Agent for pre-cleaning keratin fibers, especially human hair, containing a reducing agent and a special surfactant system

Abstract

The present invention relates to a cosmetic agent (V) for pre-cleaning keratin fibers, in particular human hair, containing in a cosmetic carrier (V-1) at least one reducing agent, and (V-2) at least one anionic surfactant, and (V-3) at least one surfactant from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants.

Description

[0001] The present application relates to an agent for pre-cleaning keratin fibers, in particular human hair, comprising at least one reducing agent, at least one anionic surfactant and at least one surfactant from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants.

[0002] A second subject matter of the present application is a method for dyeing keratin fibers or hair, which comprises the application of the pretreatment agent described above and the application of a dyeing agent containing at least one silane and a coloring compound from the group of pigments and direct dyes.

[0003] Altering the shape and color of keratin fibers, especially hair, represents an important area of ​​modern cosmetics. Depending on the coloring requirements, hair coloring experts 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 typically 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.

[0004] 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.

[0005] 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.

[0006] Coloring with pigments offers several significant advantages. Because the pigments only attach to the keratin fibers, especially the hair fibers, from the outside, unwanted coloring can be removed quickly and easily without leaving any residue, thus offering the user the opportunity to return to their original hair color immediately and without much effort. This coloring process is therefore particularly attractive for consumers who do not want to recolor their hair regularly.

[0007] Despite these many advantages, the pigment-based coloring system still has some disadvantages, which are due to the pigments' limited penetration into the keratin material. Since the pigments do not diffuse into the keratin fibers, but rather merely deposit themselves on the outer surface of the fiber in the form of a shell or film, the washfastness of the colorations produced with this system still requires improvement. Various studies have attempted to bond the pigment(s) more permanently to the hair surface using film-forming materials, usually polymers.

[0008] 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.

[0009] However, a closer examination of the dyeing processes disclosed in EP 2168633 B1 revealed that the dyes produced on hair using these agents or processes still require improvement. In particular, the color intensity and abrasion resistance of the dyes from the hair still need to be optimized, and the durability, especially the washfastness of these dyes, also requires further improvement.

[0010] Various studies have already been conducted to improve the washfastness of dyes produced with silanes and pigments, including the effects of various pretreatment agents. For example, WO 2022 / 184357 A1 attempted to improve washfastness by pretreating with an enzyme from the lipase group, and WO 2022 / 184337 A1 used a pretreatment agent containing hydrogen peroxide.

[0011] However, further work on WO 2022 / 184337 A1 revealed that the oxidative pretreatment, which was performed here with an aqueous hydrogen peroxide solution, also resulted in hair lightening and damage. This can be particularly disadvantageous if the user resorts to pigment-based colorants because they want to avoid hair lightening and damage.

[0012] In WO 2021 / 121721 A1, a pretreatment with an anionic surfactant system consisting of sodium lauryl sulfate and / or sodium laureth sulfate was performed. Furthermore, WO 2022 / 184344 A1 described a reductive pretreatment with cysteine. The pretreatment agent investigated contained surfactants such as sodium lauryl sulfate and decyl glucoside in addition to the reducing agent. Although these studies have already produced initial good results, the washfastness and uniformity of the dyeings achievable in this way still require further improvement.

[0013] Building on previous work, the theory was developed that while the sulfate surfactants sodium lauryl sulfate and / or sodium laureth sulfate already provide a fairly good pre-cleansing effect on the hair, a pre-treatment applied prior to coloring should free the surface even more completely and comprehensively of all adhering contaminants. In particular, for long-lasting film-based coloring, it also appears necessary to remove as completely as possible the covalently bound 18-methyleicosanoic acid (18-MEA) present on the hair surface. 18-methyleicosanoic acid (18-MEA) is a branched-chain fatty acid. It is covalently bound, possibly via a thioester or ester bond, to the cuticle surface of the hair fibers. 18-MEA is known to form a hydrophobic surface and, as a boundary lubricant, reduce frictional resistance between hair fibers.

[0014] If 18-MEA is removed from the hair surface, the surface becomes more hydrophilic, and friction increases. In the literature, the loss of 18-MEA is described as one of the reasons for the increase in friction at the cuticle surface. This can influence the sensory perception of the hair, so that the user or test subject feels that the hair is dry and difficult to comb or run their fingers through. Due to these negative properties, the loss of 18-MEA during daily hair cleansing with shampoo is undesirable. However, if a film-based coloring is applied after cleansing, the roughening of the hair surface initiated by the loss of 18-MEA appears to lead to better adhesion of the film to the surface.

[0015] It is therefore assumed that a sulfate surfactant alone does not sufficiently remove 18-methyleicosanoic acid (18-MEA) from the hair fiber, and that a surfactant combination specifically tailored to the surface of the hair could clean the hair more comprehensively and completely, so that a film formed on the hair fiber can wrap around the surface more evenly and without gaps and adhere better to it.

[0016] Another disadvantage remains that the films formed from the silanes adhere to different hair types and to different degrees of damage. It has been found that the silane films generally adhere better to damaged hair than to hair with lesser degrees of damage. When coloring the entire head, this results in the colored film peeling off relatively quickly at the roots, whereas the color remains visible much longer in the more damaged areas of the ends. Even though longer-lasting films are desirable in principle, the varying degrees of peeling off at the roots and tips lead to a very uneven or patchy color result, which the user dislikes.

[0017] The object of the present application was to find a pretreatment agent that can be used to pre-clean keratin fibers and thus improve the durability and uniformity of a subsequently applied colorant. In particular, the pre-cleaning should bond the films formed from silanes and pigments very permanently and evenly to the keratin fibers, deliver high color intensities, and exhibit very good washfastness. Furthermore, a uniform and long-lasting color should be achieved both at the roots and at the tips of the hair, and the hair should be lightened as little as possible by the coloring process. Furthermore, a uniform color result should be achieved over the entire length of the keratin fiber, regardless of the degree of damage to the keratin fiber, and the silane film should remain as evenly as possible on the fibers over multiple hair washes, even on hair sections with varying degrees of damage.

[0018] Surprisingly, it has now been found that the color intensity and washfastness of colored keratin fibers could be massively improved if the keratin fibers are treated in a pretreatment step before coloring with a pre-cleansing agent that contains at least one reducing agent and a special surfactant combination in a cosmetic carrier.

[0019] A first subject of the present invention is a cosmetic agent (V) for pre-cleaning keratin fibers, in particular human hair, containing in a cosmetic carrier (V-1) at least one reducing agent, and (V-2) at least one anionic surfactant, and (V-3) at least one surfactant from the group consisting of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants.

[0020] The work leading to this invention has shown that this pretreatment or precleaning agent (V), when applied to the keratin fibers before the application of a film-based coloring agent, enables the creation of very stable and washfast films on the keratin fibers. This approach has made it possible to achieve particularly uniform and washfast colorations with good resistance to abrasion and / or shampooing, even on different hair types or hair with varying degrees of damage. Keratin material

[0021] Keratin fibers include hair, but also wool and fur. Human hair is particularly preferred as keratin fibers. cosmetic product (V) for pre-cleaning

[0022] The cosmetic agent (V) according to the invention for pre-cleaning, which can alternatively also be referred to as pre-cleaning agent (V) or pre-treatment agent (V), contains at least one reducing agent (V-1).

[0023] A reducing agent is a substance that donates electrons, thus reducing other substances and itself being oxidized in the process. A reducing agent therefore acts as an electron donor.

[0024] In cosmetics, for example, reducing agents can be used which are selected from the group consisting of dithioerythritol, dithiothreitol, acetylcysteine, dimercaptosuccinic acid, thioglycerin, thiolactic acid, sodium dithionite, zinc dithionite, potassium dithionite, formamidine sulfinic acid, 2-hydroxy-2-sulfinoacetic acid and the salts of the aforementioned compounds.

[0025] With the help of the pretreatment agent, the adhesion and thus the durability of film-based dyes on the keratin material could be significantly increased. In this context, it is assumed that the pretreatment agent (V) hydrophilizes the surface of the keratin material and creates additional reactive sites on the surface of the keratin material.

[0026] It has been found that this surface modification was particularly well possible with the reducing agents dithioerythritol, dithiothreitol, acetylcysteine, dimercaptosuccinic acid, thioglycerol, thiolactic acid, sodium dithionite, zinc dithionite, potassium dithionite, formamidine sulfinic acid, 2-hydroxy-2-sulfinoacetic acid or the salts of these compounds.

[0027] In a preferred embodiment, an agent according to the invention is therefore characterized in that it contains at least one reducing agent (V-1) which is selected from the group consisting of dithioerythritol, dithiothreitol, acetylcysteine, dimercaptosuccinic acid, thioglycerol, thiolactic acid, cysteine, thioglycolic acid, sodium dithionite, zinc dithionite, potassium dithionite, formamidine sulfinic acid, 2-hydroxy-2-sulfinoacetic acid and salts thereof.

[0028] Dithioerythritol is also known as 1,4-dithioerythritol, erythro-1,4-dimercapto-2,3-butanediol, (2R,3S)-1,4-bis(sulfanyl)butane-2,3-diol, or (2R*,3S*)-1,4-bis(sulfanyl)butane-2,3-diol and has the CAS numbers 6892-68-8 (dithioerythritol) and 7634-42-6 (1,4-dimercapto-2,3-butanediol, unspecified). With dithioerythritol, a particularly uniform color result was observed after repeated shampooing on hair strands with varying degrees of damage. The wash fastness could also be significantly improved when dithioerythritol was used as a reducing agent, therefore the use of dithioerythritol in the pretreatment agent (V) is most preferred.

[0029] Dithiothreitol is formally derived from the sugar alcohol threitol, which belongs to the threose structural type. It occurs in two stereoisomers. The (2S,3S) form is derived from D-threose, the (2R,3R) form from L-threose. Both stereoisomeric forms, as well as a mixture of the two forms, are within the scope of the invention. Dithiothreitol is also alternatively known as 1,4-dimercapto-2,3-butanediol, butane-2,3-diol-1,4-dithiol, and has the CAS numbers 3483-12-3 (DL-threo), 16096-97-2 (L-threo), and 7634-42-6 (unspecified). Very fast colorings have also been achieved with dithiothreitol, which wash out particularly evenly from hair strands. Therefore, the use of dithiothreitol in the pretreatment agent (V) is explicitly preferred.

[0030] Acetylcysteine ​​can also be abbreviated as ACC and has alternative names such as mercapturic acid, L-α-acetamido-β-mercaptopropionic acid, (R)-2-acetylamino-3-sulfanylpropanoic acid, or N-acetylcysteine. Acetylcysteine ​​has the CAS number 616-91-1. The carboxyl group of acetylcysteine ​​can also be deprotonated and neutralized by a corresponding equivalent of a cationic counterion. Suitable salts of acetylcysteine ​​include the sodium salt, the potassium salt, the ammonium salt, the magnesium salt, and the calcium salt. Very good results have been achieved with acetylcysteine. The use of acetylcysteine ​​and / or its salts in the pretreatment agent (V) is therefore also particularly preferred.

[0031] Dimercaptosuccinic acid, or dimercapto succinic acid, is an organic acid that has two stereocenters substituted by the same residues. Three stereoisomers of dimercaptosuccinic acid exist, all of which are within the scope of the invention. (2R,3R)-2,3-Dimercaptosuccinic acid has the CAS number 10008-75-0. (2S,3R)-2,3-Dimercaptosuccinic acid is also known as meso-2,3-Dimercaptosuccinic acid and has the CAS number 304-55-2. (2S,3S)-2,3-Dimercaptosuccinic acid has the CAS number 27887-82-7. 2418-14-6 is the CAS number of unspecified dimercaptosuccinic acid. One or both of the carboxyl groups present in dimercaptosuccinic acid can also be deprotonated and neutralized by a corresponding equivalent of a cationic counterion. Suitable salts of dimercaptosuccinic acid include the sodium salt, the potassium salt, the ammonium salt, the magnesium salt, and the calcium salt.

[0032] Thioglycerol is glycerol in which one of the three hydroxyl groups has been replaced by a thiol group. Thioglycerol is also alternatively referred to as 1-thioglycerol or 3-mercaptopropane-1,2-diol and has the CAS number 96-27-5. The use of thioglycerol in the pretreatment agent (V) is also preferred.

[0033] Another suitable reducing agent for the pretreatment agent (V) is thiolactic acid, alternatively referred to as 2-mercaptopropionic acid. 2-Mercaptopropionic acid is chiral, so the substance comprises the two enantiomers (R)-thiolactic acid and (S)-thiolactic acid. Both enantiomers, as well as their mixture, are within the scope of the invention. When thiolactic acid is referred to without further reference symbols, a 1:1 mixture of (R)-thiolactic acid and (S)-thiolactic acid is meant. Thiolactic acid has the CAS number 79-42-5. The carboxyl group of thiolactic acid can also be deprotonated and neutralized by a corresponding equivalent of a cationic counterion. Suitable salts of thiolactic acid include, for example, the sodium salt, the potassium salt, the ammonium salt, the magnesium salt, and the calcium salt.

[0034] Cysteine ​​is an α-amino acid with the side chain -CH 2-SH and is alternatively also referred to as 2-amino-3-sulfanylpropanoic acid and has the CAS numbers 52-90-4 (L-enantiomer), 921-01-7 (D-enantiomer), 3374-22-9 (DL-cysteine), 52-89-1 (L-cysteine ​​hydrochloride), 207121-46-8 (D-cysteine ​​hydrochloride monohydrate), and 7048-04-6 (L-cysteine ​​hydrochloride monohydrate). All stereoisomers, salts, and hydrates of cysteine ​​are according to the invention. Cysteine ​​is a mild reducing agent and is capable of breaking disulfide bridges in keratinic material. Cysteine ​​is oxidized to cystine in the process. According to a preferred embodiment, the pretreatment agent (V) comprises L-cysteine ​​as cysteine.

[0035] Thioglycolic acid can also be referred to as mercaptoacetic acid or sulfanylacetic acid and has the CAS number 68-11-1. Particularly suitable salts of thioglycolic acid include the ammonium salt (ammonium thioglycolate), the sodium salt, and the potassium salt of thioglycolic acid.

[0036] Sodium dithionite is an inorganic reducing agent with the molecular formula Na 2 S 2 O 4 and CAS No. 7775-14-6.

[0037] Zinc dithionite is an inorganic reducing agent with the molecular formula ZnS 2 O 4 and CAS No. 7779-86-4.

[0038] Potassium dithionite is an inorganic reducing agent with the molecular formula K 2 S 2 O 4 and CAS No. 14293-73-3.

[0039] Formamidine sulfinic acid is also known as thiourea dioxide or aminoiminomethanesulfinic acid. Formamidine sulfinic acid has the structure of formula (Red-I), but can also exist in the form of its tautomers. Formamidine sulfinic acid has the CAS number 1758-73-2.

[0040] Formamidine sulfinic acid can also be used in the form of its salts. Suitable examples include the sodium, potassium, and ammonium salts of formamidine sulfinic acid.

[0041] The above-mentioned compounds are commercially available from various chemical suppliers such as Fluka, Merck or Aldrich.

[0042] 2-Hydroxy-2-sulfinoacetic acid is preferably used in the form of its salt, particularly the sodium salt. The compound is commercially available, for example, under the trade name Brüggolit FF7 from Brüggemann.

[0043] The cosmetic agent (V) preferably contains dithioerythritol, dithiothreitol, acetylcysteine ​​and / or their salts for pre-cleaning.

[0044] The pre-cleaning agent (V) particularly preferably contains dithioerythritol and / or dithiothreitol.

[0045] The pretreatment agent (V) preferably contains the reducing agent(s) in an amount of 0.1 to 15.0 wt. %, preferably 0.2 to 10.5 wt. %, more preferably 0.3 to 7.5 wt. %, and most preferably 0.5 to 5.5 wt. %. The amounts stated here refer to the total amounts of reducing agents according to the invention, which are related to the total amount of the precleaning agent (V).

[0046] The pre-cleaning agent (V) particularly preferably contains - based on the total weight of the pre-cleaning agent (V) - one or more reducing agents (V-1) in a total amount of 0.1 to 15.0 wt.%, preferably 0.2 to 10.5 wt.%, more preferably 0.3 to 7.5 wt.% and very particularly preferably 0.5 to 5.5 wt.%.

[0047] The pretreatment agent (V) very particularly preferably contains - based on the total weight of the pretreatment agent (V) - one or more reducing agents (V-1) from the group consisting of dithioerythritol, dithiothreitol, acetylcysteine ​​and / or their salts, particularly preferably dithioerythritol and / or dithiothreitol, in a total amount of 0.1 to 15.0 wt.%, preferably 0.2 to 10.5 wt.%, more preferably from 0.3 to 7.5 wt.% and very particularly preferably from 0.5 to 5.5 wt.%.

[0048] In a further very particularly preferred embodiment, an agent (V) according to the invention is characterized in that it contains - based on the total weight of the agent - one or more reducing agents (V-1), preferably dithioerythritol, dithiothreitol, acetylcysteine ​​and / or their salts, particularly preferably dithioerythritol and / or dithiothreitol, in a total amount of 0.1 to 15.0% by weight, preferably 0.2 to 10.5% by weight, more preferably from 0.3 to 7.5% by weight and very particularly preferably from 0.5 to 5.5% by weight. Cosmetic carrier and pH of the pretreatment agent

[0049] The pre-cleaning agent (V) contains the reducing agent(s) in a cosmetic carrier, which is particularly preferably aqueous or water-containing.

[0050] It has been found that the surface modification of keratin fibers works particularly well when the reducing agent(s) act on the keratin fibers in an alkaline environment. Particularly suitable pH values ​​are in the range of 7.0 to 12.0, preferably 7.5 to 11.5, more preferably 8.0 to 11.0, and especially preferably 8.5 to 10.5.

[0051] In a further very particularly preferred embodiment, an agent according to the invention is characterized in that it contains water and has a pH of 7.0 to 12.0, preferably 7.5 to 11.5, more preferably 8.0 to 11.0 and particularly preferably 8.5 to 10.5.

[0052] To adjust the desired pH, the pretreatment agents (V) may therefore also contain at least one alkalizing agent. The pH values ​​within the meaning of the present invention are pH values ​​measured at a temperature of 22°C.

[0053] As alkalizing agents, the pretreatment agent (V) may contain, for example, ammonia, alkanolamines and / or basic amino acids.

[0054] The alkanolamines which can be used in the agent are preferably selected from primary amines having a C 2 -C 6 -Alkyl parent structure which carries at least one hydroxyl group. Preferred alkanolamines are selected from the group consisting of 2-aminoethanol-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, and 2-amino-2-methylpropan-1,3-diol.

[0055] Particularly preferred alkanolamines are selected from 2-aminoethane-1-ol and / or 2-amino-2-methylpropane-1-ol. A particularly preferred embodiment is therefore characterized in that the agent contains an alkanolamine selected from 2-aminoethane-1-ol and / or 2-amino-2-methylpropane-1-ol as an alkalizing agent.

[0056] An amino acid within the meaning of the invention is an organic compound which has in its structure at least one protonatable amino group and at least one -COOH- or -SO 3 H group. Preferred amino acids are aminocarboxylic acids, especially α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0057] Basic amino acids are those amino acids which have an isoelectric point pl of greater than 7.

[0058] Basic α-aminocarboxylic acids contain at least one asymmetric carbon atom. Within the scope of the present invention, both possible enantiomers can be used equally as specific compounds or as mixtures thereof, particularly as racemates. However, it is particularly advantageous to use the naturally occurring isomer form, usually in the L-configuration.

[0059] The basic amino acids are preferably selected from the group consisting of arginine, lysine, ornithine, and histidine, particularly preferably arginine and lysine. In another particularly preferred embodiment, an agent is characterized in that the alkalizing agent is a basic amino acid from the group consisting of arginine, lysine, ornithine, and / or histidine.

[0060] In addition, the agent may contain other alkalizing agents, particularly inorganic alkalizing agents. Inorganic alkalizing agents usable according to the invention are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, and potassium carbonate.

[0061] Very particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

[0062] Although the pretreatment agents (V) are preferably adjusted to pH values ​​in the alkaline range, it may still be necessary in principle to use small amounts of acidifying agents to fine-tune the desired pH value. Suitable acidifying agents according to the invention include, for example, citric acid, lactic acid, acetic acid, or diluted mineral acids (such as hydrochloric acid, sulfuric acid, phosphoric acid). anionic sulfate and / or sulfonate surfactants (V-2)

[0063] As the second ingredient (V-2) essential to the invention, the agent according to the invention contains at least one anionic surfactant. The anionic surfactant is particularly preferably an anionic sulfate and / or sulfonate surfactant.

[0064] Anionic sulfate or sulfonate surfactants are characterized by the presence of at least one sulfate or sulfonate group, which, depending on the pH prevailing in the cleaning agent, can be present in the form of their free acid or in the form of their physiologically acceptable salt. Examples of physiologically acceptable salts of sulfate groups include the sodium salts, potassium salts, and ammonium salts of sulfates. Examples of physiologically acceptable salts of sulfonate groups include the sodium salts, potassium salts, and ammonium salts of sulfonates.

[0065] The molecular structure of the anionic sulfate or sulfonate surfactants does not contain any cationic or cationizable groups, i.e. the structure of these surfactants does not include any amino or ammonium groups.

[0066] In the tests carried out, particularly good pre-cleaning was observed when the surfactant system contained in the cleaning agent contained at least one anionic sulfate and / or sulfonate surfactant (a) from the group consisting of - Dialkyl sulfosuccinates whose two alkyl groups are selected from identical or different, branched or unbranched C 2 to C 12 alkyl groups, - Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R 9 -O-(CH 2 -CH 2 O) n -SO 3 X, in the R 9 preferably represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl radical having 8 to 22 carbon atoms, n represents 0 or 1 to 12, and X represents an alkali or alkaline earth metal ion or protonated triethanolamine or the ammonium ion, - straight-chain or branched, saturated or mono- or polyunsaturated alkylsulfonates with 8 to 22 C atoms, - linear alpha-olefin sulfonates with 8 to 22 C atoms, - Acyl isethionates whose acyl group is selected from a branched or unbranched C 8 to C 22 alkyl group, - N-acyl taurates whose acyl group is selected from a branched or unbranched C 8 to C 22 alkyl group, and / or the salts of the aforementioned compounds.

[0067] In a further preferred embodiment, an agent for pre-cleaning the keratin fibers or hair is characterized in that it contains at least one anionic surfactant (V-2) selected from the group consisting of - Dialkyl sulfosuccinates whose two alkyl groups are selected from identical or different, branched or unbranched C 2 to C 12alkyl groups, - Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R 9 -O-(CH 2 -CH 2 O) n -SO 3 X, in the R 9 preferably represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl radical having 8 to 22 carbon atoms, n represents 0 or 1 to 12, and X represents an alkali or alkaline earth metal ion or protonated triethanolamine or the ammonium ion, - straight-chain or branched, saturated or mono- or polyunsaturated alkylsulfonates with 8 to 22 C atoms, - linear alpha-olefin sulfonates with 8 to 22 C atoms, - Acyl isethionates whose acyl group is selected from a branched or unbranched C 8 to C 22 alkyl group, - N-acyl taurates whose acyl group is selected from a branched or unbranched C 8 to C 22 alkyl group, and / or the salts of the aforementioned compounds.

[0068] A suitable anionic sulfate surfactant is sodium laureth sulfate, which is an ethoxylated, sulfated C12-C14 fatty alcohol whose sulfate groups are present in the form of the sodium salt. Sodium laureth sulfate has the CAS number 68891-38-3, and the raw material is commercially available, for example, under the trade name Texapon N 70.

[0069] Another suitable anionic sulfate surfactant is sodium lauryl sulfate, also known as sodium dodecyl sulfate, which is obtained by sulfation of dodecanol. In sodium lauryl sulfate, the sulfate group is present in the form of its sodium salt; the substance has the CAS number 151-21-3.

[0070] Particularly good results in pre-cleaning were obtained with anionic sulfonate surfactants, especially with sulfosuccinate surfactants.

[0071] Particularly suitable examples are ethoxylated monoalkyl sulfosuccinates, diisodecyl sulfosuccinates, sodium dioctyl sulfosuccinates, disodium lauryl sulfosuccinates, and butane diacid sulfoalkyl esters. Diethylhexyl sulfosuccinate and its salts are the most suitable.

[0072] Sodium ethylhexyl sulfosuccinate, also known as sulfosuccinic acid bis(2-ethylhexyl) ester, sodium salt, sodium bis(2-ethylhexyl) sulfocuccinate, or docusate sodium salt, is commercially available. This surfactant is also known by the abbreviation AOT, has the CAS number 577-11-7, and is a compound of the formula (AOT).

[0073] The agent (V) preferably contains the anionic surfactant(s) (V-2) in specific amounts. Particularly thorough pre-cleaning and comprehensive removal of all adhering constituents from the surface of the keratin substrate was achieved when the agent contained one or more anionic surfactants (V-2) in an amount of 0.1 to 20.0 wt. %, preferably 0.5 to 15.0 wt. %, more preferably 1.0 to 10.0 wt. %, and particularly preferably 1.5 to 7.5 wt. %, based on the total weight of the agent.

[0074] In a further very particularly preferred embodiment, an agent (V) according to the invention is characterized in that it contains - based on the total weight of the agent (V) - one or more anionic surfactants (V-2), preferably one or more dialkyl sulfosuccinates and / or salts thereof, particularly preferably 1,4-bis(2-ethylhexyl) sulfosuccinate in the form of its sodium salt, in an amount of 0.1 to 20.0 wt.%, preferably 0.5 to 15.0 wt.%, further preferably from 1.0 to 10.0 wt.% and particularly preferably from 1.5 to 7.5 wt.%. Surfactants (V-3) from the group of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants

[0075] As the third component (V-3) essential to the invention, the agent according to the invention contains at least one surfactant from the group of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants.

[0076] In interaction with the reducing agent (V-1) and the anionic surfactant(s) (V-2), the surfactants of group (V-3) enable a particularly effective and comprehensive removal of all components that are adhesively and covalently bound to the surface of the keratin fibers.

[0077] The agent preferably contains one or more surfactants from the group of alkoxylated fatty alcohols (V-3), preferably from the group of ethoxylated fatty alcohols, particularly preferably from the group of ethoxylated C 8 -C 22 -Alcohols with 1 to 15 EO, especially C 12 -C 18 -Alcohols with 7 EO.

[0078] Alkoxylated fatty alcohols are alkylene oxide addition products with saturated or unsaturated linear fatty alcohols, each containing 1 to 120 moles of ethylene oxide (EO) per mole of fatty alcohol. Particularly suitable fatty alcohols are C8-C22 alcohols with 1 to 15 EO, especially C12-C18 alcohols with 6 to 9 EO (calculated in moles of EO per mole of fatty alcohol).

[0079] Fatty alcohols that can be subjected to alkylation or, in particular, ethoxylation include 1-octanol, 1-decanol, 1-lauryl alcohol, 1-myristyl alcohol, 1-cetyl alcohol, and / or 1-steryl alcohol, or even 1-stearyl alcohol. These fatty alcohols can be single substances. However, it is generally preferred to start from native plant or animal raw materials in the production of these substances, resulting in mixtures of substances with different alkyl chain lengths, depending on the respective raw material.

[0080] For surfactants that are addition products of ethylene and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. "Normal" homolog distribution refers to mixtures of homologs obtained from the reaction of fatty alcohols and alkylene oxide using alkali metals, alkali metal hydroxides, or alkali metal alkoxides as catalysts. Narrow homolog distributions, on the other hand, are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides, or alkoxides are used as catalysts. The use of products with a narrow homolog distribution may be preferred.

[0081] A very suitable surfactant of this type bears the trade name Brij S 100 or Brij S 100 PA SG. This is stearyl alcohol ethoxylated with 100 EO, which is commercially available from Croda and has the CAS number 9005-00-9.

[0082] Another particularly suitable surfactant of this type is ceteareth-30. Ceteareth-30 is a mixture of cetyl alcohol and stearyl alcohol, each ethoxylated with 30 units of ethylene oxide. The mixture of cetyl alcohol and stearyl alcohol is referred to as cetearyl alcohol. Ceteareth-30 has the CAS number 68439-49-6 and is commercially available from BASF, for example, under the trade name Eumulgin B3.

[0083] Another particularly suitable raw material is Dehydol LT 7, a C12-C18 fatty alcohol, ethoxylated with 7 EO (or 7 mol ethylene oxide per mol fatty alcohol).

[0084] In a further particularly preferred embodiment, an agent according to the invention is characterized in that it comprises one or more surfactants (V-3) from the group of alkoxylated fatty alcohols, preferably from the group of ethoxylated fatty alcohols, preferably from the group of ethoxylated C 8 -C 22 -Alcohols with 1 to 30 EO, particularly preferably C 12 -C 18 -alcohols with 1 to 15 EO.

[0085] Particularly suitable ethoxylated fatty alcohols can be selected from the surfactants of the general formula (TI)wherein Ra is a saturated or unsaturated, unbranched or branched C 8 -C 24 -alkyl group, preferably a saturated, unbranched C 12 - to C 18- alkyl group, and n is an integer from 1 to 120, preferably an integer from 1 to 30, more preferably an integer from 1 to 15 and most preferably an integer from 6 to 9.

[0086] In a further embodiment, therefore, a cosmetic agent (V) for pre-cleaning keratin fibers, in particular human hair, containing in a cosmetic carrier (V-1) at least one reducing agent, and (V-2) at least one anionic surfactant from the group of dialkyl sulfosuccinates, whose two alkyl groups are selected from identical or different, branched or unbranched C 2 to C 12 alkyl groups, and (V-3) at least one surfactant from the group of alkoxylated fatty alcohols of the general formula (TI)wherein Ra is a saturated or unsaturated, unbranched or branched C 8 -C 24-alkyl group, preferably a saturated, unbranched C 12 - to C 18 - alkyl group, and n is an integer from 1 to 120, preferably an integer from 1 to 30, more preferably an integer from 1 to 15 and most preferably an integer from 6 to 9.

[0087] In addition to or instead of the ethoxylated fatty alcohols (V-3), the pre-cleaning agent (V) may also contain at least one amphoteric and / or zwitterionic surfactant.

[0088] Ampholytic or amphoteric surfactants are surface-active compounds which, in addition to a C 8 - C 24 - Alkyl or acyl group in the molecule at least one free amino group and at least one -COOH- or -SO 3H group and are capable of forming internal salts. Examples of suitable ampholytic or amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids, and alkylaminoacetic acids, each with approximately 8 to 24 C atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines, and sulfobetaines.

[0089] Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12 - C 18 - Acylsarcosine.

[0090] Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO (-) - or so3 (-) -group. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acyl-aminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, each with 8 to 18 C atoms in the alkyl or acyl group, as well as cocoacylaminoethyl hydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

[0091] The surfactant(s) of group (V-3) are contained in the agent (V) - based on the total weight of the agent (V) - preferably in an amount of 0.1 to 20 wt.%, preferably 0.4 to 11.0 wt.%, more preferably 0.8 to 9.5 wt.% and particularly preferably 1.2 to 3.8 wt.%.

[0092] In a further very particularly preferred embodiment, an agent (V) according to the invention is characterized in that it contains - based on the total weight of the agent - one or more surfactants from group (V-3) in a total amount of 0.1 to 20 wt.%, preferably 0.4 to 11.0 wt.%, more preferably 0.8 to 9.5 wt.% and particularly preferably 1.2 to 3.8 wt.%.

[0093] In a further very particularly preferred embodiment, an agent (V) according to the invention is characterized in that it contains - based on the total weight of the agent - one or more surfactants (V-3) from the group of ethoxylated C 8 -C 22 -alcohols with 1 to 15 EO in a total amount of 0.1 to 20 wt.%, preferably 0.4 to 11.0 wt.%, more preferably 0.8 to 9.5 wt.% and particularly preferably 1.2 to 3.8 wt.%. Non-ionic sugar surfactants (V-4)

[0094] Optionally, as a further component (V-4), the pretreatment agent (V) according to the invention may additionally contain one or more non-ionic sugar surfactants.

[0095] Nonionic sugar surfactants are uncharged, i.e., neither cationic nor cationizable, nor anionic or anionizable, surfactants whose molecular structure includes at least one sugar unit. Suitable sugar surfactants (V-4) include, for example, alkyl polyglycosides, the esters of fatty acids with sugars or sugar derivatives.

[0096] Alkylglucosides, alkylpolyglucosides can be described by the structural formula (T-II) where Rb a linear or branched C 6 -C 24 -alkyl radical and P represents an integer from 1 to 100, preferably from 1 to 30 and particularly preferably from 1 to 10.

[0097] Alkylpolyglucosides are also known to those skilled in the art by the abbreviation APG.

[0098] Particularly preferred are decyl polyglucoside and lauryl polyglucoside, which are marketed by BASF under the trade names Plantacare 2000, Plantaren 2000, and Plantaren 1200, respectively. Lauryl glucoside is commercially available from BASF under the trade names Plantacare 1200 UP or NP in the form of an approximately 51% aqueous solution. The CAS numbers for lauryl glucoside are 59122-55-3, 27836-64-2, 110615-47-9, and 113976-90-2.

[0099] Furthermore, particularly good results were obtained in the pre-cleaning of the keratin fibers with surfactants (V-4) from the group of mannosylerythritol lipids, which the expert also knows under the abbreviation MEL or MEL surfactants.

[0100] Mannosylerythritol lipids (MELs) are surface-active substances consisting of a hydrophilic moiety, 4-ObD-mannopyranosyl-meso-erythritol, and a hydrophobic moiety, which is a fatty acid or an acetyl group. They are obtained by fermentation from various microorganisms, primarily Pseudozyma sp., but also from Ustilago sp. and Schizonella melanogramma. Due to their origin, they are classified as so-called biosurfactants. The MELs used according to this invention are particularly preferably compounds of the general formula (T-III) where Rc and Rd independently represent a hydrogen atom or an acetyl group r is an integer from 6 to 10 and s is an integer from 6 to 10.

[0101] A distinction is made between MEL-A: Rc = Rd = Ac MEL-B: Rc = Ac, Rd = H MEL-C: Rc= H, Rd = Ac MEL-D: Rc = Rd = H.

[0102] In a preferred embodiment, a mixture of MEL-A and MEL-B is used in the surfactant system according to the invention.

[0103] In a particularly preferred embodiment, an agent (V) according to the invention is characterized in that it additionally contains one or more non-ionic sugar surfactants (V-4), preferably one or more non-ionic sugar surfactants (V-4) from the group of alkyl (poly)glucosides and mannosyl erythritol lipids.

[0104] Other suitable sugar surfactants include nonionic surfactants of the sugar fatty acid ester or alkyl sugar ester type. These are the esters of C 6 -C 24 -fatty acids and sugars or alkyl sugars.

[0105] Methyl glucoside monostearate is a corresponding product sold under the name GRILLOCOSE IS by the company GRILLOWERKE.

[0106] Methyl glucoside sesquistearate is sold under the name GLUCATE SS by AMERCHOL.

[0107] Ethyl 6-glucoside decanoate is sold under the name BIOSURF 10 by NOVO. A mixture of ethyl 6-glucoside mono- and dicocoate (82 / 7), like the product sold under the name BIOSURF COCO by NOVO.

[0108] The mixture of ethyl 6-glucoside mono- and dilaurate (84 / 8) is sold under the name BIOSURF 12 by NOVO. C-fatty acid monoesters 12 -C 18 Butyl glucoside monocoats, such as butyl glucoside monocoat, are sold by REWO under the names REWOPOL V3101 or REWOSAN V3101. Butyl glucoside monocoats, polyoxyethylated with 3 mol ethylene oxide, are sold by REWO under the name REWOPOL V3122.

[0109] The surfactant(s) of group (V-4) are preferably present in the detergent in specific amounts, based on the total weight of the detergent. The detergent preferably contains one or more nonionic sugar surfactants (V-4) in a total amount of 0.1 to 15.0 wt.%, preferably 0.2 to 9.5 wt.%, more preferably 0.5 to 4.5 wt.%, and particularly preferably 0.8 to 3.0 wt.%.

[0110] In a further very particularly preferred embodiment, an agent (V) according to the invention is characterized in that it contains - based on the total weight of the agent - one or more non-ionic sugar surfactants (V-4), preferably one or more alkyl (poly)glucosides, in a total amount of 0.1 to 15.0 wt.%, preferably from 0.2 to 9.5 wt.%, more preferably from 0.5 to 4.5 wt.% and particularly preferably from 0.8 to 3.0 wt.%. further surfactants other than (V-2), (V-3) and optionally (V-4)

[0111] In principle, the surfactant system of the pre-cleaning agent (V) can optionally also comprise additional surfactants different from (V-2), (V-3), and (V-4). This may be particularly the case if, in addition to the primarily desired cleaning effect, additional properties are desired. In this case, the surfactant system can, for example, also contain a cationic surfactant or another surfactant different from (V-2), (V-3), and (V-4).

[0112] However, since the surfactant system comprising (V-2), (V-3) and optionally (V-4) is specifically tailored to detach or remove as comprehensively as possible all components located on the surface of the keratin fiber, it is particularly preferred if the surfactant system of the pre-cleaning agent (V) either does not comprise any further surfactants other than (V-2), (V-3) and (V-4) or if it contains them only in very small quantities that do not significantly influence the cleaning performance.

[0113] Particularly preferably, the pre-cleaning agent (V) contains no further surfactants apart from the surfactants (V-2), (V-3) and (V-4).

[0114] In a further very particularly preferred embodiment, the pre-cleaning agent (V) according to the invention is characterized in that it contains no further surfactants apart from the surfactants (V-2), (V-3) and optionally (V-4).

[0115] In other words, the pre-cleaning agent (V) is preferably characterized in that it does not contain any surfactants other than (V-2), (V-3) and (V-4). Process for coloring keratin fibers

[0116] The pre-cleaning agent (V) described above is used for the pretreatment before the dyeing of keratin fibers in order to comprehensively clean the keratin fibers, to reductively treat their surface and thus to prepare them for dyeing, in which a pigment and / or a direct dye is deposited on or near the surface of the keratin fiber and immobilized there by forming a film.

[0117] A second subject of the present application is therefore a process for dyeing keratin fibers, in particular human hair, comprising the following steps: - application of a pre-cleaning agent (V) to the keratin fibers, wherein the pre-cleaning agent (V) was disclosed in detail in the description of the first subject matter of the invention, and - Application of a colorant (F) to the keratin fibers, wherein the colorant (F) contains (F-1) at least one organic silicon compound from the group of silanes having one, two or three silicon atoms, and (F-2) at least one coloring compound from the group of pigments and direct dyes. Coloring agents

[0118] In the context of this invention, the term "coloring agent" refers to the coloring of keratin fibers, particularly hair, achieved through the use of pigments and / or direct dyes. During this coloring, the pigments or direct dyes are deposited on or near the surface of the keratin fiber.

[0119] Following the application of the pre-cleansing agent (V), the colorant (F) is then applied to the keratin material in the process according to the invention. The colorant contains at least one organic silicon compound from the group of silanes with one, two, or three silicon atoms (F-1), and at least one colorant compound from the group of pigments and direct dyes (F-2). Silanes with one, two or three silicon atoms (F-1)

[0120] According to IUPAC 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.

[0121] Particularly suitable silanes (F-1) are the silanes of the formula (I) R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b (I), stand - R 1 , R 2 independently represent a hydrogen atom or a C 1 -C 6 -alkyl group, - L for a linear or branched, divalent C 1 -C 20 -alkylene group, - R 3 for a hydrogen atom or for a C 1 -C 6 -alkyl group, - R 4 for a C 1 -C 6 -alkyl group, - a, for an integer from 1 to 3, and - b for the integer 3 - a, and / or their hydrolysis and / or condensation products.

[0122] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one silane (F-1) of the formula (I) and / or its hydrolysis and / or condensation products R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b (I), where - R 1 , R 2 independently represent a hydrogen atom or a C 1 -C 6 -alkyl group, - L for a linear or branched, divalent C 1 -C 20 -alkylene group, - R 3 , R 4 independently of each other for a C 1 -C 6 -alkyl group, - a, stands for an integer from 1 to 3, and - b stands for the integer 3 - a.

[0123] The substituents R 1 , R 2 , R 3 , R 4and L in the compounds of formula (I) and (II) are exemplified below: Examples of a C 1 -C 6 Alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl, and n-hexyl. Propyl, ethyl, and methyl are preferred alkyl radicals.

[0124] Examples of a C 2 -C 6 -Alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, preferred C 2 -C 6 -Alkenyl radicals are vinyl and allyl. Examples of a linear divalent C 1 -C 20 -Alkylene group are, for example, the methylene group (-CH 2 -), the ethylene group (-CH 2 -CH 2 -), the propylene group (-CH 2 -CH 2 -CH 2 -) and the butylene group (-CH 2 -CH 2 -CH 2 -CH 2 -). The propylene group (-CH 2 -CH 2 -CH 2-) is particularly preferred. From a chain length of 3 C atoms, divalent alkylene groups can also be branched. Examples of branched, divalent C 3 -C 20 -Alkylene groups are (-CH 2 -CH(CH 3 )-) and (-CH 2 -CH(CH 3 )-CH 2 -).

[0125] In the organic silicon compounds of formula (I) R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b (I), the residues R 1 and R 2 independently represent a hydrogen atom or a C 1 -C 6 -alkyl group. The radicals R 1 and R 2 both represent a hydrogen atom.

[0126] In the middle part of the organic silicon compound is the structural unit or linker -L- which stands for a linear or branched, divalent C 1 -C 20 -alkylene group.

[0127] A divalent C 1 -C 20 -Alkylene group can alternatively be represented as a divalent or divalent C 1 -C 20 -alkylene group, which means that each group L can form two bonds. One bond is formed by the amino group R 1 R 2 N to the linker L, and the second bond is between the linker L and the silicon atom.

[0128] Preferably, -L- represents a linear, bivalent (i.e. divalent) C 1 -C 20 -alkylene group. More preferably, -L- represents a linear divalent C 1 -C 6 -alkylene group. Particularly preferably, -L- represents a methylene group (-CH 2 -), an ethylene group (-CH 2 -CH 2 -), a propylene group (-CH 2 -CH 2 -CH 2 -) or a butylene group (-CH 2 -CH 2 -CH 2 -CH 2-). Most preferably, L represents a propylene group (-CH 2 -CH 2 -CH 2 -).

[0129] The linear propylene group (-CH 2 -CH 2 -CH 2 -) can alternatively be referred to as propane-1,3-diyl group.

[0130] The organic silicon compounds of formula (I) R 1 R 2 NL-Si(OR 3 ) a (R 4 ) b (I), each carry the silicon-containing group -Si(OR 3 ) a (R 4 ) b .

[0131] In the terminal structural unit -Si(OR 3 ) a (R 4 ) b the remainder R 3 for a hydrogen atom or a C 1 -C 6 -alkyl group, and the residue R 4 stands for a C 1 -C 6 -alkyl group. R 3 and R 4independently represent a methyl group or an ethyl group.

[0132] 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.

[0133] If the index number a stands for the number 2 or 3, several OR 3 Units in the silane molecule of formula (I). In this case, the radical R 3 in each of the OR 3 Units independent of the other OR 3 units can be chosen. For example, if a stands for the number 3, the silane molecule comprises three OR 3 Units of which, for example, one unit can represent a hydroxy group and two units can represent an ethoxy group.

[0134] Particularly resistant films could be produced if the colorant (F) contains at least one organic silicon compound (F-1) of the formula (I), in which independently of one another the radical R 3 represents a hydrogen atom, a methyl group or an ethyl group and the radical R 4 represents a methyl group or an ethyl group.

[0135] When using the process for dyeing human hair, dyeings with the best washfastness properties could be obtained if the dyeing agent (F) contains at least one organic silicon compound (F-1) of the formula (I), in which, independently of one another, - the remainder R 3 a hydrogen atom is a methyl group or an ethyl group, and - the remainder R 4 represents a methyl group or an ethyl group.

[0136] Furthermore, dyeings with the best washfastness properties could be obtained when the dyeing agent (F) contains at least one organic silicon compound of the formula (I) in which the radical a represents the number 3. In this case, the radical b represents the number 0.

[0137] In a further preferred embodiment, the colorant (F) used in the process is characterized in that it contains at least one organic silicon compound (F-1) of the formula (I), where - R 3 represents a hydrogen atom, a methyl group or an ethyl group, and - R 4 represents a methyl group or an ethyl group, and - a stands for the number 3, and - b stands for the number 0.

[0138] Organic silicon compounds of the formula (I) which are particularly suitable for solving the problem according to the invention are - (3-Aminopropyl)triethoxysilane- (3-Aminopropyl)trimethoxysilane- (2-Aminoethyl)triethoxysilane- (2-Aminoethyl)trimethoxysilane- (3-Dimethylaminopropyl)triethoxysilane- (3-Dimethylaminopropyl)trimethoxysilane- (2-Dimethylaminoethyl)triethoxysilane.- (2-Dimethylaminoethyl)trimethoxysilane and

[0139] The complete hydrolysis product of 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane is 1-(3-aminopropyl)silanetriol

[0140] The complete hydrolysis product of 3-aminoethyltriethoxysilane and 3-aminoethyltrimethoxysilane is 1-(2-aminoethyl)silanetriol

[0141] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one silane (F-1) selected from the group consisting of - (3-Aminopropyl)triethoxysilane - (3-Aminopropyl)trimethoxysilane - (2-Aminoethyl)triethoxysilane - (2-Aminoethyl)trimethoxysilane - (3-Dimethylaminopropyl)triethoxysilane - (3-Dimethylaminopropyl)trimethoxysilane - (2-Dimethylaminoethyl)triethoxysilane. - (2-Dimethylaminoethyl)trimethoxysilane and / or their hydrolysis and / or condensation products.

[0142] The aforementioned organic silicon compounds of formula (I) are commercially available. (3-Aminopropyl)trimethoxysilane, for example, can be purchased from Sigma-Aldrich. (3-Aminopropyl)triethoxysilane is also commercially available from Sigma-Aldrich.

[0143] In further dyeing experiments, it has been found to be particularly advantageous if the dyeing agent (F) used in the process additionally contained at least one organic silicon compound (F-1) of the formula (II) R 5 Si(OR 6 ) k (R 7 ) m (II).

[0144] The organic silicon compound(s) of formula (II) can also be referred to as silanes of the alkylalkoxysilane or alkylhydroxysilane type, R 5 Si(OR 6 ) k (R 7 ) m (II), where - R 5 for a C 1 -C 18 -alkyl group, - R 6 for a hydrogen atom or a C 1 -C 6 -alkyl group, - R 7 for a C 1 -C 6 -alkyl group - k stands for an integer from 1 to 3, and - m stands for the integer 3 - k.

[0145] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one silane (F-1) of the formula (II) and / or its hydrolysis and / or condensation products, R 5 Si(OR 6 ) k (R7 ) m (II), where - R 5 for a C 1 -C 18 -alkyl group, - R 6 for a hydrogen atom or a C 1 -C 6 -alkyl group, - R 7 for a C 1 -C 6 -alkyl group - k stands for an integer from 1 to 3, and - m stands for the integer 3 - k.

[0146] In the organic silicon compounds of formula (II), the radical R 5 for a C 1 -C 18 -alkyl group. This C 1 -C 18 -Alkyl group is saturated and can be linear or branched. Preferably, R 5 for a linear C 1 -C 18 -alkyl group. R is preferably 5represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group or an n-octadecyl group. R is particularly preferably 5 for a methyl group, an ethyl group, an n-hexyl group or an n-octyl group.

[0147] In the organic silicon compounds of form (II) the radical R 6 for a hydrogen atom or a C 1 -C 6 -alkyl group. R is particularly preferably 6 for a methyl group or for an ethyl group.

[0148] If the index number k stands for the number 2 or 3, several OR 6 Units in the silane molecule of formula (II). In this case, the radical R 6 in each of the OR 6 Units independent of the other OR 6 units can be chosen. For example, if k stands for the number 3, the silane molecule comprises three OR 6Units of which, for example, one unit can represent a hydroxy group and two units can represent an ethoxy group.

[0149] In the organic silicon compounds of form (II) the radical R 7 for a C 1 -C 6 -alkyl group. R is particularly preferably 7 for a methyl group or for an ethyl group.

[0150] 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 equal to 0. If k represents the number 2, then m is equal to 1. If k represents the number 1, then m is equal to 2.

[0151] Particularly stable films, ie dyeings with particularly good washfastness properties, could be obtained when a dyeing agent (F) was used in the process which, in addition to the silane(s) (F-1) of formula (I), contained at least one organic silicon compound of formula (II) in which the radical k stands for the number 3. In this case, the radical m stands for the number 0.

[0152] Organic silicon compounds of the formula (II) which are particularly suitable for solving the problem according to the invention are - Methyltrimethoxysilane - Methyltriethoxysilane - Ethyltrimethoxysilane - Ethyltriethoxysilane - n-hexyltrimethoxysilane - n-Hexyltriethoxysilane - n-octyltrimethoxysilane - n-octyltriethoxysilane - n-dodecyltrimethoxysilane and / or - n-Dodecyltriethoxysilane. n-octadecyltrimethoxysilane and / or n-octadecyltriethoxysilane.

[0153] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one silane (N-1) selected from the group consisting of - Methyltrimethoxysilane - Methyltriethoxysilane - Ethyltrimethoxysilane - Ethyltriethoxysilane - Propyltrimethoxysilane - Propyltriethoxysilane - Hexyltrimethoxysilane - Hexyltriethoxysilane - Octyltrimethoxysilane - Octyltriethoxysilane - Dodecyltrimethoxysilane, - Dodecyltriethoxysilane, - Octadecyltrimethoxysilane, - Octadecyltriethoxysilane and / or their hydrolysis and / or condensation products.

[0154] The best results were obtained when the colorant (F) contains at least one silane (F-1) selected from the group consisting of (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (2-dimethylaminoethyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane and / or their hydrolysis and / or condensation products, and / or - the colorant (F) contains at least one silane (F-1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, Octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane and / or their hydrolysis and / or condensation products.

[0155] In a further particularly preferred embodiment, a method according to the invention is characterized in that - the colorant (F) contains at least one silane (F-1) selected from the group consisting of (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (2-dimethylaminoethyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane and / or their hydrolysis and / or condensation products, and / or - the colorant (F) contains at least one silane (F-1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane and / or their hydrolysis and / or condensation products.

[0156] It has been found to be preferred if the colorant (F) - based on the total weight of the colorant (F) - contained one or more organic silicon compounds (F-1) in a total amount of 0.1 to 20 wt.%, preferably 1 to 15 wt.% and particularly preferably 2 to 12 wt.%.

[0157] It has been found to be preferred if the colorant (F) - based on the total weight of the colorant (F) - contained one or more organic silicon compounds (F-1) of the formula (I) and the formula (II) in a total amount of 0.1 to 20 wt.%, preferably 1 to 15 wt.% and particularly preferably 2 to 12 wt.%. Oligomers and / or condensation products of organosilicon compounds

[0158] In the case of the previously described organic silicon compounds or silanes of formulas (I) and (II), even the addition of small amounts of water leads to hydrolysis or oligomerization and / or polymerization. The extent of oligomerization or polymerization depends on the amount of water that comes into contact with the silane(s) of formulas (I) or (II). The aim of the process according to the invention is that the formation of the colored film, i.e. the final polymerization starting from the silanes (F-1), takes place when the colorant (F) is already on the keratin fibers. However, due to the high reactivity of the silanes (F-1), oligomerization or precondensation may have already taken place before the colorant (F) is applied, and the silanes may already be hydrolyzed, oligomerized or, to a small extent, even polymerized in the colorant (F).

[0159] For this reason, both the silanes of formulas (I) and (II) and their hydrolysis products, oligomers, and / or condensation products can be present in the colorant (F). According to the invention, the term "silanes of formula (I) and (II)" therefore also encompasses their hydrolysis products, oligomers, and / or condensation products.

[0160] The corresponding hydrolysis products, oligomers and / or condensation products are, for example, the following compounds.

[0161] Hydrolysis of C 1 -C 6 -Alkoxysilane of formula (I) with water (reaction scheme using the example of 3-aminopropyltriethoxysilane):

[0162] Depending on the amount of water used, the hydrolysis reaction can also be repeated several times per C used. 1 -C 6 -Alkoxy-silane take place:or.

[0163] Hydrolysis of C 1 -C 6-Alkoxysilane of formula (II) with water (reaction scheme using the example of methyltrimethoxysilane):

[0164] Depending on the amount of water used, the hydrolysis reaction can also be repeated several times per C used. 1 -C 6 -Alkoxy-silane take place:or.

[0165] Possible condensation reactions are, for example (shown using the mixture (3-aminopropyl)triethoxysilane and methyltrimethoxysilane): and / or and / or and / or and / or and / or and / or

[0166] 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.

[0167] A condensation product is a product formed by the reaction of at least two organic silicon compounds, each containing at least one hydroxyl group or hydrolyzable group per molecule, with the elimination of water and / or an alkanol. The condensation products can be, for example, dimers, but also trimers or oligomers, with the condensation products being in equilibrium with the monomers. Depending on the amount of water used or consumed in the hydrolysis, the equilibrium shifts from monomeric organic silicon compounds to condensation product.

[0168] Particularly good results were obtained when organic silicon compounds of formulas (I) and (II) were used in the process. Since, as already described above, hydrolysis / condensation begins even with traces of moisture, the hydrolysis and / or condensation products of the organic silicon compounds (I) and (II) are also encompassed by this embodiment. color-providing compounds (F-2)

[0169] The colorant (F) contains at least one coloring compound (F-2) from the group of pigments and direct dyes.

[0170] Pigments within the meaning of the present invention are understood to be coloring compounds which have a solubility in water at 25°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 25°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 pigments remains on the filter paper, the solubility of the pigment is below 0.5 g / L.

[0171] 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.

[0172] 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).

[0173] 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 the pearlescent pigments in combination with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.

[0174] 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).

[0175] In a further preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one inorganic pigment, which is preferably selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and / or colored pigments based on mica or mica, which are coated with at least one metal oxide and / or one metal oxychloride.

[0176] In a further preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one pigment 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).

[0177] 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.

[0178] Please be sure to drink the color pigments with the Handelsbezeichnung Colorona® and beispielsweise: Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE) Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE) Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRON OXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES) Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide), Silica, CI 77491 (Iron oxides), Tin oxide Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, CI 77891, CI 77491 (EU) Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iron oxides) Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

[0179] Weiterhin besonders bevorzugte Farbpigmente mit der Handelsbezeichnung Xirona® sind beispielsweise: Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0180] In addition, particularly preferred color pigments with the trade name Unipure® are, for example: Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0181] In a further embodiment, the applied colorant may also contain one or more organic pigments.

[0182] 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.

[0183] 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 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] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one organic pigment, which is preferably 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.

[0185] 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 above-mentioned conditions. The particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum.

[0186] Alizarin varnish, for example, can be used as a colored varnish.

[0187] Pigments with a specific shape can also be used to color the keratin fibers. For example, a pigment based on a lamellar and / or lenticular substrate plate can be used. Furthermore, coloring based on a substrate plate containing a vacuum-metallized pigment is also possible.

[0188] In a further preferred embodiment, a process according to the invention is characterized in that the colorant contains at least one pigment selected from the group of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet and vacuum metallized pigments.

[0189] The substrate platelets of this type have an average thickness of at most 50 nm, preferably less than 30 nm, more 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, more 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. Each substrate platelet preferably has a thickness that is as uniform as possible. Due to the low thickness of the substrate platelets, the pigment has particularly high hiding power.

[0190] The substrate platelets are preferably monolithic in 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 in structure, meaning that no concentration gradient occurs within the platelets. In particular, the substrate platelets are not layered and do not contain any particles or particles distributed within them.

[0191] The size of the substrate platelet can be tailored to the specific application, especially the desired effect on the keratinous material. Typically, the substrate platelets have an average diameter of approximately 2 to 200 µm, particularly approximately 5 to 100 µm.

[0192] 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 Helos device with Quixel wet dispersion. For sample preparation, the sample to be tested was predispersed in isopropanol for 3 minutes.

[0193] The substrate platelets can be made of any material that can be formed into platelets.

[0194] 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).

[0195] 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.

[0196] Lamellar substrate platelets are characterized by an irregularly structured edge and are also called “cornflakes” due to their appearance.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] The substrate plates made of metal or metal alloy can be passivated, for example by anodizing (oxide layer) or chromating.

[0201] Uncoated lamellar, lenticular, and / or VPM substrate plates, especially those made of metal or metal alloy, reflect incident light to a high degree and produce a light-dark flop. These have proven particularly preferred for use in the dye.

[0202] Suitable pigments based on a lamellar substrate platelet include, for example, the pigments of the VISIONAIRE series from Eckart.

[0203] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH.

[0204] Pigments based on a substrate platelet comprising a vacuum metallized pigment are available, for example, under the name Alegrace® Marvelous or Alegrace® Aurous from Schlenk Metallic Pigments GmbH.

[0205] Due to their excellent light and temperature resistance, the use of the aforementioned pigments in the agent according to the invention is 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 D 50 from 1.0 to 50 µm, preferably from 5.0 to 45 µm, preferably from 10 to 40 µm, in particular from 14 to 30 µm. The average particle size D 50 can be determined, for example, using dynamic light scattering (DLS).

[0206] The colorant can also contain at least one substantive dye as a coloring agent. Substantive dyes are dyes that are absorbed directly into the hair and do not require an oxidative process to develop the color. Substantive dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0207] Direct dyes can be non-ionic, cationic or anionic.

[0208] Anionic direct dyes are also called acid dyes. Acid dyes are understood to be direct dyes that contain at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO 3 H) and / or a sulfate group (-OSO 3 H). Depending on the pH value, the protonated forms (-COOH, -SO 3H) the carboxylic acid or sulfonic acid groups with their deprotonated forms (-COO - , -SO 3 - or -OSO 3 - presumably) in equilibrium. With decreasing pH, the proportion of protonated forms increases. If direct dyes are used in the form of their salts, the carboxylic acid groups or sulfonic acid groups are present in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electroneutrality. Acid dyes according to the invention can also be used in the form of their sodium salts and / or their potassium salts.

[0209] The alkaline earth metal salts (such as calcium and magnesium salts) and aluminum salts of acid dyes often have lower solubility than the corresponding alkali metal salts. If the solubility of these salts is below 0.5 g / L (25 °C, 760 mmHg), they do not fall under the definition of a direct dye.

[0210] A key feature of acid dyes is their ability to form anionic charges, with the carboxylic acid or sulfonic acid groups responsible for this being typically linked to various chromophoric systems. Suitable chromophoric systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes, and / or indophenol dyes.

[0211] Als Beispiele für Säurefarbstoffe können genannt werden: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403,CI 10316, COLIPA n° B001), Acid Yellow 3 (COLIPA n° : C 54, D&C Yellow N° 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA n° C 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA n° C015), Acid Orange 10 (C.I. 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1;CI20170;KATSU201;nosodiumsalt;Brown No.201;RESORCIN BROWN;ACID ORANGE 24;Japan Brown 201;D & C Brown No.1), Acid Red 14 (C.I.14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red 27 (E 123, CI 16185, C-Rot 46, Echtrot D, FD&C Red Nr.2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CI C.I.18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, lodeosin), Acid Red 52 (CI 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA n° C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine,Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet n° 2, C.I. 60730, COLIPA n° C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), Acid Blue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blau V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133, Patentblau AE, Amidoblau AE, Erioglaucin A, CI 42090, C.I.Food Blue 2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585), Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI 42095), Acid Green 9 (C.I.42100), Acid Green 22 (C.I.42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, C.I. 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n° 401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n° B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 und / oder D&C Brown 1.

[0212] In the context of a further embodiment, a method according to the invention is characterized in that the dye contains at least one acid dye selected from the group consisting of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Orange Red 14, Acid Red 18, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33,D&C Violet 2 and / or D&C Brown 1.,

[0213] Since alkaline earth metal salts (such as calcium and magnesium salts) or aluminum salts of acid dyes are less soluble than the corresponding alkali metal salts, an organic dye that, in the form of its alkali metal salt, is considered an acid dye can also exist in the form of a pigment if the counterion for the acid group(s) is not an alkali metal ion, but rather an alkaline earth metal ion or an analogous, correspondingly more highly charged counterion. If the solubility of these salts is below 0.5 g / L (25 °C, 760 mmHg), the compounds do not fall under the definition of a direct dye.

[0214] The water solubility of anionic direct dyes can be determined, for example, as follows: 0.1 g of the anionic direct dye is placed in a beaker. A stir bar is attached. Then 100 ml of water is added. This mixture is heated to 25 °C on a magnetic stirrer while stirring. It is stirred for 60 minutes. The aqueous mixture is then visually assessed. If undissolved residues remain, the amount of water is increased – for example, in 10 ml increments. Water is added until the added amount of dye has completely dissolved. If the dye-water mixture cannot be visually assessed due to the high intensity of the dye, the mixture is filtered. If a portion of undissolved dye remains on the filter paper, the solubility test is repeated using a larger amount of water.If 0.1 g of the anionic direct dye dissolves in 100 ml of water at 25 °C, the solubility of the dye is 1.0 g / L.

[0215] Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40 g / L (25°C).

[0216] Acid Yellow 3 is a mixture of the sodium salts of mono- and disulfonic acids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a water solubility of 20 g / L (25 °C).

[0217] Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its water solubility is above 40 g / L (25 °C).

[0218] Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylic acid and is readily soluble in water at 25 °C.

[0219] Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulfonate. Its water solubility is greater than 7 g / L (25 °C).

[0220] Acid Red 18 is the trisodium salt of 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl]-1,3-naphthalenedisulfonate and has a very high water solubility of more than 20 wt%. Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulfonate; its water solubility is 2.5 g / L (25 °C).

[0221] Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, whose water solubility is stated to be greater than 10 g / L (25 °C).

[0222] Brilliant Blue FCF, alternatively known as Food Blue 2 or Acid Blue 9, is known as disodium 2-[(Z)-{4-[ethyl(3-sulfonatobenzyl)amino]phenyl}{(4Z)-4-[ethyl(3-sulfonatobenzyl)iminio]-2,5-cyclohexadien-1-ylidene}methyl]benzenesulfonate in its disodium salt and has the CAS number 3844-45-9. The disodium salt of Acid Blue 9 has a water solubility of more than 20 wt.% (25 °C).

[0223] Acid Blue 74 is also known as Indigo Carmine, Food Blue 1, or FD&C Blue 2 and has the chemical name Indigo-5,5'-disulfonic acid, disodium salt, or disodium 5,5'-(2-(1,3-dihydro-3-oxo-2H-indazol-2-ylidene)-1,2-dihydro-3H-indol-3-one)disulfonate. Acid Blue 74 in the form of the disodium salt has a solubility in water of 10 g / L at 25 °C.

[0224] The coloring compound(s) are preferably used in the colorant in specific quantity ranges. Particularly good results were obtained when the colorant contained one or more coloring compounds from the group of pigments and direct dyes in a total amount of 0.01 to 10.0 wt. %, preferably 0.1 to 5.0 wt. %, more preferably 0.2 to 2.5 wt. %, and most preferably 0.25 to 1.5 wt. %, based on the total weight of the colorant. Cosmetic carrier of the colorant (F)

[0225] The colorant is understood to be the ready-to-use colorant that contains the silane(s) (F-1) and the colorant(s) (F-2), particularly preferably in a cosmetic carrier. In one embodiment, the colorant (F) can be formulated with a low water content or without water. In another embodiment, however, the cosmetic carrier can also be water or a mixture of water with a solvent.

[0226] Particularly suitable solvents are, for example, the compounds from the group of poly-C 1 -C 6 -Alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerin, phenoxyethanol and benzyl alcohol. Poly-C 1 -C 6 -Alkylene glycols, especially polyethylene glycols, have shown particularly good suitability in this regard.

[0227] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains one or more solvents from the group consisting of ethanol, poly-C 1 -C 6 -alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerin, phenoxyethanol and benzyl alcohol.

[0228] As suitable poly-C 1 -C 6 -Alkylene glycols can be mentioned in particular the polyethylene glycols, as described for example by the formula (AG)wherein p represents an integer from 1 to 1000, preferably 1 to 100, particularly preferably 2 to 50.

[0229] The alkylene glycols of formula (AG) are protic substances with at least one hydroxyl group, which, due to their repeating unit -CH2-CH2-O-, can also be referred to as polyethylene glycols, provided p represents a value of at least 2. In the alkylene glycols of formula (AG), p 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.

[0230] 1,2-Propylene glycol is alternatively referred to as 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 referred to as 1,3-dihydroxypropane or 1,3-propanediol and has the CAS number 504-63-2. 1,2-Butylene glycol can also be referred to as 1,2-butanediol and has the CAS numbers 584-03-2 (racemate), 40348-66-1 ((R)-enantiomer), and 73522-17-5 ((S)-enantiomer).

[0231] Dipropylene glycols (or oxydipropanols) form a group of substances derived from glycol ethers. The dipropylene glycol group 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.

[0232] Ethanol has the CAS No. 64-17-5. Isopropanol is also known as 2-propanol and has the CAS No. 67-63-0. Ethylene glycol is also known as 1,2-ethanediol and has the CAS No. 107-21-1.

[0233] 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.

[0234] 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. Benzyl alcohol can also be known as phenylmethanol and has the CAS number 100-51-6.

[0235] All solvents described above are commercially available from various chemical suppliers such as Aldrich or Fluka.

[0236] A particularly suitable solvent for the dye (F) is ethylene glycol, which belongs to the group of poly-C 1 -C 6 -Alkylene glycols fall and repeating - CH 2 -CH 2 -O- units. Ethylene glycols are compounds of the formula (EG-F)wherein y is an integer from 1 to 10,000, preferably an integer from 2 to 500, more preferably an integer from 3 to 100, and most preferably an integer from 5 to 30.

[0237] If y stands for the number 1, the ethylene glycol of formula (EG-F) is ethylene glycol itself, which is alternatively called 1,2-ethanediol and has the CAS number 107-21-1.

[0238] A particularly preferred low-molecular-weight polyethylene glycol is PEG-8. PEG-8 contains an average of 8 ethylene glycol units (y1 = 8), has an average molecular weight of 400 g / mol, and bears the CAS number 25322-68-3. PEG-8 is also referred to as PEG 400 and is commercially available, for example, from APS.

[0239] Other suitable low molecular weight polyethylene glycols include PEG-6, PEG-7, PEG-9 and PEG-10.

[0240] Another suitable polyethylene glycol is PEG-32. PEG-32 contains 32 ethylene glycol units (y1 = 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.

[0241] A particularly suitable high-molecular-weight polyethylene glycol is PEG 6000, which is commercially available from National Starch (China). The molecular weight of PEG 6000 is between 6000 and 7500 g / mol.

[0242] Another suitable polyethylene glycol is PEG 12000, which is marketed commercially by CG Chemicals under the trade name Polyethylene Glycol 12000 S (or PEG 12000 S). The molecular weight of PEG 12000 is stated to be between 10,500 and 15,000 g / mol.

[0243] Another suitable polyethylene glycol is PEG 20000, which is commercially available from Clariant under the trade name Polyglycol 20000 P or under the alternative name PEG-350. PEG 20000 has an average molecular weight of 20,000 g / mol.

[0244] The solvent(s) are preferably used in certain quantity ranges in the colorant (F). Preferably, the colorant (F) contains - based on the total weight of the colorant (F) - one or more solvents from the group consisting of water, poly-C 1 -C 6 -Alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol in a total amount of 10.0 to 99.0 wt.%, preferably from 30.0 to 99.0 wt.%, more preferably from 50.0 to 99.0 wt.% and most preferably from 70.0 to 99.0 wt.%. further optional ingredients in the agents (V) and / or (F)

[0245] In addition to the components essential to the invention already described, the pretreatment agent (V) and / or the colorant (F) may also contain further optional ingredients.

[0246] The products may also contain other active ingredients, auxiliary substances and additives, such as solvents, fatty components such as C 8 -C 30 -fatty alcohols, the C 8 -C 30 -fatty acid triglycerides, the C 8 -C 30 -fatty acid monoglycerides, the C 8 -C 30-Fatty acid diglycerides and / or hydrocarbons; surfactants or emulsifiers, 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 agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose; dyes for coloring the product; anti-dandruff agents 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 optionally anionically or cationically modified derivatives; vegetable oils; light protectants 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 glycerol, 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; and propellants such as propane-butane mixtures, N; 2 O, dimethyl ether, CO 2 and air.

[0247] 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. Sequence of procedural steps

[0248] As previously described, the cleansing agent (V) is applied to pre-clean the keratin fibers and thus prior to the application of the colorant (F). In this context, it has proven particularly preferable to apply the cleansing agent to the keratin material, allow it to work for a certain period of time, and then rinse it off with water.

[0249] Particularly preferred is therefore a method for coloring keratin fibers, in particular human hair, comprising the following steps in the given order: (1a) Applying the pre-cleaning agent (V), as disclosed in detail in the description of the first subject matter of the invention, to the keratin fibers, (1b) allowing the pre-cleansing agent applied in step (1) to act on the keratin fibres for a period of 2 to 45 minutes, preferably from 2 to 30 minutes and particularly preferably from 2 to 20 minutes, (1c) Rinse out the pre-cleaning agent with water, (2a) applying the colorant (F) to the keratin fibers, and (2b) Exposing the colorant applied in step (4) to the keratin fibers for a period of 15 seconds to 45 minutes, preferably 30 seconds to 30 minutes, and particularly preferably 1 to 15 minutes.

[0250] In a further preferred embodiment, a process according to the invention is characterized in that step (2a) takes place directly after step (1c). Step (2a) involves the application of the colorant.

[0251] The action of the colorant (F) on the keratin fibers in step (2b) can, for example, take place for a period of 15 seconds to 30 minutes, preferably for a period of 30 seconds to 15 minutes, particularly preferably for a period of 1 to 15 minutes.

[0252] In principle, the user can freely choose the period of time between the application of the two products.

[0253] However, it may be preferable that no further products, such as other conditioners, shampoos, or styling products, are applied between the application of the two products (V) and (F). For this reason, the maximum period between the application of the two products (V) and (F) is particularly preferably limited to a maximum time interval of 24 hours.

[0254] It has been found to be preferable if there is a period of maximum 24 hours, preferably maximum 12 hours, more preferably maximum 6 hours and most preferably maximum 3 hours between the application of the pre-cleaning agent (V) and the coloring agent (F).

[0255] Furthermore, it has also been found to be preferable if there is a period of maximum 24 hours, preferably maximum 12 hours, more preferably maximum 6 hours and most preferably maximum 3 hours between rinsing out the pre-cleaning agent (V) with water and applying a coloring agent (F) to the keratin fibers.

[0256] In a further embodiment, a method comprising the following steps in the given order is particularly preferred: - Application of the pre-cleansing agent (V) on the keratin fibers, then - Application of the coloring agent (F) to the keratin fibers, wherein between the application of the pre-cleaning agent (V) and the application of the coloring agent (F) there is a period of maximum 24 hours, preferably of maximum 12 hours, more preferably of maximum 6 hours and most preferably of maximum 3 hours. Multi-component packaging unit (kit of parts)

[0257] To increase user convenience, all required resources are preferably provided to the user in the form of a multi-component packaging unit (kit of parts).

[0258] A further subject of the present invention is therefore a multi-component packaging unit (kit-of-parts) for treating keratin fibers, in particular human hair, comprising separately packaged - a first container with a pretreatment agent (V), and - a second container with a colorant (F), wherein the pretreatment agent (V) and the colorant (F) were disclosed in detail in the description of the first subject matter of the invention.

[0259] With regard to the further preferred embodiments of the multi-component packaging units, what has been said about the agent and method according to the invention applies mutatis mutandis. Examples1. Formulations

[0260] The following formulations were prepared (unless otherwise stated, all data are in wt% active ingredient) Pretreatment agent (V) V1 (wt%) V2 (wt%) V3 (wt%) V4 (wt%) V5 (wt%) Dithioerythritol - 1,0 5,0 1,0 5,0 Sodium bis-(2-ethylhexyl)sulfocuccinate (as AOT) 6,2 - - 6,2 6,2 C12-C18 fatty alcohols, ethoxylated (7 EO, as Dehytol LT 7) 2,8 - - 2,8 2,8 Lauryl glucoside (as APG 600) 2,3 - 2,3 2,3 Monoethanolamine / Citric acid to pH 10 to pH 10 to pH 10 to pH 10 to pH 10 Water (distilled) to 100 to 100 to 100 to 100 to 100

[0261] The pretreatment agent (V1) contains the surfactants according to the invention, but no reducing agent.

[0262] The pretreatment agents (V2) and (V3) contain different concentrations of the reducing agent dithioerythritol, but no surfactants.

[0263] The pretreatment agents (V4) and (V5) contain different concentrations of the reducing agent dithioerythritol and the surfactants according to the invention. Dye (F) Dye (F) % by weight (3-Aminopropyl)triethoxysilane 3,0 Methyltriethoxysilane 6,0 Water 1,0 NaOH 0,01 Unipure Red LC 3079 (Pigment Red 7, CAS No. 5281-04-9) 1,0 Ethanol to 100 2. Application

[0264] Hair strands with varying degrees of damage (Kerling 9-0, slightly damaged, and Euronaturhaar white, heavily bleached, and heavily damaged) were pretreated with the respective pretreatment agent (V). For this purpose, 0.4 g of pretreatment agent (V) was applied per 1 g of strand, massaged in, and left to work for 25 minutes at room temperature. The strands were then rinsed with warm water for 1 minute and dried.

[0265] Immediately afterward, each strand of hair was briefly moistened. The dye (F) was then applied to the towel-dried strand (1.0 g of dye (F) per 1 g of hair) and massaged into each strand for 30 seconds. Another 4 g of water was applied to the hair still coated with the dye, and the hair was massaged again. After a 5-minute exposure time, each strand of hair was dried with a hairdryer without rinsing out the dye (F). The dyed strands were visually assessed by trained personnel under a daylight lamp. 3. Measurement of wash-out behavior on hair strands with different degrees of damage

[0266] Following the coloring procedure, each colored strand was manually shampooed. For each wash, the strand was moistened, then a commercially available shampoo (Schwarzkopf, Schauma 7 Kräuter) was massaged into the strand for 25 seconds (0.25 g of shampoo per gram of hair). The strand was then rinsed with lukewarm tap water for 30 seconds and dried. After 4, 8, and 12 washes, each strand was visually assessed again under a daylight lamp.

[0267] The hair strands were assessed for their color intensity using a scale from 1 (very low color intensity) to 5 (very high color intensity). K = Kerling 9-0 (little damage) ENH = Euronatural hair white (severely damaged) HW = hair washing 0 HW = Color result directly after coloring 0 HW 4 HW 8 HW 12 HW ENH K ENH K ENH K ENH K Pretreatment with (V1) Staining with (F) 5 5 4 4 4 4 4 4 Pretreatment with (V2) Staining with (F) 5 5 4 4 4 3 3 3 Pretreatment with (V3) Staining with (F) 5 5 5 5 4 4 4 4 Pretreatment with (V4) Staining with (F) 5 5 5 5 5 5 5 4 Pretreatment with (V5) Staining with (F) 5 5 5 5 5 5 5 5 Color intensity: 5 = very high 1 = very low

[0268] The best wash fastness properties were achieved with the successive application of the pretreatment agents (V4) or (V5) and the dye (F). QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] WO 2022 / 184357 A1

[0010] WO 2022 / 184337 A1 [0010, 0011] WO 2021 / 121721 A1

[0012]

Claims

[1] Cosmetic agent (V) for pre-cleaning keratin fibers, in particular human hair, containing in a cosmetic carrier (V-1) at least one reducing agent, and (V-2) at least one anionic surfactant, and (V-3) at least one surfactant from the group of alkoxylated fatty alcohols, amphoteric surfactants and zwitterionic surfactants. [2] Agent according to claim 1, characterized by that it contains at least one reducing agent (V-1) which is selected from the group consisting of dithioerythritol, dithiothreitol, acetylcysteine, dimercaptosuccinic acid, thioglycerol, thiolactic acid, cysteine, thioglycolic acid, sodium dithionite, zinc dithionite, potassium dithionite, formamidine sulfinic acid, 2-hydroxy-2-sulfino-acetic acid and salts thereof. [3] Agent according to one of claims 1 to 2, characterized bythat it contains - based on the total weight of the agent - one or more reducing agents (V-1), preferably dithioerythritol, dithiothreitol, acetylcysteine and / or their salts, particularly preferably dithioerythritol and / or dithiothreitol, in a total amount of 0.1 to 15.0 wt.%, preferably 0.2 to 10.5 wt.%, more preferably 0.3 to 7.5 wt.% and very particularly preferably 0.5 to 5.5 wt.%. [4] Agent according to one of claims 1 to 3, characterized by that it contains water and has a pH of 7.0 to 12.0, preferably 7.5 to 11.5, more preferably 8.0 to 11.0 and particularly preferably 8.5 to 10.

5. [5] Agent according to one of claims 1 to 4, characterized by that it contains at least one anionic surfactant (V-2) selected from the group consisting of - Dialkyl sulfosuccinates whose two alkyl groups are selected from identical or different, branched or unbranched C2 to C 12alkyl groups, - Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R9-O-(CH2-CH2O) n -SO3X, in which R9 preferably represents a straight-chain or branched, saturated or mono- or polyunsaturated alkyl or alkenyl radical having 8 to 22 carbon atoms, n represents 0 or 1 to 12, and X represents an alkali or alkaline earth metal ion or protonated triethanolamine or the ammonium ion, - straight-chain or branched, saturated or mono- or polyunsaturated alkylsulfonates with 8 to 22 C atoms, - linear alpha-olefin sulfonates with 8 to 22 C atoms, - Acyl isethionates whose acyl group is selected from a branched or unbranched C8 to C 22 alkyl group, - N-acyl taurates whose acyl group is selected from a branched or unbranched C8 to C 22 alkyl group, and / or the salts of the aforementioned compounds. [6] Agent according to one of claims 1 to 5, characterized by that it contains - based on the total weight of the agent - one or more anionic surfactants (V-2), preferably one or more dialkyl sulfosuccinates and / or salts thereof, particularly preferably 1,4-bis(2-ethylhexyl) sulfosuccinate in the form of its sodium salt, in an amount of 0.1 to 20.0 wt.%, preferably 0.5 to 15.0 wt.%, more preferably 1.0 to 10.0 wt.% and particularly preferably 1.5 to 7.5 wt.%. [7] Agent according to one of claims 1 to 6, characterized by that there are one or more surfactants (V-3) from the group of alkoxylated fatty alcohols, preferably from the group of ethoxylated fatty alcohols, preferably from the group of ethoxylated C8-C 22 -alcohols with 1 to 30 EO, particularly preferably C 12 -C 18 -alcohols with 1 to 15 EO. [8] Agent according to one of claims 1 to 7, characterized bythat it contains - based on the total weight of the agent - one or more surfactants (V-3) from the group of ethoxylated C8-C 22 -alcohols with 1 to 15 EO in a total amount of 0.1 to 20 wt.%, preferably 0.4 to 11.0 wt.%, more preferably 0.8 to 9.5 wt.% and particularly preferably 1.2 to 3.8 wt.%. [9] Agent according to one of claims 1 to 8, characterized by that it additionally contains one or more non-ionic sugar surfactants (V-4), preferably one or more non-ionic sugar surfactants (V-4) from the group of alkyl (poly)glucosides and mannosyl erythritol lipids. [10] Means according to claim 9, characterized bythat it contains - based on the total weight of the agent - one or more non-ionic sugar surfactants (V-4), preferably one or more alkyl (poly)glucosides, in a total amount of 0.1 to 15.0 wt.%, preferably 0.2 to 9.5 wt.%, more preferably 0.5 to 4.5 wt.% and particularly preferably 0.8 to 3.0 wt.%. [11] Agent according to one of claims 1 to 10, characterized by that it contains no other surfactants apart from the surfactants (V-2), (V-3) and optionally (V-4). [12] A process for dyeing keratin fibres, in particular human hair, comprising the following steps: - application of a pre-cleaning agent (V) to the keratin fibers, wherein the pre-cleaning agent (V) is an agent according to any one of claims 1 to 11, and - Application of a colorant (F) to the keratin fibers, wherein the colorant (F) contains (F-1) at least one organic silicon compound from the group of silanes having one, two or three silicon atoms, and (F-2) at least one coloring compound from the group of pigments and direct dyes. [13] Method according to claim 12, characterized by , that - the colorant (F) contains at least one silane (F-1) selected from the group consisting of (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, (2-aminoethyl)triethoxysilane, (2-aminoethyl)trimethoxysilane, (3-dimethylaminopropyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane, (2-dimethylaminoethyl)triethoxysilane, (2-dimethylaminoethyl)trimethoxysilane and / or their hydrolysis and / or condensation products, and / or - the colorant (F) contains at least one silane (F-1) selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane and / or their hydrolysis and / or condensation products. [14] Method according to one of claims 11 to 13, characterized by that the colorant (F) contains one or more solvents from the group consisting of ethanol, poly-C1-C6-alkylene glycols, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, phenoxyethanol and benzyl alcohol. [15] Method according to one of claims 11 to 14, comprising the steps in the order given: - Application of the pre-cleansing agent (V) on the keratin fibers, then - Application of the colorant (F) on the keratin fibers, wherein between the application of the pre-cleaning agent (V) and the application of the coloring agent (F) there is a period of maximum 24 hours, preferably maximum 12 hours, more preferably maximum 6 hours and most preferably maximum 3 hours.