Method for dyeing keratinous material comprising the leave-on application of a dye that has a low water content and comprises c1-c6 alkoxy silane, pigment and solvent

Abstract

The present invention relates to a method for dyeing keratinous material, in particular human hair, comprising the following steps in the specified order: (1) providing a dye (F), wherein the dye (F) - in relation to the total weight of the dye (F) - contains: (F1) one or more organic C1-C6 alkoxy silanes and / or condensation products thereof, (F2) at least one pigment, (F3) less than 25.0 wt.% water, and (F4) at least one solvent different from water, (2) administering the dye (F) to moistened or dry keratinous material, (3) optionally applying a defined amount of water to the keratinous material, which is still loaded with the dye (F), wherein the weight of the amount of water applied in step (3) is at most twice the weight of the dye (F) administered in step (2), and (4) drying the keratinous material without washing out the dye (F) beforehand.

Description

[0001] Henkel AG & Co. KGaA

[0002] 2022P00033WO

[0003] A method for coloring keratinic material comprising the leave-on application of a low-water colorant containing Ci-Ce-alkoxy-silane, pigment and solvent

[0004] The present application relates to a method for dyeing keratinic material, in particular human hair, in which a low-water dye containing at least one Ci-Ce-alkoxysilane, a pigment and a solvent is applied to the keratin material as a leave-on product.

[0005] Altering the shape and color of keratinous material, especially human hair, represents an important area of ​​modern cosmetics. Depending on the coloring requirements, hair coloring specialists are familiar with various coloring systems. For permanent, intense colorings with good fastness properties and good gray coverage, oxidation dyes are typically used. Such dyes contain oxidation dye precursors, so-called developer components, and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes. Oxidation dyes are characterized by very long-lasting coloring results.

[0006] When using direct dyes, the fully formed pigments diffuse from the dyeing agent into the hair fiber. Compared to oxidative hair coloring, the colors obtained with direct dyes are less durable and wash out more quickly. Colorations with direct dyes typically remain on the hair for between 5 and 20 washes.

[0007] The use of color pigments is known for temporary color changes on hair and / or skin. Color pigments are generally understood to be insoluble, color-imparting substances. These are present undissolved in the form of small particles in the coloring formulation and are deposited only externally on the hair fibers and / or the skin surface. Therefore, they can usually be removed without residue after several washes with surfactant-containing cleansers. Various products of this type are available on the market under the name hair mascara.

[0008] If the user desires particularly long-lasting coloring, the use of oxidative colorants has so far been the only option. However, despite numerous optimization attempts, an unpleasant ammonia or amine odor cannot be completely avoided with oxidative hair coloring. The hair damage still associated with the use of oxidative colorants also has a detrimental effect on the user's hair. Therefore, the search for alternative, high-performance coloring methods remains a challenge.

[0009] EP 2168633 B1 addresses the problem of creating long-lasting hair colorings using pigments. The document teaches that using a combination of pigment, organic silicon compound, hydrophobic polymer, and a solvent, it is possible to create hair colorings that are said to be particularly resistant to shampooing. For example, 3-aminopropyltriethoxysilane was used as the organic silicon compound.

[0010] The coloring processes of EP 2168633 B1 utilize organosilicon compounds from the silane group, the molecular structure of which includes at least one hydroxyl group and / or hydrolyzable group. Due to the presence of the hydroxyl groups or hydrolyzable groups, the silanes are reactive substances that hydrolyze, oligomerize, or polymerize in the presence of water. The oligomerization or polymerization of the silanes, initiated by the presence of water, ultimately leads, when applied to the keratin material, to the formation of a film that fixes the color-imparting compounds, thus producing very long-lasting colorations.

[0011] However, a closer examination of the coloring processes disclosed in EP 2168633 B1 revealed that the colorations produced on hair using these agents or processes still require improvement. In particular, the color intensity and abrasion resistance of the colorations from the hair still need to be optimized, and the durability, especially the washfastness of these colorations, also requires further improvement.

[0012] The objective of the present invention was to find a method for coloring keratin material such as hair, with which the pigments known from the prior art can be fixed to the hair in an extremely permanent manner. The colorants should have very good storage stability, and the user should be required to perform as few steps as possible when applying the products. Furthermore, the application should be as sustainable as possible and use as little water as possible. Furthermore, the color intensity, durability, and especially the washfastness of the colorations should be improved.

[0013] Surprisingly, it has now been found that the aforementioned objects can be excellently achieved if, in a coloring process, a low-water colorant (F) is applied to the keratin material, which contains one or more organic Ci-Ce-alkoxysilanes (F1), at least one pigment (F2), less than 25.0 wt. % water (F3), and at least one solvent other than water (F4). The core aspect of the invention is that the colorant (F) is not washed out, but rather the keratin material, on which the colorant (F) is still present, is dried.The work leading to this invention has surprisingly shown that this dyeing process is not only more efficient and the user consumes less water when applying the dye, but that the keratin materials dyed in this way could also be dyed more intensively and the resulting dyeings had better durability, in particular better washfastness.

[0014] The subject of the present invention is a process for dyeing keratin material, in particular human hair, comprising the following steps in the given order:

[0015] (1) Providing a colorant (F), wherein the colorant (F) contains - based on the total weight of the colorant (F):

[0016] (F1) one or more organic Ci-Ce-alkoxysilanes and / or their condensation products,

[0017] (F2) at least one pigment,

[0018] (F3) less than 25.0 wt% water, and

[0019] (F4) at least one solvent other than water,

[0020] (2) Application of the colorant (F) on moistened or dry keratin material,

[0021] (3) optionally applying a defined amount of water to the keratinic material which is still coated with the coloring agent (F), the weight of the amount of water applied in step (3) being at most twice the weight of the coloring agent (F) applied in step (2), and

[0022] (4) Drying of the keratin material without prior washing out of the colorant (F). keratin material

[0023] Keratinous material includes hair, skin, and nails (such as fingernails and / or toenails). Wool, fur, and feathers also fall under the definition of keratinous material.

[0024] Keratin material is preferably understood to mean human hair, human skin, and human nails, especially fingernails and toenails. Keratin material is most preferably understood to mean human hair.

[0025] Dye (F) for coloring keratin material

[0026] In step (1) of the process according to the invention, a colorant (F) is provided. The colorant (F) is characterized in that it contains, based on the total weight of the colorant (F):

[0027] (F1) one or more organic Ci-Ce-alkoxysilanes and / or their condensation products, (F2) at least one pigment,

[0028] (F3) less than 25.0 wt% water, and

[0029] (F4) at least one solvent other than water.

[0030] The term "coloring agent" is used in the context of this invention for a coloring of the keratin material, in particular of the hair, caused by the use of pigments. During this coloring, the aforementioned pigments (F2) are deposited in a particularly homogeneous and smooth film on the surface of the keratin material. The film forms in situ through oligomerization or polymerization of the organic Ci-Ce-alkoxysilane(s) (F1) and encloses the pigment(s) (F2).

[0031] Organic Ci-Cs-alkoxysilanes (F1) and / or their condensation products,

[0032] As the first substance class essential to the invention, the colorant (F) contains one or more organic Ci-Ce-alkoxysilanes (F1) and / or their condensation products.

[0033] The organic Ci-Ce-alkoxysilanes (F1) contained in the colorant (F) are reactive compounds. Organic silicon compounds, alternatively also referred to as organosilicon compounds, are compounds that either have a direct silicon-carbon bond (Si-C) or in which the carbon is linked to the silicon atom via an oxygen, nitrogen, or sulfur atom. The organic Ci-Ce-alkoxysilanes according to the invention are compounds that contain one to three silicon atoms. The organic Ci-Ce-alkoxysilanes particularly preferably contain one or two silicon atoms.

[0034] According to the lUPAC rules, the term silane refers to a group of chemical compounds based on a silicon backbone and hydrogen. In organic silanes, the hydrogen atoms are completely or partially replaced by organic groups such as (substituted) alkyl groups and / or alkoxy groups. In organic silanes, some of the hydrogen atoms can also be replaced by hydroxy groups.

[0035] Organic Ci-Ce-alkoxysilanes comprising at least one C1-C6-alkoxy group directly bonded to the silicon atom. The alkoxy group is reactive and can first be hydrolyzed in the presence of water and subsequently condensed with another organic Ci-Ce-alkoxysilane (or its hydrolysis product). The Ci-Ce-alkoxy group is preferably an ethoxy group or a methoxy group. If, for example, the hydrolyzable group is an ethoxy group, the organic silicon compound preferably contains a structural unit R'R“R“'Si-O-CH2-CH3. The radicals R', R" and R"' represent the three remaining free valences of the silicon atom. Particularly good results were obtained when the colorant (F) according to the invention contained at least one first organic Ci-Ce-alkoxysilane (F1) of the formula (I).

[0036] In a particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one organic Ci-Ce-alkoxysilane (F1) of the formula (I) and / or its condensation products,

[0037] RiR2N-L-Si(OR3)a(R4)b (l), where

[0038] - Ri, R2 independently represent a hydrogen atom or a Ci-Ce-alkyl group,

[0039] - L represents a linear or branched, divalent Ci-C2o-alkylene group,

[0040] - R3, R4 independently represent a Ci-Ce-alkyl group,

[0041] - a, stands for an integer from 1 to 3, and

[0042] - b stands for the integer 3 - a.

[0043] The substituents Ri, R2, R3, R4 and L in the compounds of formula (I) are exemplified below:

[0044] Examples of a C1-C8-alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkyl radicals. Examples of a C2-C8-alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl; preferred C2-C8-alkenyl radicals are vinyl and allyl. Preferred examples of a hydroxy-C1-C8-alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group; a 2-hydroxyethyl group is particularly preferred. Examples of an amino-Ci-Ce-alkyl group are the aminomethyl group, the 2-aminoethyl group, and the 3-aminopropyl group. The 2-aminoethyl group is particularly preferred.Examples of linear divalent C1-C2o-alkylene groups include the methylene group (-CH2-), the ethylene group (-CH2-CH2-), the propylene group (-CH2-CH2-CH2-), and the butylene group (-CH2-CH2-CH2-CH2-). The propylene group (-CH2-CH2-CH2-) is particularly preferred. From a chain length of 3 carbon atoms, divalent alkylene groups can also be branched. Examples of branched, divalent C3-C2o-alkylene groups are (-CH2-CH(CH3)-) and (-CH2-CH(CH3)-CH2-).

[0045] In the organic silicon compounds of formula (I)

[0046] Ri R2N-L-Si(OR3) a (R4)b (I), the radicals R1 and R2 independently represent a hydrogen atom or a C1-C6 alkyl group. Most preferably, the radicals R1 and R2 both represent a hydrogen atom.

[0047] In the middle part of the organic silicon compound is the structural unit or linker -L- which represents a linear or branched, divalent Ci-C2o-alkylene group.

[0048] Preferably, -L- represents a linear, divalent C1-C20-alkylene group. More preferably, -L- represents a linear, divalent C1-C8-alkylene group. More preferably, -L- represents a methylene group (-CH2-), an ethylene group (-CH2-CH2-), a propylene group (-CH2-CH2-CH2-), or a butylene group (-CH2-CH2-CH2-CH2-). Most preferably, L represents a propylene group (-CH2-CH2-CH2-).

[0049] The organic silicon compounds of the formula (I) according to the invention

[0050] Ri R2N-L-Si(OR3) a (R4)b (l), each carry at one end the silicon-containing group -Si(OR3)a(R4)b

[0051] In the terminal structural unit -Si(OR3)a(R4)b, the radical R3 represents a hydrogen atom or a C1-C8 alkyl group, and the radical R4 represents a C1-C8 alkyl group. Particularly preferably, R3 and R4 independently represent a methyl group or an ethyl group.

[0052] Here, a represents an integer from 1 to 3, and b represents the integer 3 - a. If a represents the number 3, then b is 0. If a represents the number 2, then b is 1. If a represents the number 1, then b is 2.

[0053] Dyes with the best wash fastness properties could be obtained if the agent according to the invention contains at least one first organic silicon compound (a1) of the formula (I) in which the radicals R3, R4 independently of one another represent a methyl group or an ethyl group.

[0054] Furthermore, dyeings with the best washfastness properties could be obtained when the agent according to the invention contains at least one first organic silicon compound (a1) of formula (I), in which the radical a represents the number 3. In this case, the radical b represents the number 0.

[0055] In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one first organic silicon compound (a1) of the formula (I), wherein

[0056] - R3, R4 independently represent a methyl group or an ethyl group and

[0057] - a stands for the number 3 and - b stands for the number 0.

[0058] In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one first organic silicon compound (a1) of the formula (I),

[0059] Ri R2N-L-Si(OR3) a (R4)b (l), where

[0060] - Ri, R2 both represent a hydrogen atom, and

[0061] - L represents a linear, divalent Ci-Ce-alkylene group, preferably a propylene group (-CH2-CH2-CH2-) or an ethylene group (-CH2-CH2-),

[0062] - R3, R4 independently represent a methyl group or an ethyl group and

[0063] - a stands for the number 3 and

[0064] - b stands for the number 0.

[0065] Organic compounds particularly suitable for solving the problem according to the invention

[0066] Silicon compounds of formula (I) are

[0067] - (3-Aminopropyl)triethoxysilane

[0068] - (3-Aminopropyl)trimethoxysilane

[0069] - (2-Aminoethyl)triethoxysilane

[0070]

[0071] - (2-Aminoethyl)trimethoxysilane

[0072] - (3-Dimethylaminopropyl)triethoxysilan

[0073] - (3-Dimethylaminopropyl)trimethoxysilan

[0074] -1 -(3-Dimethylaminopropyl)silantriol

[0075] - (2- D i met hy la m i n oethy l)t riet h oxys i la n .

[0076] - (2-Dimethylaminoethyl)trimethoxysilan und / oder

[0077] -1-(2-Dimethylaminoethyl)silantriol

[0078] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one organic Ci-Ce-alkoxysilane (F1) which is 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, (2-dimethylaminoethyl)triethoxysilane and their condensation products.

[0079] It is particularly preferred if the colorant contains (3-aminopropyl)triethoxysilane and / or its condensation products.

[0080] The aforementioned organic O-Ce-alkoxysilanes of formula (I) are commercially available. (3-Aminopropyl)trimethoxysilane can be purchased, for example, from Sigma-Aldrich. (3-Aminopropyl)triethoxysilane is also commercially available from Sigma-Aldrich. To achieve dyeings with particularly good rubfastness and particularly high washfastness, it has proven particularly advantageous if the inventive dyeing agent (F) contains, in addition to or alternatively to the organic Ce-Ce-alkoxysilanes of formula (I), at least one organic Ce-Ce-alkoxysilane of formula (II) R5Si(OR6)k(R7)m (II).

[0081] The organic Ci-Ce-alkoxysilane(s) of formula (II) can also be referred to as silanes of the alkyl-alkoxysilane or alkyl-hydroxysilane type,

[0082] R5Si(OR6)k(R7)m (II), where

[0083] - R5 represents a Ci-Ci2 alkyl group,

[0084] - Re represents a hydrogen atom or a Ci-Ce alkyl group,

[0085] - R7 represents a Ci-Ce-alkyl group

[0086] - k is an integer from 1 to 3, and

[0087] - m stands for the integer 3 - k.

[0088] In a further preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one organic Ci-Ce-alkoxysilane (F1) of the formula (II).

[0089] R5Si(OR6)k(R7)m (II), where

[0090] - R5 represents a Ci-Ci2 alkyl group,

[0091] - Re represents a hydrogen atom or a Ci-Ce alkyl group,

[0092] - R7 represents a Ci-Ce-alkyl group

[0093] - k is an integer from 1 to 3, and

[0094] - m stands for the integer 3 - k.

[0095] In a further preferred embodiment, a colorant (F) used in the process according to the invention is characterized in that, in addition to the organic Ci-Ce-alkoxysilane(s) of the formula (I), it contains at least one further organic Ci-Ce-alkoxysilane of the formula (II)

[0096] R5Si(OR6)k(R7)m (II), where

[0097] - R5 represents a Ci-Ci2-alkyl group, - Re represents a hydrogen atom or a Ci-Ce-alkyl group,

[0098] - R7 represents a Ci-Ce-alkyl group

[0099] - k is an integer from 1 to 3, and

[0100] - m stands for the integer 3 - k.

[0101] In the organic C1-C12 alkoxysilanes of formula (II), the radical R5 represents a C1-C12 alkyl group. This C1-C12 alkyl group is saturated and can be linear or branched. R5 preferably represents a linear C1-C12 alkyl group. R5 preferably 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, or an n-dodecyl group. R5 particularly preferably represents a methyl group, an ethyl group, or an n-octyl group.

[0102] In the organic silicon compounds of form (II), the radical Re represents a hydrogen atom or a C1-C8 alkyl group. Particularly preferably, Re represents a methyl group or an ethyl group.

[0103] In the organic silicon compounds of form (II), the radical R represents a C1-C8 alkyl group. Particularly preferably, R7 represents a methyl group or an ethyl group.

[0104] Furthermore, k represents an integer from 1 to 3, and m represents the integer 3 - k. If k represents the number 3, then m is 0. If k represents the number 2, then m is 1. If k represents the number 1, then m is 2.

[0105] Dyes with the best washfastness properties were obtained when a dyeing agent (F) containing at least one organic Ci-Ce-alkoxysilane of formula (II) was used in the process, in which the radical k represents the number 3. In this case, the radical m represents the number 0.

[0106] Organic silicon compounds of the formula (II) which are particularly suitable for solving the problem according to the invention are

[0107] - Methyltrimethoxysilane

[0108] - Methyltriethoxysilane

[0109]

[0110] - Ethyltriethoxysilane

[0111] - n-Hexyltriethoxysilane

[0112]

[0113] - n-octyltriethoxysilane

[0114] - n-dodecyltrimethoxysilane and / or

[0115] - n-Dodecyltriethoxysilane.

[0116]

[0117] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one organic Ci-Ce-alkoxysilane (F1) which is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane and their condensation products.

[0118] Other organic silicon compounds which are particularly well suited to solving the problem according to the invention are also

[0119] - Vinyltrimethoxysilane and

[0120] - Vinyltriethoxysilane.

[0121] In an explicitly very particularly preferred embodiment, a colorant (F) according to the invention is characterized in that it contains at least one first organic Ci-Ce-alkoxysilane of the formula (I), which is selected from the group consisting of (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and additionally contains at least one second organic Ci-Ce-alkoxysilane of the formula (II), which is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.

[0122] The organic Ci-Ce-alkoxysilanes described above are reactive compounds. To achieve particularly good dyeing results, it is particularly advantageous to use the organic Ci-Ce-alkoxysilanes of formula (I) and / or (II) in specific amounts in the dye (F).

[0123] In this context, it has been found to be preferred if the coloring agent (F) according to the invention - based on the total weight of the agent - contains one or more organic Ci-Ce-alkoxysilanes (F1) and / or their condensation products in a total amount of 0.1 to 30.0 wt.%, preferably of 0.5 to 20.0 wt.%, more preferably of 5.0 to 15.0 wt.% and very particularly preferably of 6.0 to 12.5 wt.%. Within the scope of a further very particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains one or more organic Ci-Ce-alkoxysilanes (F1) and / or their condensation products in a total amount of 0.1 to 30.0 wt.%, preferably of 0.5 to 20.0 wt.%, more preferably of 5.0 to 15.0 wt.% and very particularly preferably of 6.0 to 12.5 wt.%.

[0124] Oligomers or condensates of organic silicon compounds

[0125] The organic Ci-Ce-alkoxysilanes (F1) according to the invention, in particular those of formula (I) and / or (II), are reactive compounds which can undergo hydrolysis and condensation reactions with water.

[0126] The reaction of organic Ci-Ce-alkoxysilanes with water can occur in several ways. The reaction starts as soon as the Ci-Ce-alkoxysilanes come into contact with water through mixing. As soon as Ci-Ce-alkoxysilanes and water come into contact, an exothermic hydrolysis reaction takes place according to the following scheme (reaction scheme using 3-aminopropyltriethoxysilane as an example):

[0127] Depending on the number of hydrolyzable Ci-Ce alkoxy groups per silane molecule, the hydrolysis reaction can also take place multiple times per Ci-Ce alkoxy silane used:

[0128] Hydrolysis using the example of methyltrimethoxysilane: OMe OMe

[0129] CH3— S —OMe + H2O - ► CH3— Si I— OH + MeOH

[0130] OMe OMe

[0131] Depending on the amount of water used, the hydrolysis reaction can also take place several times per Ci-Ce-alkoxy silane used:

[0132] Following the hydrolysis, or almost simultaneously with the hydrolysis, a condensation of the partially (or partially completely) hydrolyzed Ci-Ce-alkoxysilanes takes place. The precondensation can, for example, proceed according to the following scheme:

[0133] OH OH OMe OH

[0134] H3C— -Si— OMe H3C — Si — OMe MeO — Si — O — Si — OMe + MeOH

[0135] OMe OMe CH3CH3

[0136] Both partially hydrolyzed and fully hydrolyzed Ci-Ce alkoxysilanes can participate in the condensation reaction, undergoing condensation with unreacted, partially, or fully hydrolyzed Ci-Ce alkoxysilanes. Possible condensation reactions include (shown using the mixture of (3-aminopropyl)triethoxysilane and methyltrimethoxysilane): and / or

[0137] In the above exemplary reaction schemes, the condensation to a dimer is shown, but further condensations to oligomers with several silane atoms are also possible and preferred.

[0138] This hydrolysis or condensation reaction begins even in the presence of very small amounts of water, therefore the oligomers and / or condensation products of the aforementioned organic silicon compounds are also encompassed by this invention.

[0139] Pigments (F2)

[0140] As a second essential component, the colorant (F) used in the process according to the invention contains at least one pigment (F2).

[0141] Pigments in the sense of the present invention are understood to be color-imparting compounds which have a solubility in water at 20°C of less than 0.5 g / L, preferably less than 0.1 g / L, even more preferably less than 0.05 g / L. The water solubility can be determined, for example, using the method described below: 0.5 g of the pigment is weighed into a beaker. A stirring bar is added. Then, one liter of distilled water is added. This mixture is heated to 20°C for one hour while stirring on a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is below 0.5 g / L. If the pigment-water mixture cannot be visually assessed due to the high intensity of the pigment, which may be present in finely dispersed form, the mixture is filtered.If a portion of undissolved pigment remains on the filter paper, the solubility of the pigment is below 0.5 g / L.

[0142] Suitable pigments or color pigments can be of inorganic and / or organic origin. In a preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one pigment (F2) from the group of inorganic pigments, organic pigments, and / or metallic pigments.

[0143] Preferred color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be made from chalk, ochre, umber, green earth, burnt sienna, or graphite, for example. Other inorganic color pigments that can be used include black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, as well as fluorescent or phosphorescent pigments.

[0144] Particularly suitable are colored metal oxides, hydroxides, and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates, and / or molybdates. Particularly preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), iron blue (ferric ferrocyanide, CI 77510), and / or carmine (cochineal).

[0145] Also particularly preferred color pigments according to the invention are colored pearlescent pigments. These are typically based on mica and / or mica and can be coated with one or more metal oxides. Mica belongs to the class of 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, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.

[0146] As an alternative to natural mica, synthetic mica, optionally coated with one or more metal oxides, can also be used as a pearlescent pigment. Particularly preferred pearlescent pigments are based on natural or synthetic mica and coated with one or more of the aforementioned metal oxides. The color of the respective pigments can be varied by varying the layer thickness of the metal oxide(s).

[0147] In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one pigment selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored pigments based on mica or mica, which are coated with at least one metal oxide and / or one metal oxychloride.In a further preferred embodiment, a colorant (F) according to the invention is characterized in that it contains at least one pigment (F2) which is selected from mica- or mica-based pigments coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (ferric ferrocyanide, CI 77510).

[0148] Examples of particularly suitable color pigments are commercially available under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® from Sunstar.

[0149] Please be sure to drink the color pigments with the Handelsbezeichnung Colorona® and beispielsweise:

[0150] Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

[0151] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

[0152] Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

[0153] Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

[0154] Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA

[0155] Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0156] Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA

[0157] Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)

[0158] 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 GREENS)

[0159] Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (Cl 77510)

[0160] Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES) Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

[0161] Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE

[0162] Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES) Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES)

[0163] Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES)

[0164] Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

[0165] Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0166] Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA

[0167] Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES)

[0168] Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

[0169] Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891 , Cl 77491 (EU)

[0170] Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides) Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

[0171] Other particularly preferred color pigments with the trade name Xirona® include:

[0172] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0173] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0174] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0175] Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0176] In addition, particularly preferred color pigments with the trade name Unipure® are, for example:

[0177] Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica

[0178] Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica

[0179] Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0180] In a further embodiment, the colorant (F) according to the invention may also contain one or more organic pigments.

[0181] The organic pigments according to the invention are correspondingly insoluble, organic dyes or lakes which can be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo, thioindido, dioxazine and / or triarylmethane compounds.

[0182] Particularly suitable organic pigments are, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 1 1725, CI 15510, CI 45370, CI 71105, red Pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0183] In a further particularly preferred embodiment, a colorant (F) according to the invention is characterized in that it contains at least one organic pigment (F2) selected from the group consisting of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0184] The organic pigment can also be a colored lake. For the purposes of the invention, the term colored lake refers to particles comprising a layer of absorbed dyes, the particle-dye unit being insoluble under the aforementioned conditions. The particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum.

[0185] Alizarin lake, for example, can be used as a colored varnish.

[0186] To color the keratin material, pigments with a specific shape can also be used in the colorant (F). For example, a pigment based on a lamellar and / or lenticular substrate platelet can be used. Furthermore, coloring based on a substrate platelet comprising a vacuum-metallized pigment is also possible.

[0187] Within the scope of a further embodiment, a process according to the invention can be characterized in that the colorant (F) also contains one or more color-imparting compounds from the group of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet, and vacuum-metallized pigments. The substrate platelets 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 platelets is at least 1 nm, preferably at least 2.5 nm, particularly preferably at least 5 nm, for example at least 10 nm. Preferred ranges for the thickness of the substrate platelets are 2.5 to 50 nm, 5 to 50 nm, 10 to 50 nm; 2.5 to 30 nm, 5 to 30 nm, 10 to 30 nm; 2.5 to 25 nm, 5 to 25 nm, 10 to 25 nm, 2.5 to 20 nm, 5 to 20 nm and 10 to 20 nm.Preferably, each substrate platelet has a thickness that is as uniform as possible.

[0188] Due to the low thickness of the substrate platelets, the pigment has a particularly high covering power.

[0189] The substrate platelets have a monolithic structure. Monolithic in this context means consisting of a single, closed unit without fractures, stratification, or inclusions, although structural changes may occur within the substrate platelets. The substrate platelets are preferably homogeneous, meaning that no concentration gradient occurs within the platelets. In particular, the substrate platelets do not have a layered structure and do not contain any particles or particles distributed within them.

[0190] The size of the substrate platelet can be tailored to the specific application, especially the desired effect on the keratin material. Typically, the substrate platelets have an average diameter of approximately 2 to 200 pm, particularly approximately 5 to 100 pm.

[0191] In a preferred embodiment, the aspect ratio, expressed as the ratio of the average size to 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 platelets is understood to be the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Heios device with Quixel wet dispersion. For sample preparation, the sample to be tested was predispersed in isopropanol for 3 minutes.

[0192] The substrate platelets can be made of any material that can be formed into platelets.

[0193] They can be of natural origin or synthetically produced. Materials from which the substrate platelets can be constructed include metals and metal alloys, metal oxides, preferably aluminum oxide, inorganic compounds and minerals such as mica and (semi-)precious stones, as well as plastics. The substrate platelets are preferably made of metal alloys.

[0194] Any metal suitable for metallic luster pigments can be considered. Such metals include iron and steel, as well as all air- and water-resistant (semi)metals such as platinum, zinc, chromium, molybdenum, and silicon, as well as their alloys such as aluminum bronze and brass. Preferred metals are aluminum, copper, silver, and gold. Preferred substrate platelets are aluminum platelets and brass platelets, with aluminum platelets being particularly preferred.

[0195] Lamellar substrate platelets are characterized by an irregularly structured edge and are also called "cornflakes" due to their appearance.

[0196] Due to their irregular structure, pigments based on lamellar substrate platelets generate a high degree of scattered light. Furthermore, pigments based on lamellar substrate platelets do not completely cover the existing color of a keratinous material, and effects similar to natural graying can be achieved, for example.

[0197] Lenticular (= lens-shaped) substrate platelets have a generally regular, round edge and are also called "silver dollars" due to their appearance. Due to their regular structure, the proportion of reflected light predominates in pigments based on lenticular substrate platelets.

[0198] Vacuum metallized pigments (VMPs) can be obtained, for example, by releasing metals, metal alloys, or metal oxides from appropriately coated foils. They are characterized by a particularly thin substrate platelet thickness in the range of 5 to 50 nm and a particularly smooth surface with increased reflectivity. Substrate platelets comprising a vacuum-metallized pigment are also referred to as VMP substrate platelets in this application. VMP substrate platelets made of aluminum can be obtained, for example, by releasing aluminum from metallized foils.

[0199] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0200] Uncoated lamellar, lenticular, and / or VPM substrate platelets, especially those made of metal or metal alloy, reflect incident light to a high degree and produce a light-dark flop, but no color impression. A color impression can be created, for example, due to optical interference effects. Such pigments can be based on substrate platelets with at least a single coating. These exhibit interference effects due to the superposition of differently refracted and reflected light rays.

[0201] Accordingly, preferred pigments are pigments based on a coated lamellar substrate platelet. The substrate platelet preferably has at least one coating B made of a high-index metal oxide with a coating thickness of at least 50 nm. A further coating A is preferably present between the coating B and the surface of the substrate platelet. Optionally, a further coating C, which is different from the underlying layer B, is present on the layer B.

[0202] Suitable materials for coatings A, B, and C are all substances that can be applied to the substrate platelets in a film-like and permanent manner and, in the case of layers A and B, have the required optical properties. In general, coating part of the surface of the substrate platelets is sufficient to obtain a pigment with a glossy effect. For example, only the top and / or bottom side of the substrate platelets can be coated, leaving the side surface(s) uncoated. Preferably, the entire surface of the optionally passivated substrate platelets, including the side surfaces, is covered by coating B. The substrate platelets are therefore completely encased in coating B. This improves the optical properties of the pigment and increases the mechanical and chemical strength of the pigments. The above also applies to layer A and preferably also to layer C, if present.

[0203] Although several coatings A, B and / or C may be present, the coated substrate platelets preferably have only one coating A, B and, if present, C.

[0204] Coating B is composed of at least one high-index metal oxide. High-index materials have a refractive index of at least 1.9, preferably at least 2.0, and particularly preferably at least 2.4. Coating B preferably comprises at least 95% by weight, particularly preferably at least 99% by weight, of high-index metal oxide(s).

[0205] Coating B has a thickness of at least 50 nm. Preferably, the thickness of coating B is no more than 400 nm, particularly preferably at most 300 nm. High-refractive-index metal oxides suitable for coating B are preferably selectively light-absorbing (i.e., colored) metal oxides, such as, for example, iron(I) oxide (α- and γ-Fe2O3, red), cobalt(II) oxide (blue), chromium(III) oxide (green), titanium(III) oxide (blue, usually present in a mixture with titanium oxynitrides and titanium nitrides) and vanadium(V) oxide (orange), as well as mixtures thereof. Colorless high-refractive-index oxides such as titanium dioxide and / or zirconium oxide are also suitable.

[0206] Coating B may contain a selectively absorbing dye, preferably 0.001 to 5 wt.%, particularly preferably 0.01 to 1 wt.%, in each case based on the total amount of coating B. Suitable dyes are organic and inorganic dyes that can be stably incorporated into a metal oxide coating.

[0207] Coating A preferably comprises at least one low-refractive-index metal oxide and / or metal oxide hydrate. Coating A preferably comprises at least 95% by weight, particularly preferably at least 99% by weight, of low-refractive-index metal oxide (hydrate). Low-refractive-index materials have a refractive index of at most 1.8, preferably at most 1.6.

[0208] Low-refractive-index metal oxides suitable for coating A include, for example, silicon dioxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide, magnesium oxide, and mixtures thereof, with silicon dioxide being preferred. Coating A preferably has a thickness of 1 to 100 nm, more preferably 5 to 50 nm, and most preferably 5 to 20 nm.

[0209] Preferably, the distance between the surface of the substrate platelets and the inner surface of coating B is at most 100 nm, more preferably at most 50 nm, especially preferably at most 20 nm. By keeping the thickness of coating A and thus the distance between the surface of the substrate platelets and coating B in the range specified above, it can be ensured that the pigments have a high hiding power.

[0210] If the pigment based on a lamellar substrate platelet has only one layer A, it is preferred that the pigment has a lamellar substrate platelet made of aluminum and a layer A of silicon dioxide. If the pigment based on a lamellar substrate platelet has a layer A and a layer B, it is preferred that the pigment has a lamellar substrate platelet made of aluminum, a layer A of silicon dioxide, and a layer B of iron oxide.

[0211] According to a preferred embodiment, the pigments have a further coating C of a metal oxide (hydrate), which is different from the underlying coating B. Suitable metal oxides are, for example, silicon (di)oxide, silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, zinc oxide, tin oxide, titanium dioxide, zirconium oxide, iron(III) oxide, and chromium(III) oxide. Silicon dioxide is preferred.

[0212] Coating C preferably has a thickness of 10 to 500 nm, particularly preferably 50 to 300 nm. By providing coating C, for example based on TiO2, better interference can be achieved while maintaining high hiding power.

[0213] Layers A and C serve in particular as corrosion protection as well as for chemical and physical stabilization. Layers A and C particularly preferably contain silicon dioxide or aluminum oxide, which are applied using the sol-gel process. This process comprises dispersing the uncoated lamellar substrate platelets or the lamellar substrate platelets already coated with layer A and / or layer B in a solution of a metal alkoxide such as tetraethyl orthosilicate or aluminum triisopropoxide (usually in a solution of organic solvent or a mixture of organic solvent and water with at least 50 wt.% organic solvent such as a C1 to C4 alcohol), and adding a weak base or acid to hydrolyze the metal alkoxide, thereby forming a film of the metal oxide on the surface of the (coated) substrate platelets.

[0214] Layer B can be produced, for example, by hydrolytic decomposition of one or more organic metal compounds and / or by precipitation of one or more dissolved metal salts and, if necessary, subsequent post-treatment (for example, transferring a formed hydroxide-containing layer into the oxide layer by tempering).

[0215] Although each of the coatings A, B and / or C may be composed of a mixture of two or more metal oxide (hydrates), each of the coatings is preferably composed of one metal oxide (hydrate).

[0216] The pigments based on coated lamellar or lenticular substrate platelets or the pigments based on coated VMP substrate platelets preferably have a thickness of 70 to 500 nm, more preferably 100 to 400 nm, especially preferably 150 to 320 nm, for example 180 to 290 nm. Due to the low thickness of the substrate platelets, the pigment has particularly high hiding power. The low thickness of the coated substrate platelets is achieved in particular by keeping the thickness of the uncoated substrate platelets low, but also by setting the thicknesses of coatings A and, if present, C to the smallest possible value. The thickness of coating B determines the color impression of the pigment.

[0217] The adhesion and abrasion resistance of pigments based on coated substrate platelets in the keratinic material can be significantly increased by additionally modifying the outermost layer, layer A, B, or C, depending on the structure, with organic compounds such as silanes, phosphoric acid esters, titanates, borates, or carboxylic acids. The organic compounds are bound to the surface of the outermost, preferably metal oxide-containing, layer A, B, or C. The outermost layer is the layer spatially furthest away from the lamellar substrate platelet. The organic compounds are preferably functional silane compounds that can bind to the metal oxide-containing layer A, B, or C. These can be either monofunctional or bifunctional compounds.Beispiele für bifunktionelle organische Verbindungen sind Methacryloxypropenyltrimethoxysilan, 3- Methacryloxypropyltrimethoxysilan, 3- Acryloxypropyltrimethoxysilan, 2- Acryloxyethyltrimethoxysilan, 3-Methacryloxy- propyltriethoxysilan, 3-Acryloxypropyltrimethoxysilan, 2-Methacryloxyethyl- triethoxysilan, 2-Acryloxyethyltriethoxysilan, 3-Methacryloxypropyltris(methox- yethoxy)silan, 3-Methacryloxypropyltris(butoxyethoxy)silan, 3-Methacryloxy- propyltris(propoxy)silan, 3-Methacryloxypropyltris(butoxy)silan, 3-Acryloxy- propyltris(methoxyethoxy)silan, 3-Acryloxypropyltris(butoxyethoxy)silan, 3-Acryl- oxypropyltris(butoxy)silan, Vinyltrimethoxysilan, Vinyltriethoxysilan, Vinylethyl- dichlorsilan, Vinylmethyldiacetoxysilan, Vinylmethyldichlorsilan, Vinylmethyldiethoxysilan, Vinyltriacetoxysilan, Vinyltrichlorsilan, Phenylvinyldiethoxysilan, oder Phenylallyldichlorsilan.Furthermore, modification can be carried out with a monofunctional silane, in particular an alkylsilane or arylsilane. This has only one functional group, which can bond covalently to the surface of the pigment based on coated lamellar substrate platelets (i.e., to the outermost metal oxide-containing layer) or, if not completely covered, to the metal surface. The hydrocarbon radical of the silane points away from the pigment. Depending on the type and nature of the hydrocarbon radical of the silane, a different degree of hydrophobization of the pigment is achieved. Examples of such silanes are hexadecyltrimethoxysilane, propyltrimethoxysilane, etc. Particular preference is given to pigments based on silicon dioxide-coated aluminum substrate platelets surface-modified with a monofunctional silane. Particular preference is given to octyltrimethoxysilane, octyltriethoxysilane, hecadecyltrimethoxysilane, and hecadecyltriethoxysilane.The modified surface properties / hydrophobization can result in improvements in adhesion, abrasion resistance and alignment during application.

[0218] Suitable pigments based on a lamellar substrate platelet include, for example, the pigments of the VISIONAIRE series from Eckart.

[0219] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH. Pigments based on a substrate platelet containing a vacuum metallized pigment are available, for example, under the names Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

[0220] Due to their excellent light and temperature stability, the use of the aforementioned pigments in the colorant (F) of the process according to the invention is very particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. It is therefore advantageous according to the invention if the at least one pigment has an average particle size D50 of 1.0 to 50 pm, preferably of 5.0 to 45 pm, more preferably of 10 to 40 pm, in particular of 14 to 30 pm. The average particle size D50 can be determined, for example, using dynamic light scattering (DLS).

[0221] The pigment(s) can preferably be used in an amount of 0.1 to 20.0 wt.%, preferably 0.2 to 10.0 wt.%, in each case based on the total weight of the colorant (F).

[0222] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains one or more pigments (F2) in a total amount of 0.1 to 20.0 wt.%, preferably 0.2 to 10.0 wt.%.

[0223] Water content of the dye (F)

[0224] Another characteristic feature of the colorant (F) is its water content (F3), which must be below 25% by weight. Based on its total weight, the colorant (F) therefore contains less than 25.0% water.

[0225] The low water content in the colorant (F) ensures the storage stability of the colorant (F) and also ensures that the organic Ci-Ce-alkoxysilanes are still in a reactive form and are not yet fully polymerized. If the complete crosslinking of the organic Ci-Ce-alkoxysilanes only occurs after the colorant (F) has been applied to the keratin material, the film formed during crosslinking is characterized by particularly high robustness and resistance. Robust films are already obtained when the colorant (F) contains less than 25.0 wt.% water. It has proven preferable if the water content in the colorant (F) is reduced even further.

[0226] Particularly preferably, the colorant (F) is formulated with such a low water content that the water content of the colorant (F) - based on the total weight of the colorant (F) - is in the range from 0 to 20.0 wt. %, preferably from 0.1 to 10.0 wt. %, more preferably from 0.1 to 5.0 wt. %, and particularly preferably from 0.5 to 3.0 wt. % water (F3). In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains from 0 to 20.0 wt. %, preferably from 0.1 to 10.0 wt. %, more preferably from 0.1 to 5.0 wt. %, and particularly preferably from 0.5 to 3.0 wt. % water (F3).

[0227] Solvent (F4) in dye (F)

[0228] As a fourth component essential to the invention, the colorant (F) contains at least one solvent (F4) other than water. A solvent is a standard term used in chemistry for a substance that is liquid at room temperature (20 °C) and capable of dissolving other chemical substances. The solvent(s) (F4) ensure a fine dispersion of the pigments (F2) and ensure a homogeneous mixing of the pigments (F2) with the C1-C8 alkoxysilanes (F1). At the same time, the addition of at least one solvent also increases the storage stability of the colorant (F).

[0229] Since the colorant (F) is formulated with a low water content, the solvent (F4) preferably forms the cosmetic carrier - either together with the water or alone - and thus preferably represents the main component of the colorant (F).

[0230] Suitable solvents include, for example, compounds from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-alkylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate.

[0231] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one solvent (F4) other than water, which is selected from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-alkylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate.

[0232] In another explicitly particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one solvent (F4) other than water, which is selected from the group consisting of ethanol and isopropanol. Ethanol has the CAS No. 64-17-5. Isopropanol is alternatively also referred to as 2-propanol and has the CAS No. 67-63-0. 1,2-Propylene glycol is alternatively also called 1,2-propanediol and has the CAS numbers 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane] and 4254-153 [(S)-1,2-dihydroxypropane]. 1,3-Propylene glycol is alternatively also called 1,3-dihydroxypropane or 1,3-propanediol and has the CAS number 504-63-2. Ethylene glycol is alternatively also called 1,2-ethanediol and has the CAS number 107-21-1.1,2-Butylene glycol can also be called 1,2-butanediol and has the CAS numbers 584-03-2 (racemate), 40348-66-1 ((R)-enantiomer) and 73522-17-5 ((S)-enantiomer).

[0233] Dipropylene glycols (or oxydipropanols) form a group of substances derived from glycol ethers. The group of dipropylene glycols includes 2,2'-oxydi-1-propanol (CAS No. 108-61), 2,1,1'-oxydi-2-propanol (CAS No. 110-98-5), and 2-(2-hydroxypropoxy)-1-propanol (CAS No. 106-62-7). The mixture of these three isomers has CAS No. 25265-71-8.

[0234] Diethylene glycol monoethyl ether can alternatively be referred to as ethoxydiglycol or ethyldiglycol or 2-(2-ethoxyethoxy)ethanol) and has the CAS No. 111-90-0.

[0235] Glycerin is also known as 1,2,3-propanetriol and has the CAS number 56-81-5. Phenoxyethanol has the CAS number 122-99-6.

[0236] Benzyl alcohol can also be referred to as phenylmethanol and has the CAS No. 100-51-6.

[0237] Suitable poly-Ci-Ce-alkylene glycols include, in particular, the polyethylene glycols as described, for example, by the formula (AG) where x is an integer from 1 to 1000, preferably 1 to 100, particularly preferably 2 to 50.

[0238] The alkylene glycols of formula (AG) are protic substances containing at least one hydroxyl group, which, due to their repeating unit -CH2-CH2-O-, where x represents a value of at least 2, can also be referred to as polyethylene glycols. In the alkylene glycols (a1) of formula (AG), x represents an integer from 1 to 10,000. The work leading to this invention has shown that these polyethylene glycols are particularly suitable for improving the fastness properties of colorants and for optimally adjusting the viscosity of the agents.

[0239] Polyethylene glycols with a molecular weight between 200 g / mol and 400 g / mol are non-volatile liquids at room temperature. PEG 600 has a melting range of 17 to 22 °C and thus a paste-like consistency. With molecular weights above 3000 g / mol, PEGs are solid substances and are marketed as flakes or powders.

[0240] A particularly preferred low-molecular-weight polyethylene glycol is PEG-8. PEG-8 contains an average of 8 ethylene glycol units (x1 = 8), has an average molecular weight of 400 g / mol, and bears the CAS number 25322-68-3. PEG-8 is also known as PEG 400 and is commercially available, for example, from APS.

[0241] Other suitable low molecular weight polyethylene glycols include PEG-6, PEG-7, PEG-9 and PEG-10.

[0242] Another suitable polyethylene glycol is PEG-32. PEG-32 contains 32 ethylene glycol units (x1 = 32), has an average molecular weight of 1500 g / mol, and carries the CAS number 25322-68-3. PEG-32 is also known as PEG 1500 and can be purchased commercially, for example, from Clariant.

[0243] Dimethyl carbonate is also known as dimethyl carbonate and has the CAS number 616-38-6. Diethyl carbonate is also known as diethyl carbonate and has the CAS number 105-58-8.

[0244] Ethylene carbonate is also known as 1,3-dioxolan-2-one. Ethylene carbonate corresponds to the compound of formula (I), where R1 and R2 are hydrogen and n is 0. Ethylene carbonate has the CAS number 96-49-1.

[0245] Propylene carbonate is alternatively also known as 4-methyl-1,3-dioxolan-2-one. Propylene carbonate corresponds to the compound of formula (I) in which R1 represents a methyl group, R2 represents hydrogen and n represents the number 0. Propylene carbonate has the CAS numbers 108-32-7 [(RS)-4-methyl-1,3-dioxolan-2-one], 51260-39-0 [(S)-4-methyl-1,3-dioxolan-2-one] and

[0246] 16606-55-6 [(R)-4-Methyl-1,3-dioxolan-2-one]. All of the aforementioned stereoisomers are encompassed by the invention.

[0247] For the purposes of the invention, butylene carbonate is understood to mean 1,2-butylene carbonate, which is alternatively also referred to as 4-ethyl-1,3-dioxolan-2-one and which has the CAS number 4437-85-8. Butylene carbonate corresponds to the compound of formula (I) in which R1 represents an ethyl group, R2 represents a hydrogen atom, and n represents the number 0.

[0248] Glycerol carbonate is also known as 4-hydroxymethyl-1,3-dioxolan-2-one and has the CAS number 931-40-8. Glycerol carbonate corresponds to the compound of formula (I), in which R1 represents a hydroxymethyl group, R2 represents a hydrogen atom, and n represents the number 0.

[0249] In a preferred embodiment, the solvent(s) (F4) constitute the cosmetic carrier of the agent and are therefore preferably used as the main ingredient in the colorant (F). In this context, the main ingredient is an ingredient whose amount used exceeds that of all other ingredients.

[0250] When used as the main component, it may prove advantageous to select a correspondingly high amount of the solvent(s) (F4). For example, the colorant (F) may contain one or more solvents (F4) other than water in a total amount of 20 to 95 wt.%, preferably 30 to 85 wt.%, more preferably 40 to 80 wt.%, and most preferably 45 to 75 wt.%, based on the total weight of the colorant (F).

[0251] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains one or more solvents (F4) other than water in a total amount of 20 to 95 wt.%, preferably 30 to 85 wt.%, more preferably 40 to 80 wt.% and most preferably 45 to 75 wt.%.

[0252] Fat components (F5) in the dye

[0253] As a further optional component, the colorant can additionally contain at least one fatty component (F5) that is liquid at 20 °C. Like the solvents (F4), the liquid fatty components (F5) can ensure fine dispersion of the pigments (F2) and homogeneous mixing with the silanes (F1). At the same time, the addition of the fatty components (F5) can further increase the storage stability of the product.

[0254] For the purposes of the invention, “fatty constituents” are understood to mean organic compounds with a solubility in water at room temperature (22°C) and atmospheric pressure (760 mmHg) of less than 1% by weight, preferably less than 0.1% by weight. A fatty constituent that is liquid at 20°C has a melting point below 20°C (measured under atmospheric pressure (760 mmHg)). The definition of fatty constituents explicitly includes only uncharged (i.e., non-ionic) compounds. Fatty constituents have at least one saturated or unsaturated alkyl group with at least 8 carbon atoms. The molecular weight of the fatty constituents is a maximum of 5000 g / mol, preferably a maximum of 2500 g / mol, and particularly preferably a maximum of 1000 g / mol. The fatty constituents are neither polyoxyalkylated nor polyglycerylated compounds.

[0255] Particularly suitable fatty components include, for example, linear or cyclic silicone oils, hydrocarbon oils, liquid fatty acid triglycerides, liquid fatty alcohols and ester oils, provided that each compound from the aforementioned substance classes has a melting point below 20°C.

[0256] For the purposes of the present invention, only non-ionic substances are explicitly considered fatty components. Charged compounds such as fatty acids and their salts are not considered fatty components.

[0257] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one fatty component (F5) which is liquid at 20 °C and is selected from the group of linear or cyclic silicone oils, hydrocarbon oils, liquid fatty acid triglycerides, liquid fatty alcohols, ester oils and mixtures thereof.

[0258] Silicone oils can also be referred to as oligoalkylsiloxanes and polyalkylsiloxanes that are liquid at 20 °C, i.e. the silicone oils have a melting point below 20 °C (at atmospheric pressure (760 mmHg). Preferred linear silicone oils are oligoalkylsiloxanes of the general formula (V) where z is an integer from 0 to 10000, preferably an integer from 0 to 1000, more preferably an integer from 0 to 100, and most preferably an integer from 0 to 10.

[0259] Particularly preferred linear oligoalkylsiloxanes are, for example,

[0260] - Hexamethyldisiloxane CH3CH3

[0261] H3C-SI-O-SI-CH3

[0262] CH3CH3

[0263] - Octamethyltrisiloxane

[0264] CH3CH3CH3

[0265] H3C — Si — o— Si — o— Si — CH3

[0266] CH3CH3CH3

[0267] - Decamethyltetrasiloxane

[0268] CH3CH3CH3CH3

[0269] H3c—Si—o—Si—o—Si—O—Si—CH3

[0270] CH3CH3CH3CH3

[0271] Hexamethyldisiloxane has the CAS number 107-46-0 and can be purchased commercially, for example, from Sigma-Aldrich.

[0272] Octamethyltrisiloxane has the CAS number 107-51-7 and is also commercially available from Sigma-Aldrich.

[0273] Decamethyltetrasiloxane has the CAS number 141-62-8 and is also commercially available from Sigma-Aldrich.

[0274] Another particularly suitable silicone oil can be purchased commercially under the trade name Dimethicone Fluid 5 cSt from Clearco. This silicone oil has the generic name polydimethylsiloxane and has the CAS number 63148-62-9. The substance is a clear, colorless, and odorless liquid with a low viscosity.

[0275] Another particularly suitable silicone oil is available from Dow Corning under the trade name Xiameter PMX 200 (1.5 cSt). This oil is also a dimethicone, or polydimethylsiloxane, with the CAS number 63148-62-9.

[0276] Preferred cyclic oligoalkylsiloxanes are compounds of the general formula (VI)

[0277] where y is an integer from 1 to 5. Preferably, z is the number 1, 2, or 3.

[0278] Particularly preferred cyclic oligoalkylsiloxanes are, for example,

[0279] - Hexamethylcyclotrisiloxane

[0280] - Octamethylcyclotetrasiloxane

[0281] - Decamethylcyclopentasiloxane

[0282] In a further preferred embodiment, an agent according to the invention is characterized in that it contains as fat component (c) at least one silicone oil of formula (V) and / or (VI), where z is an integer from 0 to 10000, preferably an integer from 0 to 1000, more preferably an integer from 0 to 100, and most preferably an integer from 0 to 10, where y is an integer from 1 to 5, preferably an integer from 1 to 3. In a further preferred embodiment, an agent according to the invention is characterized in that it contains at least one oligoalkylsiloxane (c) selected from the group consisting of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane.

[0283] In contrast to the reactive organic silicon compounds, in particular the silanes of formulas (I) and (II), the oligoalkylsiloxanes are composed exclusively of dialkylsilyl groups (especially dimethylsilyl groups) and trialkylsilyl groups (especially trimethylsilyl groups) linked to one another via oxygen atoms. Thus, the oligoalkylsiloxanes themselves are not reactive compounds within the meaning of this invention and do not possess any hydrolyzable groups.

[0284] Hydrocarbon oils are also particularly suitable fat components that are liquid at 20 °C.

[0285] Hydrocarbons are compounds with 8 to 80 carbon atoms consisting exclusively of carbon and hydrogen atoms. Aliphatic hydrocarbons such as mineral oils, liquid paraffin oils (e.g., paraffinium liquidum or paraffinum perliquidum), isoparaffin oils, and polydecenes are particularly preferred in this context. The hydrocarbons according to the invention are also characterized by having a melting point below 20°C under atmospheric pressure.

[0286] Liquid fatty acid triglycerides are also particularly suitable fat components that are liquid at 20 °C.

[0287] For the purposes of the present invention, a C12-C30 fatty acid triglyceride is understood to be the triester of the trihydric alcohol glycerol with three equivalents of fatty acid. Both structurally identical and different fatty acids within a triglyceride molecule can participate in the ester formation, provided that the fatty acid triglyceride has a melting point below 20 °C.

[0288] For the purposes of the present invention, fatty acids are saturated or unsaturated, unbranched or branched, unsubstituted or substituted C12-C30 carboxylic acids. Unsaturated fatty acids can be monounsaturated or polyunsaturated. In an unsaturated fatty acid, its C–C double bond(s) can have the cis or trans configuration.

[0289] The fatty acid triglycerides are particularly suitable in which at least one of the ester groups is formed from glycerol with a fatty acid selected from dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid], linoleic acid [(9Z, 12Z)-octadeca-9,12-diene acid, linolenic acid [(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid, elaeostearic acid [(9Z,11E,13E)-octadeca-9,11,3-trienoic acid], arachidonic acid [(5Z,8Z,11Z,14Z)-lcosa-5,8,11,14-tetraenoic acid] and / or nervonic acid [(15Z)-tetracos-15-enoic acid],

[0290] A further particularly preferred embodiment is therefore an agent for coloring keratinic material, which is characterized in that it contains, as the fatty component (c) liquid at 20 °C, a naturally occurring fatty acid triglyceride and / or mixtures of naturally occurring fatty acid triglycerides which are contained in soybean oil, peanut oil, olive oil, sunflower oil, macadamia nut oil, moringa oil, apricot kernel oil, marula oil and / or optionally hydrogenated castor oil.

[0291] Liquid fatty alcohols are also particularly suitable fat components that are liquid at 20 °C.

[0292] Preferred linear, unsaturated fatty alcohols are (9Z)-octadec-9-en-1-ol (oleyl alcohol), (9E)-octadec-9-en-1-ol (elaidyl alcohol), (9Z,12Z)-octadeca-9,12-dien-1-ol (linoleyl alcohol), (9Z,12Z,15Z)-octadeca-9,12,15-trien-1-ol (linolenoyl alcohol), gadoleyl alcohol ((9Z)-eicos-9-en-1-ol), arachidonic alcohol ((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraen-1-ol), erucyl alcohol ((13Z)-docos-13-en-1-ol) and / or brassidyl alcohol ((13E)-Docosen-1-ol). An example of a branched liquid fatty alcohol is 2-octyldodecanol.

[0293] Ester oils are also particularly suitable fat components that are liquid at 20 °C.

[0294] Ester oils are esters of C12-C30 fatty acids with aliphatic C1-C24 alcohols that are liquid at room temperature (20 °C). In other words, ester oils according to the invention are characterized by a melting point below 20 °C at atmospheric pressure (1013 mbar).

[0295] A particularly significant improvement in the hair feel was achieved when a post-treatment agent containing at least one ester oil selected from the group consisting of monoesters of C12-C24 fatty acids with aliphatic, monohydric C12-C24 alcohols was applied to previously colored hair. Within the scope of another particularly preferred embodiment, the method according to the invention is characterized in that the post-treatment agent contains at least one fatty component (N-3) from the group consisting of esters of a C12-C30 fatty acid and an aliphatic, monohydric C12-C24 alcohol.

[0296] Within the group of C12-C30 fatty acids, C12-C24 fatty acids are particularly well-suited. Examples of C12-C24 fatty acids suitable for the formation of ester oils (N-3) are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid, and erucic acid, as well as their technical mixtures.Examples of the fatty alcohol components in the ester oils are isopropyl alcohol, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol as well as their technical mixtures.

[0297] These C12-C24 fatty acids are esterified by reaction with an aliphatic C12-C24 alcohol, which is particularly preferably a monoalcohol, so that a monoester is formed during esterification.

[0298] The aliphatic Ci-C24 alcohols can be linear or branched, saturated, or mono- or polyunsaturated.

[0299] As an aliphatic saturated Ci-C24 alcohol, for example, an alcohol selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, 2-ethylhexanol, n-hexanol, n-octanol, n-decanol and n-dodecanol can be used.

[0300] Examples of monohydric, unsaturated, Ci-C24 alcohol are oleyl alcohol (octadec-9-en-1-ol), palmitoleyl alcohol (c / s-9-hexadecen-1-ol), elaidyl alcohol (trans-9-octadecen-1-ol) and c / s-11-octadecen-1-ol.

[0301] To form the esters, the Ci2-C24 fatty acids and the Ci-Ci2 alcohols are selected so that the ester formed by esterification of both reactants is an ester oil, ie it has a melting point below 20 °C at 1013 mbar.

[0302] Some ester oils according to the invention can be used in the form of commercially available raw materials, which are mixtures of esters obtained from fatty acids of different chain lengths and / or alcohols of different chain lengths. These raw materials can have a melting range. For these raw materials, a melting point below 20°C means that the melting process begins at a temperature below 20°C.

[0303] For example, if an ester oil in the form of a specific raw material can be used in the medium, whereby this raw material has a melting range of 16 to 27 °C, then this raw material contains at least one ester oil with a melting point below 20 °C. This ester oil is therefore in accordance with the invention.

[0304] Particularly preferred according to the invention are 2-ethylhexyl palmitate (Cegesoft® 24), isopropyl myristate (Rilanit® IPM), isononanoic acid C16-18-alkyl esters (Cetiol® SN), 2-ethylhexyl stearate (Cetiol® 868), cetyl oleate, glycerol tricaprylate, coconut fatty alcohol caprylate Z-caprylate (Cetiol® LC), n-butyl stearate, oleyl erucate (Cetiol® J 600), isopropyl palmitate (Rilanit® IPP), oleyl oleate (Cetiol®), hexyl laurate (Cetiol® A), di-n-butyl adipate (Cetiol® B), cetearyl isononanoate (Cetiol® SN), oleic acid decyl ester (Cetiol® V).

[0305] The ester oil (N-3) is very particularly preferably selected from the group consisting of isopropyl myristate, 2-ethylhexyl palmitate, isononanoic acid C16-18 alkyl esters, 2-ethylhexyl stearate, cetyl oleate, coconut fatty alcohol caprinate, coconut fatty alcohol caprylate, n-butyl stearate, oleyl erucate, isopropyl palmitate, oleyl oleate, hexyl laurate, cetearyl isononanoate and decyl oleate.

[0306] Isopropyl myristate is also known as isopropyl myristic acid ester and has the CAS number 110-27-0. Isopropyl myristate is a colorless, odorless liquid. Its melting point is 0-1 °C.

[0307] 2-Ethylhexyl palmitate is also known as hexadecanoic acid 2-ethylhexyl ester and has the CAS number 29806-73-3. 2-Ethylhexyl palmitate is a branched, saturated ester oil of palmitic acid and ethylhexyl alcohols. At room temperature, 2-Ethylhexyl palmitate is a clear, colorless liquid with a slightly greasy odor.

[0308] Isononanoic acid C16-18-alkyl ester is also known as cetearyl isononanoate. This ester has the CAS numbers 84878-33-1 and 84878-34-2. Isononanoic acid C16-18-alkyl ester is a clear, slightly yellowish liquid. At 20 °C, it has a viscosity of 19-22 mPas.

[0309] Stearic acid 2-ethylhexyl ester is also known as ethylhexyl stearate and has the CAS number 91031-48-0. Stearic acid 2-ethylhexyl ester is a clear, slightly yellowish, thin oil. At 20 °C, stearic acid 2-ethylhexyl ester has a viscosity of 14-16 mPas and is therefore an oil at room temperature. Cetyl oleate has the CAS number 22393-86-8.

[0310] Coconut fatty alcohol caprylate / caprate has the CAS number 95912-86-0. It is a mixture of C8-C10 fatty acids with C12-C18 fatty alcohols. It is a yellow liquid with a melting point of 10 °C. n-Butyl stearate is also known as stearic acid butyl ester and has the CAS numbers 85408-76-0 (C16-C18) and 123-95-5 (C18). n-Butyl stearate is a yellowish liquid and begins to melt at 16 °C.

[0311] Oleylerucate has the CAS number 17673-56-2. Oleylerucate is a yellow liquid. At 20 °C, it has a viscosity of 40-50 mPas, making it an oil at room temperature.

[0312] Isopropyl palmitate is also known as propan-2-yl hexadecanoate and has the CAS number 142-91-6. The melting point of isopropyl palmitate is 13.5 °C.

[0313] Oleyl oleate is also known as cis-9,10-octadecenyl-cis-9,10-octadecanoate or oleic acid oleyl ester and has the CAS number 3687-45-4. Oleyl oleate is a clear, slightly yellowish oil with a viscosity of 25-30 mPas at 20 °C and is an oil at room temperature.

[0314] Lauric acid hexyl ester is also known as hexyl laurate and has the CAS number 34316-64-8. At room temperature, lauric acid hexyl ester is a clear, yellowish, odorless oil. At 20 °C, lauric acid hexyl ester has a viscosity of 5-7 mPas and is therefore an oil at room temperature.

[0315] Cetearyl Isononanoate is also known as isononanoic acid C16-18 alkyl ester and has the CAS numbers 84878-33-1 and 84878-34-2. Cetearyl Isononanoate is a yellowish liquid with a melting point of 16-22 °C.

[0316] Decyl oleate is also known as decyl oleate and has the CAS number 3687-46-5. Decyl oleate is a slightly yellowish liquid with a viscosity of 15-20 mPas at 20 °C. Decyl oleate is therefore an oil at room temperature.

[0317] Preferably, the fatty constituent(s) (F5) liquid at 20°C are used in specific quantity ranges in the agent according to the invention. Particularly good results were obtained when the colorant (F) contained one or more fatty constituents (c) liquid at 20°C in a total amount of 1.0 to 99% by weight, preferably 5.0 to 60.0% by weight, more preferably 10.0 to 30.0% by weight, and most preferably 15.0 to 25.0% by weight, based on the total weight of the colorant (F).

[0318] Within the scope of a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains one or more fatty components (F5) which are liquid at 20 °C in a total amount of 1.0 to 99% by weight, preferably of 5.0 to 60.0% by weight, more preferably of 10.0 to 30.0% by weight and very particularly preferably of 15.0 to 25.0% by weight.

[0319] Other optional components of the colorant (F)

[0320] In addition to the essential ingredients (F1), (F2), (F3) and (F4) and the optional ingredient (F5), the colorant (F) may optionally contain other ingredients.

[0321] Thus, the coloring agent (F) can also contain further active ingredients, auxiliaries and additives, such as, for example, cationic, non-ionic, amphoteric, zwitterionic and / or anionic surfactants, thickening polymers, film-forming polymers, structuring agents such as glucose, maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example lecithin and cephalins; perfume oils, dimethyl isosorbide and cyclodextrins; fiber structure-improving active ingredients, in particular mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose, fructose and lactose; dyes for coloring the agent; anti-dandruff active ingredients such as piroctone olamine, zinc omadine and climbazole; amino acids and oligopeptides; protein hydrolysates of animal and / or plant origin, as well as in the form of their fatty acid condensation products or, if appropriate, anionically or cationically modified derivatives; Sunscreens and UV blockers;Active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylic acids and their salts and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins, leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; swelling and penetrating agents such as glycerin, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates; opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers; Pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; as well as propellants such as propane-butane mixtures, N2O, dimethyl ether, CO2 and air.

[0322] The expert will select these additional substances based on the desired properties of the agent. Regarding further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the expert. The additional active ingredients and excipients are preferably used in the preparations according to the invention in amounts of 0.0001 to 25 wt.%, in particular 0.0005 to 15 wt.%, based on the total weight of the respective agent.

[0323] Steps in the dyeing process

[0324] The method according to the invention comprises the following steps in the given order:

[0325] (1) Providing the previously described colorant (F),

[0326] (2) Application of the colorant (F) on moistened or dry keratin material,

[0327] (3) optionally applying a defined amount of water to the keratinic material which is still coated with the coloring agent (F), the weight of the amount of water applied in step (3) being at most twice the weight of the coloring agent (F) applied in step (2), and

[0328] (4) Drying of the keratin material without prior washing out of the colorant (F).

[0329] Within the scope of one embodiment, the colorant (F) according to the invention can be provided directly as such in its previously described form and also applied to the keratin material or the hair. In this form, the colorant (F) according to the invention also represents the ready-to-use agent and can be provided, for example, in a bottle, a container, a tube, or a can. A major advantage of this application form is the convenient and simple form of application, since the user can simply remove the colorant (F) from the bottle or container in which it was provided and apply it to the keratin material. Mixing, shaking, and / or homogenization with one or more other components or compositions is not necessary in this embodiment.

[0330] Furthermore, however, it is also possible to first prepare the colorant (F) in or before step (1) of the process. This preparation can be carried out, for example, by mixing a silane blend containing the organic Ci-Ce-alkoxysilane(s) (F1) with another agent containing the pigment(s) (F2). Water (F3) and solvent (F4) can be present in the silane blend and / or in the pigment-containing agent. In this embodiment, the ingredients (F1) to (F4) can be present in at least two separately packaged containers and can be combined or mixed with one another during the preparation of the colorant (F).Even if this embodiment means more effort for the user, it may be preferred to increase the storage stability of the Ci-Ce alkoxysilanes (F1), to avoid premature conglomeration between silane (F1) and pigments (F2) or to prevent undesirable interactions between silane (F1) and solvent (F4).

[0331] In the second step of the method according to the invention, the colorant (F) is applied to moistened or dry keratin material. The application can be carried out, for example, using a brush, a brush nozzle, or the user can use their gloved hand.

[0332] In one embodiment, the colorant can be applied to dry keratin material or hair. In this case, the hydrolysis and condensation of the organic Ci-Ce alkoxysilanes occurs due to the amount of water (F3) contained in the colorant (F) itself.

[0333] Particularly good, intense, and long-lasting color results were achieved when the colorant (F) was applied to previously damp or towel-dried hair. Since the colorant (F) itself is low in water or anhydrous, the additional water in the hair supports the condensation of the organic Ci-Ce alkoxysilanes directly on the surface of the keratin. This creates a particularly uniform and durable coating that tightly envelops the hair fiber and forms directly where the film is intended.

[0334] Damp or towel-dried hair refers to hair that has been thoroughly wetted with water at the sink or in the shower, then squeezed out and rubbed dry with a towel (e.g., for 30 seconds). Damp or towel-dried hair is therefore no longer dripping wet, but still damp.

[0335] In a further particularly preferred embodiment, a method according to the invention is characterized by the

[0336] (2) Application of the colorant (F) on keratin material that has been moistened shortly before application.

[0337] Keratinous material such as hair that was moistened shortly before application was moistened within a maximum period of 30 minutes, preferably a maximum of 10 minutes, before application.

[0338] In step 3 of the process, if necessary, a defined amount of water is applied to the keratinic material which is still coated with the colorant (F), whereby the weight of the amount of water applied in step (3) is at most twice the weight of the colorant (F) applied in step (2).

[0339] Step (3) of the process according to the invention is optional and can be performed, for example, if the colorant (F) was applied to dry keratin material in step (2), or if the amount of water present in the moistened keratin material is not yet sufficient for complete crosslinking or condensation of the organic Ci-Ce alkoxysilanes. By additionally applying the defined amount of water in step (3), post-condensation or post-crosslinking of the organic O-Ce alkoxysilanes can be initiated. This post-crosslinking ensures further strengthening of the film or coating.

[0340] However, in step (3), the dye (F) should not be washed out, i.e., the additional amount of water applied to the hair treated with the dye (F) should be large enough so that the Ci-Ce alkoxysilanes can come into contact with a sufficient amount of water, but the dye (F) is not washed off the hair fiber or flows down. As the work leading to this invention has shown, this is the case if the weight of the amount of water applied in step (3) is at most twice the weight of the dye (F) applied in step (2).

[0341] The amount of water and the amount of colorant (F) are understood here as weight quantities. Thus, if 50 g of colorant (F) is applied to the hair / keratin material in step (2), a maximum of 100 g of water may be applied to the hair / keratin material in step (3).

[0342] The defined amount of water can be distributed over the keratin material in step (3) and mixed with the colorant (F) still present on the keratin material. This mixing can be assisted by massaging it in with your hand or a brush.

[0343] It is particularly preferred if step (3) is carried out. Accordingly, a method comprising

[0344] (2) the application of the coloring agent (F) on moistened keratin material, and

[0345] (3) applying a defined amount of water to the keratinic material which is still coated with the colorant (F), wherein the total amount of water applied to the keratinic material for moistening in step (2) and for application in step (3) is at most twice the weight of the colorant (F) applied in step (2).

[0346] Furthermore, a method comprising

[0347] (2) the application of the coloring agent (F) on moistened keratin material, and

[0348] (3) applying a defined amount of water to the keratin material still coated with the colorant (F), whereby the total amount of water applied to the keratin material for moistening in step (2) and for application in step (3) is at most equal to the weight of the colorant (F) applied in step (2). Therefore, if 50 g of colorant (F) is applied to the hair / keratin material in step (2), a maximum of 50 g of water may be applied to the hair / keratin material in step (3) with a maximum amount of water equal to the weight of the colorant (F).

[0349] Between steps (2) and (3) (if step (3) is carried out) there may be a period of a few seconds up to 60 minutes, preferably from 30 seconds to 30 minutes.

[0350] After step (3), the keratin material is dried in step (4) without prior washing out of the colorant (F).

[0351] During drying, the water (F3) and the solvent(s) (F4) present in the dye evaporate, and the film formed by the condensation of the Ci-Ce alkoxysilanes hardens. Drying can occur either in air or under the influence of heat, for example, using a heat cap or a hair dryer.

[0352] Between steps (3) and (4) (if step (3) is performed), there can be a period of a few seconds up to 60 minutes, preferably from 30 seconds to 30 minutes. If the keratin material is dried in the air, step (4) begins immediately after step (3).

[0353] If step (3) is not performed, a period of several seconds to 60 minutes, preferably 30 seconds to 30 minutes, can elapse between steps (2) and (4). If the keratin material is dried in the air, step (4) begins immediately after step (2).

[0354] The drying of the keratin material or hair that takes place in step (4) can be accelerated by heat treatment. Heat treatment involves bringing the keratin material into contact with a heated device or applying this heated device to or on the keratin material. Furthermore, the keratin material can also be exposed to warm / hot air for heat treatment. The device used can be, for example, a hairdryer, a blow dryer, a thermal cap, a flat iron, a curling iron, or an infrared lamp.

[0355] In a particularly preferred embodiment, a method according to the invention is characterized in that the heat treatment is carried out by using a hair dryer, a blow dryer, a heat cap, a straightening iron, a curling iron or an infrared lamp.

[0356] Furthermore, it has been found that it is preferred if the treatment temperature during the heat treatment is between 40 °C and 210 °C, preferably from 50 °C to 190 °C, more preferably from 50 °C to 170 °C, even more preferably from 50 °C to 150 °C and most preferably from 50 °C to 100 °C. In other words, it has proven particularly preferred if the heat treatment is carried out using a device that is heated to a temperature of 40 °C to 210 °C, preferably from 50 °C to 190 °C, more preferably from 50 °C to 170 °C, even more preferably from 50 °C to 150 °C and most preferably from 50 °C to 100 °C.

[0357] In a further particularly preferred embodiment, a method according to the invention is characterized by

[0358] (4) Drying the keratin material without prior washing out of the colorant (F) at a temperature of 40 °C to 210 °C, preferably from 45 °C to 190 °C, more preferably from 45 °C to 170 °C, even more preferably from 45 °C to 150 °C and most preferably from 45 °C to 100 °C.

[0359] For example, the keratin material or the hair can be treated with a hairdryer that blows warm or hot air onto the keratin material. This air is particularly preferably between 50 and 100°C. Alternatively, the keratin material or the hair can be held under an infrared lamp, which is particularly preferably set to a temperature of 50 to 100°C. For the purpose of heat treatment, hair can also be pressed between two appropriately temperature-controlled plates of a straightening iron, with the plates simultaneously moving along the fiber. The straightening iron plates can, for example, be set to a temperature of up to 210°C.

[0360] The heat treatment can expediently be carried out until the keratin material still coated with the colorant (F) has dried or is completely dry.

[0361] After or before step (4), the process according to the invention can optionally also comprise a further step. Further work has shown that the durability, in particular the washfastness of the resulting colorations can be further improved if the keratin material was tempered in air with a high level of humidity after or before step (4). Contact with the humid air led to the film or coating produced on the keratin material becoming even more resistant. Particularly good results were obtained when the dyed or dyed and dried keratin materials were tempered in air with a relative humidity of 40% to 99%, preferably 50 to 95%, more preferably 60 to 95%, and particularly preferably 70 to 95% (measured at 20°C and a pressure of 11013.25 hPa).

[0362] Within the scope of a further embodiment, a method is particularly preferred, comprising, before or after step (4), bringing the keratin material into contact with air having a relative humidity of 40% to 99%, preferably of 50 to 95%, more preferably of 60 to 95% and particularly preferably of 70 to 95% (measured at 20 °C and a pressure of 11013.25 hPa).

[0363] Humidity – or air humidity for short – refers to the proportion of water vapor in the air's gas mixture. Liquid water (e.g., raindrops, mist droplets) or ice are therefore not considered air humidity. Depending on temperature and pressure, a given volume of air can only contain a certain maximum amount of water vapor. This maximum amount of water vapor in the air is called the saturation level of the water vapor. Relative humidity, which is the most common measure of air humidity, is then 100%. In general, relative humidity, expressed as a percentage (%), indicates the weight ratio of the current water vapor content to the maximum possible water vapor content for the current temperature and pressure.

[0364] At normal pressure (1013.25 hPa), the saturation amount of water vapor in the air is, for example (corresponding to 100% relative humidity):

[0365] At a relative humidity below 100%, the amount of water vapor in the air decreases accordingly (measured at a standard pressure of 1013.25 hPa)

[0366]

[0367] Various state-of-the-art measuring devices are known and commercially available for measuring humidity.

[0368] For example, the PCE-MMK1 humidity meter from PCE Instruments can measure relative and absolute humidity. Humidity can also be measured with the Bosch PTD thermodetector from Bosch Home and Garden.

[0369] Bringing the keratin material into contact with, or in other words treating, curing, or storing it in air with a sufficiently high level of humidity can be achieved, for example, by placing the person in a climate chamber or by using a steam hood or climate hood. Steam hoods are commercially available and widely used in the hairdressing industry.

[0370] Examples

[0371] 1 . Formulations

[0372] Production of the silane blend

[0373] In a 500 ml round-bottom flask, 25 g of ethanol (abs.) and 49.7 g of methyltriethoxysilane were mixed with stirring. This mixture was heated to 50 °C with continued stirring.

[0374] Then, 6.8 g of a 1% solution of sulfuric acid in water was added dropwise over a period of approximately 5 minutes. The temperature of the reaction mixture rose to 62 °C and then decreased to 55 °C after the addition was complete. Stirring was continued for another 20 minutes. Then, 18.6 g of (3-aminopropyl)triethoxysilane were added dropwise over a period of approximately 5 minutes. After the addition was complete, the mixture was stirred for another 45 minutes at 50 °C and then transferred to an airtight glass container.

[0375] The silane blend prepared in this way was incorporated into the following colorants (F) (all data in wt.% unless otherwise stated):

[0376] 2. Application

[0377] The dyes (Fl) to (FIV) were applied to hair strands (Kerling Euronaturhaarweiß and Kerling 9-0, length approx. 5 cm) using the following procedures:

[0378] 3. Measurement of wash fastness

[0379] The dye was applied as described in step 2. After drying and curing, the strands were visually evaluated under a daylight lamp. 0 HW is the color result obtained immediately after dyeing. To measure washfastness, the strands were then washed 4 or 8 times (4 HW, 8 HW).

[0380] For each wash, a commercially available shampoo (0.25 g of Schauma 7 Herbs shampoo per 1 g of hair) was applied to the strand and massaged in with the fingers for 30 seconds. The shampoo was then rinsed out under lukewarm running water for 1 minute, and the strand was dried. The previously described procedure corresponds to one wash. The process was repeated for each subsequent wash. After the appropriate number of washes, the strands were visually assessed again under a daylight lamp.

[0381] Color intensity: ++++ very high +++ high ++ medium + low

[0382] The following color results were obtained

[0383] When using the colorants (Fl) to (FIV) in the leave-on coloring process according to the invention, colorations with improved color intensity and improved washfastness could be achieved on hair strands of various types.

Claims

Patent claims 1. A process for dyeing keratinous material, in particular human hair, comprising the following steps in the specified order: (1) Providing a colorant (F), wherein the colorant (F) contains - based on the total weight of the colorant (F): (F1) one or more organic Ci-Ce-alkoxysilanes and / or their condensation products, (F2) at least one pigment, (F3) less than 25.0 wt% water, and (F4) at least one solvent other than water, (2) Application of the colorant (F) on moistened or dry keratin material, (3) optionally applying a defined amount of water to the keratinic material which is still coated with the coloring agent (F), the weight of the amount of water applied in step (3) being at most twice the weight of the coloring agent (F) applied in step (2), and (4) Drying of the keratin material without prior washing out of the colorant (F).

2. Process according to claim 1, characterized in that the colorant (F) contains at least one organic Ci-Ce-alkoxysilane (F1) of formula (I) and / or its condensation products, RiR2N-L-Si(OR3) a (R4)b (l), where - Ri, R2 independently represent a hydrogen atom or a Ci-Ce-alkyl group, - L represents a linear or branched, divalent Ci-C2o-alkylene group, - R3, R4 independently represent a Ci-Ce-alkyl group, - a, stands for an integer from 1 to 3, and - b stands for the integer 3 - a.

3. The method according to one of claims 1 to 2, characterized in that the colorant (F) contains at least one organic Ci-Ce-alkoxysilane (F1) which is 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, (2-dimethylaminoethyl)triethoxysilane and their condensation products. Process according to one of claims 1 to 3, characterized in that the colorant contains at least one organic Ci-Ce-alkoxysilane (F1) of formula (II). R5Si(OR6)k(R7)m (II), where - Re represents a Ci-Ci2-alkyl group, - Re represents a hydrogen atom or a Ci-Ce alkyl group, - R? stands for a Ci-Ce-alkyl group - k is an integer from 1 to 3, and - m represents the integer 3 - k. Process according to one of claims 1 to 4, characterized in that the colorant (F) contains at least one organic Ci-Ce-alkoxysilane (F1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, and condensation products thereof. Process according to one of claims 1 to 5, characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains one or more organic Ci-Ce-alkoxysilanes (F1) and / or their condensation products in a total amount of 0.1 to 30.0 wt.%, preferably of 0.5 to 20.0 wt.%, more preferably of 5.0 to 15.0 wt.% and very particularly preferably of 6.0 to 12.5 wt.%.The agent according to any one of claims 1 to 6, characterized in that the colorant (F) contains at least one pigment (F2) from the group of inorganic pigments, organic pigments, and / or metallic pigments. The method according to any one of claims 1 to 7, characterized in that the colorant (F) contains, based on the total weight of the colorant (F), 0 to 20.0 wt. %, preferably 0.1 to 10.0 wt. %, more preferably 0.1 to 5.0 wt. %, and particularly preferably 0.5 to 3.0 wt. % water (F3). Method according to one of claims 1 to 8, characterized in that the colorant (F) contains at least one solvent (F4) other than water, which is selected from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-alkylene glycols, dimethyl carbonate. Diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and glycerol carbonate, preferably from the group consisting of ethanol and isopropanol. The process according to any one of claims 1 to 9, characterized in that the colorant (F) contains—based on the total weight of the colorant (F)—one or more solvents (F4) other than water in a total amount of 20 to 95 wt.%, preferably 30 to 85 wt.%, more preferably 40 to 80 wt.%, and most preferably 45 to 75 wt.%. The process according to any one of claims 1 to 10, characterized in that the colorant (F) contains at least one fatty constituent (F5) that is liquid at 20°C and is selected from the group consisting of linear or cyclic silicone oils, hydrocarbon oils, liquid fatty acid triglycerides, liquid fatty alcohols, ester oils, and mixtures thereof.Process according to one of claims 1 to 11, characterized in that the coloring agent (F) - based on the total weight of the coloring agent (F) - contains one or more fatty components (F5) which are liquid at 20 °C in a total amount of 1.0 to 99 wt. %, preferably of 5.0 to 60.0 wt. %, more preferably of 10.0 to 30.0 wt. % and most preferably of 15.0 to 25.0 wt. %. Process according to one of claims 1 to 12, characterized by the. (2) Applying the coloring agent (F) to keratin material that has been moistened shortly before application. Method according to one of claims 1 to 13, comprising (2) the application of the coloring agent (F) on moistened keratin material, and (3) applying a defined amount of water to the keratin material which is still coated with the coloring agent (F), wherein the total amount of water applied to the keratin material for moistening in step (2) and for application in step (3) is at most twice the weight of the coloring agent (F) applied in step (2). Method according to one of claims 1 to 14, comprising (4) drying the keratin material without prior washing out of the coloring agent (F) at a temperature of 40°C to 210°C, preferably from 45°C to 190°C, more preferably from 45°C to 170°C, even more preferably from 45°C to 150°C and most preferably from 45°C to 100°C. Method according to one of claims 1 to 15, comprising before or after step (4) the bringing the keratin material into contact with air which has a relative humidity of 40% to 99%, preferably 50 to 95%, more preferably 60 to 95% and particularly preferably 70 to 95% (measured at 20 °C and a pressure of 11013.25 hPa).

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