm, preferably at least 2.5 nm, particularly preferably 5 nm, for example at least 10 nm. Preferred ranges of thickness of the substrate plate are 2.5-50 nm, 5-50 nm, 10-50 nm, 2.5-30 nm, 5-30 nm, 10-30 nm, 2.5-25 nm, 5-25 nm, 10-25 nm, 2.5-20 nm, 5-20 nm and 10-20 nm. Preferably, each small substrate plate has a thickness as uniform as possible.

[0165] Due to the small thickness of the small substrate plates, the pigments have a particularly high hiding power.

[0166] The substrate plate is a monolithic structure. Monolithic in this specification means that it is composed of a single closed unit without any breaks, stratification or inclusions, although structural changes may occur within the small substrate plate. The small substrate plates are preferably homogeneously structured, i.e., no concentration gradients occur within the small plate. In particular, the small substrate plates are not structured in layers and do not have a particle distribution in them.

[0167] The size of the small substrate plates can be adapted to each application, in particular to the desired effect on keratinous materials. Essentially, the substrate plates have an average maximum diameter of about 2 to 200 μm, in particular about 5 to 100 μm.

[0168] In a preferred embodiment, the shape factor (aspect ratio), expressed as the ratio between the average size and the average thickness, is at least 80, preferably at least 200, more preferably at least 500, and particularly preferably more than 750. The average size of the uncoated substrate plate is understood to mean the d50 value of the uncoated substrate plate. Unless otherwise stated, the d50 value was measured using an apparatus of the Sympatec Helos type equipped with a Quixel wet dispersion. To prepare the sample, the sample to be analyzed was predispersed in isopropanol for 3 minutes.

[0169] The small substrate plate can be made from any material that can be formed into a plate shape.

[0170] They may be of natural origin or synthetically produced. Materials that may constitute the small substrate plates are, for example, 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 plates are made of metals (alloys).

[0171] Any metal suitable for metallic pearlescent pigments can be used as the metal. Such metals include, inter alia, iron and steel, as well as all air- and water-resistant (semi)metals, such as platinum, zinc, chromium, molybdenum and silicon, and their alloys, such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver and gold.

[0172] Preferred small substrate plates are small aluminum plates and small brass plates, with aluminum small substrate plates being especially preferred.

[0173] The layered substrate plates are characterized by irregularly textured edges, which give them the appearance also known as "cornflakes."

[0174] Due to their irregular structure, pigments based on layered small substrate plates produce a high percentage of scattered light. Moreover, pigments based on layered small substrate plates do not completely cover the existing color of keratinous materials, and can achieve effects similar to natural graying, for example.

[0175] Lenticular (=lenticular) small substrate plates have substantially rounded edges and are also called "silver dollars" due to their appearance. Due to their regular structure, the proportion of reflected light is predominant in the case of pigments based on lenticular small substrate plates.

[0176] Vacuum metallized pigments (VMP) can be obtained, for example, by releasing metals, metal alloys or metal oxides from a corresponding coating film. They are characterized by a particularly low thickness of the substrate plate, in the range of 5-50 nm, and a particularly smooth surface with increased reflectivity. Small substrate plates with vacuum-metallized pigments are also called VMP substrate plates in the context of the present invention. VMP substrate plates of aluminum can be obtained, for example, by releasing aluminum from a metallized film.

[0177] Small substrate plates made of metal or metal alloys can be passivated, for example, by anodizing (oxide layer) or chromate treatment.

[0178] Uncoated layered, lenticular, and / or VPM substrate plates, especially those made of metals or metal alloys, are highly reflective of incident light, producing light-dark flops, and these have proven particularly preferred for use with agent (a).

[0179] Suitable pigments based on layered small substrate plates include, for example, the VISIONAIRE series of pigments manufactured by Eckart.

[0180] Pigments based on lenticular substrate platelets are available, for example, under the name Alegrace® Gorgeous from the company Schlenk Metallic Pigments GmbH.

[0181] Pigments based on small substrate plates containing vacuum metallized pigments are available, for example, under the names Alegleaces® Mevelous or Allegrace® Aurous from the company Schlenk Metlic Pigment GmbH.

[0182] In a further embodiment, the method according to the invention is characterized in that agent (a) contains one or more pigments in a total amount of 0.001 to 20% by weight, in particular 0.05 to 5% by weight, relative to the total weight of agent (a).

[0183] The agent (a) used in the method may contain one or more direct dyes as color-forming compounds. Direct dyes are dyes that are deposited directly on the hair and do not require an oxidation process to form color. Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols.

[0184] In the sense of the present invention, direct dyes have a water solubility (760 mmHg) of greater than 0.5 g / L at 25° C. and are therefore not considered pigments. In the sense of the present invention, direct dyes have a water solubility (760 mmHg) of greater than 1 g / L at 25° C.

[0185] Direct dyes can be classified into anionic direct dyes, cationic direct dyes and non-ionic direct dyes.

[0186] In a further preferred embodiment, the method is characterized in that the agent (a) further comprises, as chromogenic compound (a3), at least one anionic, cationic and / or nonionic direct dye.

[0187] Preferred cationic direct dyes include, for example, 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.

[0188] In particular, nonionic direct dyes which can be used are, for example, nonionic nitro and quinone dyes and natural azo dyes. Suitable nonionic direct dyes are those known under the following international 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, and 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.

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

[0190] In the sense of the present invention, an acid dye has a solubility in water (760 mmHg) of greater than 0.5 g / L at 25° C. and is therefore not considered a pigment. Preferably, in the sense of the present invention, an acid dye has a solubility in water (760 mmHg) of greater than 1 g / L at 25° C.

[0191] The alkaline earth (e.g. calcium and magnesium) or aluminum salts of acid dyes often have lower solubilities than the corresponding alkali salts. If the solubility of these salts is less than 0.5 g / L (25 °C, 760 mmHg), they are not included in the definition of direct dyes.

[0192] An essential feature of acid dyes is their ability to form an anionic charge, the carboxylic or sulfonic acid groups which carry this are usually attached to various chromophore systems. Suitable chromophore systems are found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthan dyes, rhodamine dyes, oxazine dyes and / or indophenol dyes.

[0193] For example, as suitable acid dyes, one or more compounds may be selected from the following group: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n° B001), Acid Yellow 3 (COLIPA n°: C54, D&C Yellow N° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n° C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121(CI 18690), Acid Orange 6(CI 14270), Acid Orange 7(2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA n°C015), Acid Orange 10(CI 16230;Orange G sodium salt), Acid Orange 11(CI 45370), Acid Orange 15(CI 50120), Acid Orange 20(CI 14600), Acid Orange 24(BROWN 1;CI 20170;KATSU201;Sodium free;Brown No.201;RESORCIN BROWN;ACID ORANGE 24;Japan Brown 201;D & C Brown No.1), Acid Red 14(CI14720), Acid Red 18(E124, Red 18;CI 16255), Acid Red 27(E 123, CI 16185, C-Rot 46, Echtrot D, FD&C Red Nr.2、Food Red 9、Naphtholrot S)、Acid Red 33(Red 33、Fuchsia Red、D&C Red 33、CI 17200)、Acid Red 35(CI C.I.18065)、Acid Red 51(CI 45430、Pyrosin B、Tetraiodfluorescein、Eosin J、Iodeosin)、Acid Red 52(CI 45100、Food Red 106、Solar Rhodamine B、Acid Rhodamine B、Red n°106 Pontacyl Brilliant Pink)、Acid Red 73(CI 27290)、Acid Red 87(Eosin、CI 45380)、Acid Red 92(COLIPA n°C 53、CI 45410)、Acid Red 95(CI 45425、Erythtosine,Simacid Erythrosine Y)、Acid Red 184(CI 15685)、Acid Red 195、Acid Violet 43(Jarocol Violet 43、Ext.D&C Violet n°2、C.I. 60730、COLIPA n°C063)、Acid Violet 49(CI 42640)、Acid Violet 50(CI 50325)、Acid Blue 1(Patent Blue、CI 42045)、Acid Blue 3(Patent Blau V、CI 42051)、Acid Blue 7(CI 42080)、Acid Blue 104(CI 42735)、Acid Blue 9(E 133、Patentblau 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(CI 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. .

[0194] For example, the water solubility of anionic direct dyes can be measured in the following way: For example, 0.1 g of anionic direct dye is added to a beaker. A stir bar is added. Then 100 ml of water is added. The mixture is heated to 25°C on a magnetic stirrer. The mixture is stirred for 60 minutes. The aqueous mixture is then visually evaluated. If undissolved residues are still present, increase the amount of water, for example in 10 mL increments. Add water until the amount of dye used is completely dissolved. If the dye-water mixture cannot be visually evaluated due to the high strength of the dye, filter the mixture. If some of the 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.

[0195] 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.

[0196] 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.

[0197] Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, whose solubility in water is greater than 40 g / L (25°C).

[0198] 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 readily soluble in water at 25°C.

[0199] 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.

[0200] 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.

[0201] Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate and has a solubility in water of 2.5 g / L (25° C.).

[0202] 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.).

[0203] Acid Blue 9 is the disodium salt of 2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonate and has a solubility in water greater than 20% by weight (25° C.).

[0204] The direct dyes, in particular the anionic direct dyes, can be used in different amounts in the agent (a), depending on the desired coloring strength. Good results have been obtained when the agent (a) comprises one or more direct dyes (a3) ​​in a total amount of 0.01 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, very particularly preferably 0.5 to 4.5% by weight, relative to the total weight of the agent (a).

[0205] <Cosmetic medium (a4) in agent (a)> The agent (a) particularly preferably comprises an organosilane (a2) and a color-forming compound (a3) ​​in a cosmetic carrier. The cosmetic carrier is not water, since the agent (a) is low-water or anhydrous. Particularly suitable cosmetic carriers are, for example, compounds from the group poly-C1-C6 alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol. Here, poly-C1-C6 alkylene glycols, in particular polyethylene glycol, are particularly suitable.

[0206] Within the scope of a further particularly preferred embodiment, the method according to the invention comprises at least one cosmetic carrier (a4) in which the agent (a) is very particularly preferably a polyethylene glycol from the group consisting of poly-C1-C6 alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol.

[0207] Alternatively, 1,2-propylene glycol is also used as 1,2-propanediol, with CAS numbers 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane], and 4254-153 [(S)-1,2-dihydroxypropane]. Ethylene glycol is also called 1,2-ethanediol, with CAS number 107-21-1. Glycerol is also called 1,2,3-propanetriol, with CAS number 56-81-5. Phenoxyethanol has CAS number 122-99-6.

[0208] All of the above solvents are commercially available from a variety of chemical manufacturers such as Aldrich and Fluka.

[0209] Particularly suitable solvents are alkylene glycols of formula (AG). TIFF2024531458000066.tif2485[in the formula, x represents an integer of 1 to 10,000, preferably an integer of 2 to 800, more preferably an integer of 3 to 600, even more preferably an integer of 3 to 400, and very particularly preferably an integer of 4 to 200.]

[0210] Thus, in a further very particularly preferred embodiment, the method according to the invention is characterized in that the agent (a) comprises one or more alkylene glycols (a4) of formula (AG). TIFF2024531458000067.tif2485[in the formula, x represents an integer of 1 to 10,000, preferably an integer of 2 to 800, more preferably an integer of 3 to 600, even more preferably an integer of 3 to 400, and very particularly preferably an integer of 4 to 200.]

[0211] The alkylene glycols of formula (AG) are protic substances having at least one hydroxy group and, based on their repeating unit -CH2-CH2-O-, are also called polyalkylene glycols or polyethylene glycols, when x represents a value of at least 2. In the alkylene glycols of formula (AG), x represents an integer between 1 and 10,000. In the course of the research leading to the present invention, it was found that these polyethylene glycols show particularly good suitability for improving the fastness properties of the colorants, on the one hand, and for optimally adjusting the viscosity of the agents, on the other hand.

[0212] Polyethylene glycols are liquid or solid water-soluble polymers depending on their chain length. Polyethylene glycols with molecular weights between 200 g / mol and 400 g / mol are non-volatile liquids at room temperature. PEG 600 has a melting point between 17 and 22 °C and a paste-like consistency. PEGs with molecular weights above 3,000 g / mol are solid substances and are commercially available as flakes or powders.

[0213] In particular, the use of low molecular weight alkylene glycols (or polyethylene glycols) has proven suitable for achieving the objectives according to the invention. In the sense of the present invention, in the case of low molecular weight alkylene glycols (or polyethylene glycols), x represents an integer from 1 to 100, preferably an integer from 1 to 80, further preferably an integer from 2 to 60, further preferably an integer from 3 to 40, further preferably an integer from 4 to 20 and very particularly preferably an integer from 6 to 15.

[0214] In a further very particularly preferred embodiment, the agent according to the invention is characterized in that it comprises at least one alkylene glycol (a4) of formula (AG-1). TIFF2024531458000068.tif2488[in the formula, x1 represents an integer of 1 to 100, preferably an integer of 1 to 80, more preferably an integer of 2 to 60, even more preferably an integer of 3 to 40, still more preferably an integer of 4 to 20, and very particularly preferably an integer of 6 to 15.

[0215] A particularly preferred low molecular weight polyethylene glycol is, for example, PEG 8. PEG-8 consists of an average of 8 ethylene glycol units (x1=8), has an average molecular weight of 400 g / mol, and has the CAS number 25322-68-3. PEG-8 is also known as PEG400 and is commercially available, for example, from APS.

[0216] Further suitable low molecular weight polyethylene glycols are, for example, PEG-6, PEG-7, PEG-9, and PEG-10.

[0217] Another suitable polyethylene glycol is, for example, PEG-32. PEG-32 consists of 32 ethylene glycol units (x1=32), has an average molecular weight of 1,500 g / mol, and has the CAS number 25322-68-3. PEG-32 is also known as PEG1500, and is commercially available, for example, from Clariant.

[0218] Furthermore, the use of high molecular weight polyethylene glycols has also proven suitable for achieving the objectives according to the invention.

[0219] In the sense of the present invention, the high molecular weight polyethylene glycol can be represented by the formula (AG-2), in which the index x2 represents an integer from 101 to 10,000. TIFF2024531458000069.tif2488

[0220] In very particularly preferred high molecular weight polyethylene glycols, x2 represents an integer from 101 to 1,000, preferably an integer from 105 to 800, more preferably an integer from 107 to 600, even more preferably an integer from 109 to 400, and very particularly preferably an integer from 110 to 200.

[0221] In a further very particularly preferred embodiment, the agent according to the invention is characterized in that it comprises at least one alkylene glycol (a4) of formula (AG-2). TIFF2024531458000070.tif2488[in the formula, x2 represents an integer of 101 to 1,000, preferably an integer of 105 to 800, more preferably an integer of 107 to 600, still more preferably an integer of 109 to 400, and very particularly preferably an integer of 110 to 200.]

[0222] A particularly suitable high molecular weight polyethylene glycol is, for example, PEG 6000, available from National Starch Co., Ltd. (China). PEG 6000 has a molecular weight of 6,000-7,500 g / mol, which corresponds to an x2 value of 136-171.

[0223] Another suitable polyethylene glycol is PEG 12000, which is commercially available, for example, from CG Chemikalien under the trade name Polyethylene Glycol 12000S (or PEG 12000S). The molecular weight of PEG 12000 is specified to be 10,500-15,000 g / mol, which corresponds to an x2 value of 238-341.

[0224] Another suitable polyethylene glycol is PEG 20000, available from Clariant under the trade name "Polyglycol 20000P" or alternatively "PEG-350". For PEG 20000, when the average molecular weight is specified as 20,000 g / mol, this corresponds to an x2 value of 454.

[0225] Preferably, agent (a) contains the above-described cosmetic carrier (a4) in a total amount of 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, even more preferably 50.0 to 99.0% by weight, very particularly preferably 70.0 to 99.0% by weight, based on the total weight of agent (a).

[0226] Within the scope of a further very particularly preferred embodiment, the method of the invention is characterized in that the agent (a) comprises one or more components of the cosmetic carrier (a4) in a total amount of 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, even more preferably 50.0 to 99.0% by weight and very particularly preferably 70.0 to 99.0% by weight, based on the total weight of the agent (a).

[0227] Within the scope of a further particularly preferred embodiment, the method according to the invention is characterized in that the agent (a) comprises one or more components (a4) selected from the group consisting of poly-C1-C6 alkylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol in a total amount of 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, even more preferably 50.0 to 99.0% by weight, very particularly preferably 70.0 to 99.0% by weight, based on the total weight of the agent (a).

[0228] In a further, explicitly very particularly preferred embodiment, the method according to the invention is characterized in that the agent (a) comprises one or more alkylene glycols (a4) of the formula (AG) in a total amount of 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, further preferably 50.0 to 99.0% by weight and very particularly preferably 70.0 to 99.0% by weight, based on the total weight of agent (a).

[0229] From the groups (a1), (a2), (a3) ​​and possibly (a4) it is understood that the sum of all components present in the agent (a) is not more than 100% by weight. If further optional components are used, they are reduced to a corresponding extent so that the sum of the aforementioned components is less than 100% by weight.

[0230] <Step (2): Applying agent (b) to keratinous material> In the second step of the method according to the invention, agent (b) is applied to the keratinous material or hair with agent (a) attached thereto. Step (2) is applied after step (1), i.e. after agent (a) has been completely applied to the keratinous material, agent (b) is applied. The successive application of the two agents (a) and (b) is carried out within one hour, preferably within 30 minutes. Agent (b) is particularly preferably applied within 10 minutes, very particularly preferably within 5 minutes, after application of agent (a) to the keratinous material. Application of agent (b) within 10 minutes means starting application of agent (b) within a time period of 10 minutes or less after application of agent (a) to the keratinous material is completed.

[0231] In a further particularly preferred embodiment, the method according to the invention is characterized in that agent (b) is applied within 10 minutes, preferably within 5 minutes, after application of agent (a).

[0232] By applying agent (b), a mixture of agent (a) and agent (b) is generated at the site of the keratinous material to which agent (a) is attached. Agent (b) contains a specific amount of water (b1), so that the silanes present on the keratinous material (a2) undergo an oligomerization or polymerization reaction, forming a colored film. Therefore, in the method of the present invention, it is essential to form a mixture of agents (a) and (b) at all sites of the keratinous material to be colored.

[0233] By mixing agents (a) and (b), the two agents are emulsified and the silane (a2) and a polymerization-initiating amount of water (b1) come into direct contact with each other. Mixing can be performed manually, for example, by massaging or working the two agents into the keratinous material with gloved hands.

[0234] In a further particularly preferred embodiment, the method according to the invention comprises the steps of: (2) The method is characterized in that agent (b) is applied to the keratinous material to which agent (a) has been attached, and the two agents (a) and (b) are mixed manually to produce a mixture of the two agents (a) and (b) on the keratinous material.

[0235] The water contained in agent (b) initiates the polymerization. For this purpose, it is particularly preferred to set the amount of water in agent (b) to a constant value. In this respect, it has been found to be particularly advantageous if agent (b) comprises 10 to 100% by weight, preferably 30 to 99.5% by weight, further preferably 50 to 99% by weight, very particularly preferably 80 to 99% by weight of water, relative to the total weight of agent (b).

[0236] In a further particularly preferred embodiment, the method according to the invention is characterized in that the agent (b) comprises 10 to 100% by weight, preferably 30 to 99.5% by weight, even more preferably 50 to 99% by weight and very particularly preferably 80 to 99% by weight of water, relative to the total weight of agent (b).

[0237] <Thickener in agent (b)> In order to ensure sufficiently high miscibility of agents (a) and (b) and to prevent agent (b) from dripping off the keratinous material or hair after application, agent (b) may further comprise a thickening agent.

[0238] In a further particularly preferred embodiment, the method according to the invention is characterized in that agent (b) comprises at least one thickening agent.

[0239] Suitable thickening agents include, for example, chemically modified celluloses, such as propyl cellulose, methyl ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, sulfoethyl cellulose, carboxymethyl sulfoethyl cellulose, hydroxypropyl sulfoethyl cellulose, hydroxyethyl sulfoethyl cellulose, methyl ethyl hydroxyethyl cellulose, methyl sulfoethyl cellulose, and / or ethyl sulfoethyl cellulose.

[0240] In a preferred embodiment, the method for coloring keratin materials is characterized in that the agent (b) further comprises a thickener selected from the group consisting of propyl cellulose, methyl ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxyethyl cellulose, sulfoethyl cellulose, carboxymethyl sulfoethyl cellulose, hydroxypropyl sulfoethyl cellulose, hydroxyethyl sulfoethyl cellulose, methyl ethyl hydroxyethyl cellulose, methyl sulfoethyl cellulose, ethyl sulfoethyl cellulose, and mixtures thereof.

[0241] Particularly suitable thickening agents are selected from hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, and mixtures thereof.

[0242] Further suitable thickening agents include galactomannans. Preferred galactomannans include those with the INCI name Cyamopsis tetragonoloba gum (guar gum), those with the INCI name Ceratonia siliqua (carob) gum (locust bean gum), those with the INCI name Cassia gum, and those with the INCI name Caesalpinia Spinosa gum (tara gum).

[0243] It is therefore particularly preferred that the method for colouring keratinous materials further comprises at least one galactomannan selected from the group consisting of the galactomannan with the INCI name Cyamopsis tetragonoloba Gum (Guar Gum), the galactomannan with the INCI name Ceratonia Siliqua (Carob) Gum (Locust Bean Gum), the galactomannan with the INCI name Cassia Gum and the galactomannan with the INCI name Caesalpinia Spinosa Gum (Tara Gum). In a particularly preferred embodiment, the galactomannan comprises the galactomannan with the INCI name Caesalpinia Spinosa Gum (Tara Gum).

[0244] The amount of the thickener is preferably 0.1 to 10% by weight, in any case, based on the total amount of agent (b).

[0245] <Further components of agents (a) and (b)> The above agents (a) and (b) may further comprise one or more optional ingredients.

[0246] The cosmetic ingredients that may be optionally used in the agent (a) may be any suitable ingredient for imparting further positive properties to the agent, for example, one or more compounds with surface-active properties from the group of nonionic, cationic, anionic or zwitterionic / amphoteric surfactants may further be contained in the agent (a) and / or (b).

[0247] The agent may also contain other active ingredients, auxiliaries and additives, such as solvents, fatty components, e.g. C8-C 30 Fatty acid triglycerides, C8-C 30 Fatty acid monoglycerides, C8-C 30fatty acid diglycerides and / or hydrocarbons; structuring agents such as glucose, maleic acid and lactic acid, phospholipids, hair conditioning compounds such as lecithin and cephalin; perfume oils, dimethyl isosorbide and cyclodextrin, fibre structure modifiers, in particular mono-, di- and oligosaccharides, such as glucose, galactose, fructose, citric acid and lactose; dyes for colouring the agent; anti-dandruff active ingredients such as piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides; animal and / or vegetable protein hydrolysates, and also their fatty acid condensates, or optionally anionic or cationic modified derivatives; vegetable oils, light stabilisers and UV screens; active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acid and their salts, bisabolol; polyphenols such as phenylalanine, ... phenols, especially hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones, flavonols, and the like; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes, such as fatty alcohols, beeswax, montan wax, paraffin, and the like; swelling and penetrating agents, such as glycerol, propylene glycol monoethyl ether, carbonates, bicarbonates, guanidine, urea, primary, secondary and tertiary phosphates, and the like; opacifying agents, such as latex, styrene / PVP, styrene / acrylamide copolymers, and the like; pearlescent agents, such as ethylene glycol mono- and distearate, and PEG-3-distearate; and propellants, such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0248] The selection of these additional substances is made by the skilled artisan depending on the desired properties of the agent. For other optional ingredients and the amounts of said ingredients to be used, explicit reference is made to reference books known to those skilled in the art. The additional active ingredients and auxiliaries are preferably used in the preparations of the invention in amounts of 0.0001 to 25% by weight, in particular 0.0005 to 15% by weight, in each case based on the total weight of the agent.

[0249] <Step (3): Applying both agents (a) and (b) to the keratin material> After the agents (a) and (b) have been mixed with one another, the mixture is applied to all those parts of the keratinous material to which the mixture of both agents has adhered.

[0250] By mixing the two agents (a) and (b), the silane (a2) contained in agent (a) comes into contact with a defined amount of water (b1) contained in agent (b), which initiates the hydrolysis and oligomerization or polymerization of the silane (a2). In this way, a coating or film is formed at the exact location of the keratinous material wetted with the mixture of both agents (a) and (b). The extent and rate of hydrolysis or polymerization is determined here by the ratio of the amount of silane (a2) to the amount of water (b1) on the hair. The smaller the quantitative ratio of (a2) to (b1), i.e. the quantitative ratio (a2) / (b)1), the greater the amount of water available for a given amount of silane and the faster and more extensive the polymerization proceeds. The quantitative ratio (a2) / (b1) is determined by the amounts of both agents (a) and (b) applied to the keratinous material or hair, respectively. Further factors are the concentration of silane (a2) in agent (a) and the concentration of water in agent (b). In this connection, it has been found that the oligomerization or polymerization can be adjusted to a rate optimal for the application when the weight ratio of the total amount of organosilicon compounds (a2) present in agent (a) to the amount of water (b1) contained in agent (b), i.e. the weight ratio (a2) / (b1), is 1:100 to 1:1, preferably 1:70 to 1:2, more preferably 1:70 to 1:5, very particularly preferably 1:70 to 1:10.

[0251] In other words, a particularly uniform and resistant coating on the keratinous materials could be produced when both the amounts of agents (a) and (b) and the concentrations of silane (a2) and water (b1) in the two agents were such that the ratio of silane (a2) and water (b1) on the keratinous materials was 1:100 to 1:1, preferably 1:70 to 1:2, more preferably 1:70 to 1:5, very particularly preferably 1:70 to 1:10.

[0252] Here, the weight ratio (a2) / (b1) of 1:70 to 1:10 means that the water (b1) derived from agent (b) is applied in an excess weight of 10 to 70 times the total amount of silanes (a2) derived from agent (a).

[0253] <Example> 40 g of agent (a) is applied to the subject's hair, and agent (a) is massaged into the entire hair for a short period of time.

[0254] The agent (a) comprises: 1.0% by weight of water (a1) (or a mixture of water and an acid, or a mixture of water and an alkaline solution), 3.0% by weight of 3-(aminopropyl)triethoxysilane (a2), 6.0% by weight of methyltriethoxysilane (a2), 1.0% by weight of a pigment (e.g., Unipure Red LC3079); 89% by weight polyethylene glycol (e.g. PEG-8).

[0255] The total amount of silanes (a2) contained in agent (a) is 3.6 g, i.e. 1.2 g of 3-(aminopropyl)-triethoxysilane and 2.4 g of methyltriethoxysilane.

[0256] After application of agent (a), 100 g of agent (b) is applied. Agent (b) is a thickening aqueous solution with a water content of 99% by weight. Agent (b) is also distributed uniformly over the entire head of the subject.

[0257] After application of agent (b), the hair is massaged vigorously with fingers for 1 minute to thoroughly mix agents (a) and (b) with each other.

[0258] Agent (b) contains 99 g of water (b1).

[0259] The weight ratio of the total amount of the organosilicon compound (a2) contained in the agent (a) to the amount of water (b1) contained in the agent (b), i.e., the weight ratio (a2) / (b1), is 3.6:99=1:27.5.

[0260] In an explicitly very particularly preferred embodiment, the process according to the invention is characterized in that the weight ratio of the total amount of organosilicon compounds (a2) contained in agent (a) to the amount of water (b1) contained in agent (b), i.e. the weight ratio (a2) / (b1), is between 1:100 and 1:1, preferably between 1:70 and 1:2, more preferably between 1:70 and 1:5 and very particularly preferably between 1:70 and 1:10.

[0261] After mixing the two agents (a) and (b), both agents are applied in the form of a mixture to the keratinous material. Preferably, both agents (a) and (b) are applied together to the keratinous material, in particular human hair, for 10 seconds to 30 minutes, preferably 30 seconds to 20 minutes, more preferably 1 minute to 15 minutes, and most preferably 5 minutes to 10 minutes.

[0262] In a further preferred embodiment, the method according to the invention comprises the steps of: (2) The method is characterized in that the two agents (a) and (b) are allowed to act together on the keratin substance for 10 seconds to 30 minutes, preferably 30 seconds to 20 minutes, more preferably 1 minute to 15 minutes, and most preferably 5 minutes to 10 minutes.

[0263] <Step (4): Rinse away both agents (a) and (b)> The experiments leading to the invention have shown that after the exposure time in step (3) of the method, a colored film is formed which is distinguished by a particularly high uniformity. When applied to the hair in the form of a full head application, the entire head of hair can be colored with a uniform coloring result. After the action of the two agents (a) and (b), they are rinsed off again from the keratinous materials or from the hair.

[0264] Thus, step (4) of the method according to the invention comprises rinsing both agents (a) and (b). The two agents (a) and (b) are preferably rinsed off with running water.

[0265] In a further preferred embodiment, the method of the present invention comprises the steps of: (3) Both agents (a) and (b) are rinsed away with running water. EXAMPLES

[0266] The following formulations were prepared (all values ​​are weight % unless otherwise noted):

[0267] [Table 1]

[0268] [Table 2]

[0269] Five tresses of hair (curling, natural, white) were dampened with running water and rubbed dry with a hand towel for 30 seconds. Agent (a) was then applied to all towel-dried tresses (0.4 g of agent (a) per tress). Agent (a) was massaged into all tresses for 30 seconds. Immediately after, agent (b) was applied to the tresses (1.0 g of agent (b) per tress). Each tress was massaged for 30 seconds to form a mixture of agent (a) and agent (b).

[0270] 0.036 g of silane (a2) was applied to the hair.

[0271] 0.99 g of water (b1) was applied to the hair.

[0272] The weight ratio (a2) / (b1) was 0.036:0.99=1:27.5.

[0273] The mixture of agents (a) and (b) was applied to the hair tress for 5 minutes. The tress was then rinsed with running water and dried. A uniform and intense coloration was obtained. In this way, all five tresses showed the same red color and had the same high color intensity.

[0274] <Comparison> Five hair tresses (curling, natural, white) were moistened with running water and rubbed dry with a hand towel for 30 seconds. Then, 40 g of agent (a) was mixed with 100 g of agent (b). This mixture was applied to the five hair tresses (in each case 1.4 g of application mixture per tress). Each tress was massaged for 30 seconds. The application mixture was then left to act on all tresses for 5 minutes each. The tresses were then rinsed with running water and dried. All tresses were dyed red. However, the tresses that were first stained with the mixture of agents (a) and (b) had a higher color intensity than the tresses that were treated last.

Claims

1. A method for dyeing keratinous materials, especially human hair, comprising the following steps: (1) applying agent (a) to the keratinous material, wherein said agent (a) contains, based on the total weight of agent (a), (a1) less than 10% by weight of water, (a2) at least one organosilicon compound from the group of silanes having 1, 2 or 3 silicon atoms, and (a3) at least one chromogenic compound, and (2) applying agent (b) to the keratinous material with agent (a) attached, wherein agent (b) contains (b1) water and (3) allowing both agents (a) and (b) to act on the keratinous material, and (4) rinsing both agents (a) and (b) in a predetermined order.

2. The method according to claim 1, characterized in that in step (1), agent (a) is applied to towel-dried or dry keratinous material.

3. Agent (a) contains, based on the total weight of agent (a), 0 to 7.5% by weight, preferably 0.0 to 5.0% by weight, more preferably 0.0 to 4.0% by weight, very particularly preferably 0.1 to 2.5% by weight of water (a1), the method according to claim 1 or 2.

4. Agent (a) contains at least one organosilicon compound (a2) represented by formula (I) and / or (II): Formula (I): [wherein, ·R １ 、R ２ are, independently of each other, a hydrogen atom or a C １ -C ６ alkyl group, - L represents a linear or branched divalent C １ - C ２０ alkylene group, ・R ３ 、R ４ are, independently of each other, C １ -C ６ alkyl group, and - a represents an integer from 1 to 3, - b represents an integer of 3 - a] Formula (II): [wherein, ・R ５ 、R ５ ’, R ５ ’’, R ６ 、R ６ ’ and R ６ ’’ are, independently of one another, C １ -C ６ alkyl group, - A, A', A'', A''' and A'''' are, independently of one another, linear or branched divalent C １ - C ２０ alkylene groups, ・R ７ and R ８ are each independently a hydrogen atom, C １ -C ６ alkyl group, hydroxy C ２ -C ６ alkyl group, C １ -C ６ alkenyl group, amino C １ -C ６ alkyl group, or a group of formula (III): represents, - c represents an integer from 1 to 3, - d represents an integer of 3 - c, - c' represents an integer from 1 to 3, - d' represents an integer of 3 - c', - c'' represents an integer from 1 to 3, - d'' represents an integer of 3 - c'', - e represents 0 or 1, - f represents 0 or 1, - g represents 0 or 1, - h represents 0 or 1, provided that at least one of the functional groups e, f, g and h is different from 0] the method according to claim 1.

5. Agent (a) contains at least one organosilicon compound (a2) represented by formula (I): [wherein, ・R １ 、R ２ each represent a hydrogen atom, - L represents a linear divalent C １ - C ６ alkylene group, preferably a propylene group (-CH ２ - CH ２ - CH ２ -), or an ethylene group (-CH ２ - CH ２ -), and ・R ３ 、R ４ each independently represents a methyl group or an ethyl group, - a represents the number 3, - b represents the number 0] the method according to claim 1.

6. Agent (a) is - (3 - aminopropyl)triethoxysilane, - (3 - aminopropyl)trimethoxysilane, - 1 - (3 - aminopropyl)silanetriol, - (2 - aminoethyl)triethoxysilane, - (2 - aminoethyl)trimethoxysilane, - 1-(2-Aminoethyl)silantriol, - (3-Dimethylaminopropyl)triethoxysilane, - (3-Dimethylaminopropyl)trimethoxysilane, - 1-(3-Dimethylaminopropyl)silantriol, - (2-Dimethylaminoethyl)triethoxysilane, - (2-Dimethylaminoethyl)trimethoxysilane, and / or, - 1-(2-Dimethylaminoethyl)silantriol, The method according to claim 1, characterized in that it comprises at least one organosilicon compound (a2) selected from the group consisting of:

7. Agent (a) is of formula (IV): [Wherein, - R ９ represents a C １ - C １８ alkyl group, ・R １０ represents a hydrogen atom or C １ -C ６ alkyl group, ・R １１ is C １ -C ６ represents an alkyl group, - k represents an integer from 1 to 3, - m represents an integer of 3 - k] The method according to claim 1, characterized in that it comprises at least one organosilicon compound (a2) represented by:

8. Agent (a) is - Methyltrimethoxysilane, - Methyltriethoxysilane, - Ethyltrimethoxysilane, - Ethyltriethoxysilane, - Propyltrimethoxysilane - Propyltriethoxysilane - Hexyltrimethoxysilane, - Hexyltriethoxysilane, - Octyltrimethoxysilane, - Octyltriethoxysilane, - Dodecyltrimethoxysilane, - Dodecyltriethoxysilane, - Octadecyltrimethoxysilane, and - Octadecyltriethoxysilane The method according to claim 1, characterized in that it comprises at least one organosilicon compound (a2) selected from the group consisting of:

9. The method according to claim 1, characterized in that agent (a) comprises at least two organosilicon compounds (a2) that are structurally different from each other.

10. The method according to claim 1, characterized in that agent (a) contains one or more organosilicon compounds (a2) in a total amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 8% by weight, based on the total weight of agent (a).

11. The method according to claim 1, characterized in that agent (a) comprises at least one chromogenic compound (a3) from the group of pigments and / or direct dyes.

12. The agent (a) contains at least one inorganic pigment, preferably selected from the group of color-developing metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfates, double metal cyanides, metal sulfates, bronze pigments, and / or at least one colored mica-based pigment coated with a metal oxide and / or metal oxychloride. The method according to claim 1 is characterized by this.

13. The agent (a) contains at least one organic pigment, preferably carmine, quinacridone, phthalocyanine, sorghum, blue pigments with Color Index numbers Cl42090, CI69800, CI69825, CI73000, CI74100, CI74160, yellow pigments with Color Index numbers CI11680, CI11710, CI15985, CI19140, CI20040, CI21100, CI21108, CI47000, CI47005, green pigments with Color Index numbers CI61565, CI61570, CI74260, orange pigments with Color Index numbers CI11725, CI15510, CI45370, CI71105, and red pigments with Color Index numbers CI12085, CI12120, CI12370, CI12420, CI12490, CI14700, CI15525, CI15580, CI15620, CI15630, CI15800, CI15850, CI15865, CI15880, CI17200, CI26100, CI45380, CI45410, CI58000, CI73360, CI73915 and / or CI75470. The method according to claim 1 is characterized by containing at least one color-developing compound (a3) selected from the group consisting of these.

14. The agent (a) contains one or more color-developing compounds (a3) from the group of pigments based on lamellar substrate plates, pigments based on lenticular substrate plates, and vacuum deposition pigments. The method according to claim 1 is characterized by this.

15. Agent (a) is poly-C １ -C ６ The method according to claim 1, characterized in that it comprises at least one cosmetic carrier (a4) chosen from the group consisting of alkylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol, and very particularly preferably polyethylene glycol.

16. The agent (a) contains, in total, 10.0 to 99.0% by weight, preferably 30.0 to 99.0% by weight, more preferably 50.0 to 99.0% by weight, and very particularly preferably 70.0 to 99.0% by weight, based on the total weight of the agent (a), of the components of one or more cosmetic carriers (a4), according to the method of claim 1.

17. The method according to claim 1, characterized in that the agent (b) is applied within 10 minutes, preferably within 5 minutes, after the application of the agent (a).

18. The method according to claim 1, characterized in that the agent (b) is applied to the keratinous material with the agent (a) adhering thereto, and a mixture of the two agents is produced by manually mixing the agents (a) and (b) on the keratinous material.

19. The method according to claim 1, characterized in that the agent (b) contains 10 to 100% by weight, preferably 30 to 99.5% by weight, more preferably 50 to 99% by weight, and very particularly preferably 80 to 99% by weight of water, based on the total weight of the agent (b).

20. The method according to claim 1, characterized in that the agent (b) contains at least one thickener.

21. The method according to claim 1, characterized in that the weight ratio of the total amount of the organosilicon compound (a2) contained in the agent (a) to the amount of water (b1) contained in the agent (b), i.e., the weight ratio (a2) / (b1), is a value of 1:100 to 1:1, preferably 1:70 to 1:2, more preferably 1:70 to 1:5, and very particularly preferably 1:70 to 1:

10.

22. The method according to claim 1, characterized in that the two agents (a) and (b) are allowed to act on the keratinous material together for a time of 10 seconds to 30 minutes, preferably 30 seconds to 20 minutes, more preferably 1 minute to 15 minutes, and most preferably 5 minutes to 10 minutes.

23. The method according to claim 1, characterized in that the two agents (a) and (b) are rinsed off with running water.

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