Method for dyeing keratin fibres comprising the application of an alkaline pre-treatment agent and the application of a dyeing agent including chitosan and a colouring compound

Abstract

The invention relates to a method for dyeing keratin fibres, in particular human hair, comprising the following steps: applying a pre-treatment agent (V) to the keratin fibres, wherein the pre-treatment agent (V-1) contains at least one alkalising agent; and applying a dyeing agent (F) to the keratin fibres, wherein the dyeing agent contains, in a cosmetic carrier, (F-1) at least one chitosan and / or a chitosan derivative, and (F-2) at least one colouring compound from the group of pigments and direct dyes.

Description

[0001] A method for dyeing keratin fibers comprising the application of an alkaline pretreatment agent and the application of a dye containing chitosan and coloring compound

[0002] The present application relates to a cosmetic method for coloring keratin fibers, in particular human hair, which comprises the application of at least two different agents (V) and (F). Agent (V) is a pretreatment agent containing at least one alkalizing agent (V-1) in a cosmetic carrier. Colorant (F) contains, in a cosmetic carrier, at least one chitosan or a derivative thereof (F-1) and at least one colorant compound (F-2) from the group of pigments and direct dyes.

[0003] Altering the shape and color of keratinous material, especially human hair, represents an important area of ​​modern cosmetics. Depending on the coloring requirements, hair coloring specialists are familiar with various coloring systems. For permanent, intense colorings with good fastness properties and good gray coverage, oxidation dyes are typically used. Such dyes contain oxidation dye precursors, so-called developer components, and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes. Oxidation dyes are characterized by very long-lasting coloring results.

[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 completely after a few washes with surfactant-containing cleansers. Various products of this type are available on the market under the name hair mascara. Coloring with pigments offers several key advantages. Because the pigments only attach themselves externally to the keratin materials, particularly the hair fibers, 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 great effort.This coloring process is particularly attractive for consumers who do not want to re-color their hair regularly.

[0006] Despite these many advantages, the pigment-based coloring system still has several 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.

[0007] For example, DE 19847883 A1 deals with the realization of pigment-based colorings using colorants containing at least one chitosan and one pigment. Combining the pigments with chitosan is intended to improve the abrasion resistance of the colorings. The major advantage of chitosans as film-forming materials is that they are based on biopolymers and therefore have improved ecological compatibility and degradability. As many users show increasing interest in products made from sustainable or renewable raw materials, the use of biopolymers is increasingly gaining attention.

[0008] In further studies described in JP2001089335 A, hair was dyed with a combination of polysaccharides, chitosans, and coloring compounds. In this case, acid dyes were used as the coloring compounds, not pigments. Acid dyes are typically used in combination with solvents to achieve sufficiently high color intensity, as the solvents enhance the penetration of the acid dyes into the hair fiber. However, acid dyes are also known to have a very strong skin coloring effect. In the presence of solvents, this skin coloring is often further intensified.

[0009] The colorations obtained with pigment / dye and chitosan still have disadvantages with regard to their washfastness. Achieving uniform colorations across the entire length of the hair cannot yet be considered optimal, as the durability of the films can vary on different hair sections, particularly in the areas at the roots and tips. Therefore, the object of the present application was to provide a colorant that binds color-imparting compounds to the surface of keratin fibers via a film and with which intensive colorations with improved washfastness can be achieved. The coloration should be carried out with the aid of biopolymers, and the keratin fibers or hair colored in this way should not feel coated or greasy, exhibit a well-groomed shine, and the curl behavior of the keratin fibers should not be negatively affected.At the same time, the dyes should have as little skin staining as possible. When used in a dyeing process, they should achieve intensive dyeing results with good fastness properties, especially good washfastness, and good color retention.

[0010] Surprisingly, it has now been found that very washfast colorations could be obtained on keratin fibers, especially when the fibers were subjected to an alkaline pretreatment or cleaning step before coloring and then colored by applying a colorant containing chitosan and pigment or dye.

[0011] A first object of the present invention is a process for dyeing keratin fibers, in particular human hair, comprising the following steps:

[0012] Application of a pretreatment agent (V) to the keratin fibers, wherein the pretreatment agent

[0013] (V-1) contains at least one alkalizing agent, and

[0014] - application of a coloring agent (F) to the keratin fibers, wherein the coloring agent is contained in a cosmetic carrier

[0015] (F-1) at least one chitosan and / or a chitosan derivative, and

[0016] (F-2) contains at least one coloring compound from the group of pigments and direct dyes.

[0017] The work leading to this invention has shown that particularly intense and fade-resistant color results can be achieved on hair when the hair is colored by successive application of the two agents (V) and (F). The alkaline pretreatment agent (V) specifically degreased and cleaned the keratin fibers, so that the application of the colorant (F) resulted in a particularly uniform and durable film, which colored the keratin fibers with an attractive, uniform, and fade-resistant color result.

[0018] Keratin fibers

[0019] Keratin fibers include hair, wool, and fur. Human hair is particularly preferred as keratin fibers. Coloring agents

[0020] In the context of this invention, the term "coloring agent" refers to the coloring of keratin material, particularly hair, achieved through the use of pigments and / or direct dyes. In this coloring process, the coloring compounds are integrated into the chitosan, which is deposited on the surface of the keratin material or surrounds the keratin fiber in the form of a particularly homogeneous, thin, uniform, and smooth film.

[0021] Pretreatment agent (V)

[0022] Before applying the coloring agent (F), the pretreatment agent (V) is applied to the keratin fibers, in particular the hair, in the process according to the invention. The pretreatment agent described below is the ready-to-use pretreatment agent that can be applied directly to the keratin fibers or hair.

[0023] Alkalizing agent (V-1) in the pretreatment agent (V)

[0024] The pretreatment agent (V) is characterized by the presence of at least one alkalizing agent (V-1). Alkalizing agents are compounds that are capable of forming hydroxide ions in aqueous solution and thereby increasing the pH of the solution.

[0025] The work carried out has shown that the alkalizing agents (V-1) contained in the pretreatment agent (V) clean the keratin fibers particularly well and free them from the fatty acids adhering to the surface. Inorganic alkalizing agents have proven particularly suitable for this purpose. Particularly preferred inorganic alkalizing agents can be selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, potassium carbonate and / or ammonia. In this context, it was discovered that these inorganic alkalizing agents can almost completely remove the fatty acids and sebum components present on the hair surface. On the fibers prepared in this way, the film formed by the coloring agent (F) then forms a particularly even and thin film around the fibers.

[0026] In a particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) contains at least one inorganic alkalizing agent (V-1) from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, potassium carbonate and / or ammonia, very particularly preferably potassium hydroxide.

[0027] Microscopic images showed that a pretreatment agent (V) containing potassium hydroxide could also partially dissolve the chitosan material located between the cuticle scales. The dyed chitosan film could adhere to or around the exposed scale edges, subsequently adhering particularly well to the keratin fibers. For this reason, it was found to be particularly preferred if the pretreatment agent contained an alkali hydroxide such as potassium hydroxide and / or sodium hydroxide, especially potassium hydroxide, as the alkalizing agent (V-1).

[0028] In a particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) contains at least one alkalizing agent (V-1) from the group consisting of potassium hydroxide and / or sodium hydroxide.

[0029] In addition to or instead of the inorganic alkalizing agents, the pretreatment agent (V) may also contain at least one organic alkalizing agent such as the salts of Cs-Cso fatty acids, alkanolamines or basic amino acids.

[0030] For the purposes of the invention, fatty acids are saturated or unsaturated, unbranched or branched, unsubstituted or substituted Cs-Cs carboxylic acids. Unsaturated fatty acids can be monounsaturated or polyunsaturated. In an unsaturated fatty acid, its C-C double bond(s) can have the cis or trans configuration. Salts of Cs-Cs fatty acids include, for example, their alkali metal salts, alkaline earth metal salts, or ammonium salts.

[0031] Particularly suitable alkali salts of Cs-Cso fatty acids can be selected from the group consisting of sodium caprylate, potassium caprylate, ammonium caprylate (i.e. the salts of octanoic acid), sodium decanoate, potassium decanoate, ammonium decanoate (i.e. the salts of decanoic acid), sodium laurate, potassium laurate, ammonium laurate (i.e. the salts of lauric acid or dodecanoic acid), sodium myristate, potassium myristate, ammonium myristate (i.e. the salts of myristic acid or tetradecanoic acid), sodium palmitate, potassium palmitate, ammonium palmitate (i.e. the salts of hexadecanoic acid or palmitic acid), sodium stearate, potassium stearate, ammonium stearate (i.e. the salts of octadecanoic acid or stearic acid), sodium arachinoate, potassium arachinoate, ammonium arachinoate (i.e. the salts of eicosanoic acid or arachidic acid), sodium behenate, potassium behenate and ammonium behenate (i.e. the salts of docosanoic acid or behenic acid).

[0032] Alkaline earth metal salts of Cs-Cso fatty acids can be selected from the group consisting of magnesium caprylate, potassium caprylate (i.e. the salts of octanoic acid), magnesium decanoate, calcium decanoate (i.e. the salts of decanoic acid), magnesium laurate, calcium laurate (i.e. the salts of lauric acid or dodecanoic acid), magnesium myristate, calcium myristate (i.e. the salts of myristic acid or tetradecanoic acid), magnesium palmitate, calcium palmitate (i.e. the salts of hexadecanoic acid or palmitic acid), magnesium stearate, calcium stearate (i.e. the salts of octadecanoic acid or stearic acid), magnesium arachinoate, calcium arachinoate (i.e. the salts of eicosanoic acid or arachidic acid), magnesium behenate and calcium behenate (i.e. the salts of docosanoic acid or behenic acid).

[0033] Ammonium salts of Cs-Cso fatty acids can be selected from the group of ammonium caprylate, ammonium decanoate, ammonium laurate, ammonium myristate, ammonium palmitate, ammonium stearate, ammonium arachinoate, ammonium behenate.

[0034] Suitable alkanolamines are preferably selected from primary amines having a C2-C6 alkyl parent structure bearing at least one hydroxyl group. Preferred alkanolamines are selected from the group consisting of 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, and 2-amino-2-methylpropan-1,3-diol.

[0035] Alkanolamines suitable according to the invention 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 according to the invention contains an alkanolamine selected from 2-aminoethane-1-ol and / or 2-amino-2-methylpropane-1-ol as an alkalizing agent.

[0036] An amino acid within the meaning of the invention is an organic compound that contains at least one protonatable amino group and at least one -COOH or -SO 3 H group in its structure. Preferred amino acids are aminocarboxylic acids, in particular α-(alpha)-aminocarboxylic acids and β-aminocarboxylic acids, with α-aminocarboxylic acids being particularly preferred.

[0037] According to the invention, basic amino acids are understood to be amino acids which have an isoelectric point pl of greater than 7.0.

[0038] 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.

[0039] The basic amino acids are preferably selected from the group consisting of arginine, lysine, ornithine, and histidine, particularly preferably arginine and lysine. In a further particularly preferred embodiment, an agent according to the invention is therefore characterized in that the alkalizing agent is a basic amino acid from the group consisting of arginine, lysine, ornithine, and / or histidine. In a particularly preferred embodiment, a method according to the invention is characterized in that the pretreatment agent (V) contains at least one organic alkalizing agent (V-1) from the group consisting of alkali metal salts of Cs-Cs0 fatty acids, alkaline earth metal salts of Cs-Cs0 fatty acids, ammonium salts of Cs-Cs0 fatty acids, Cs-Cs0 alkanolamines, and / or basic amino acids.

[0040] In order to clean the keratin fibers as effectively as possible in the pretreatment step and to remove all fatty acids and / or sebum components as completely as possible from the surface of the fibers, the pretreatment agent (V) contains the alkalizing agent(s) (V-1), preferably in certain quantity ranges. Particularly effective precleaning is possible if the pretreatment agent (V) contains one or more alkalizing agents (V-1) in a total amount of 0.1 to 10.0 wt. %, preferably 0.2 to 7.5 wt. %, more preferably 0.5 to 5.0 wt. %, and particularly preferably 1.0 to 3.5 wt. %, based on the total weight of the pretreatment agent (V).

[0041] In a particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains one or more alkalizing agents (V-1) in a total amount of 0.1 to 10.0 wt.%, preferably from 0.2 to 7.5 wt.%, more preferably from 0.5 to 5.0 wt.% and particularly preferably from 1.0 to 3.5 wt.%.

[0042] Cosmetic carrier of the pretreatment agent (V)

[0043] The alkalizing agent(s) (V-1) are preferably contained in the pretreatment agent (V) in a cosmetic carrier. In principle, various carriers are conceivable as cosmetic carriers for the pretreatment agent (V), such as, for example, an aqueous, alcoholic, or aqueous-alcoholic carrier. The carrier can also be a cream, emulsion, a paste, or even a surfactant-containing foaming solution, such as a shampoo, foam aerosol, a foam formulation, or another preparation suitable for application to the hair. Water is the most common solvent in cosmetic products; therefore, in principle, water can also be used as the main ingredient as a cosmetic carrier.

[0044] However, the work leading to this invention has shown that the nature of the cosmetic carrier in the pretreatment agent (V) can influence the cleaning effect of the pretreatment agent.

[0045] As previously described, the pretreatment agent is intended to dissolve primarily hydrophobic components of the sebum, such as non-ionized fatty acids, and remove them as completely as possible from the keratin fiber. If the pretreatment agent contains a very high amount of water, the fatty acids are partially dissolved by conversion into their salts. However, in the absence of a surfactant, they quickly precipitate and then redeposit on the surface of the keratin fiber. For this reason, it has proven particularly preferable for the pretreatment agent to contain a solvent-based cosmetic carrier. (Poly)alkylene glycols have proven to be particularly suitable solvent-based carriers. The alkylene glycols or polyalkylene glycols reduce the polarity of the cosmetic carrier, increase the solubility of the hydrophobic sebum components, and thus improve their detachment from the surface.Particularly suitable (poly)alkylene glycols according to the invention are, for example, ethylene glycols of the formula (EG). where x 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.

[0046] In a particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) contains at least one ethylene glycol (V-2) of the formula (EG), where x 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.

[0047] The ethylene glycols of formula (EG) 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 x represents a value of at least 2. In the alkylene glycols of formula (EG), x represents an integer from 1 to 10,000.

[0048] Depending on their chain length, polyethylene glycols are liquid or solid, water-soluble polymers. Polyethylene glycols with a molecular weight between 200 g / mol and 400 g / mol are non-volatile liquids at room temperature. PEG 600 has a melting range of 17 to 22 °C and thus a paste-like consistency. With molecular weights above 3000 g / mol, PEGs are solid substances and are marketed as flakes or powders.

[0049] The use of low-molecular-weight alkylene glycols (or polyethylene glycols) has proven particularly suitable for achieving the object of the invention. For low-molecular-weight alkylene glycols (or polyethylene glycols) within the meaning of the present invention, x1 represents an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20, and most preferably an integer from 6 to 15.

[0050] In a further particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) contains at least one ethylene glycol of the formula (EG-1), where

[0051] (EG-1), x1 represents an integer from 1 to 100, preferably an integer from 1 to 80, more preferably an integer from 2 to 60, even more preferably an integer from 3 to 40, even more preferably an integer from 4 to 20 and most preferably an integer from 6 to 15.

[0052] A particularly preferred low-molecular-weight polyethylene glycol is PEG-8. PEG-8 contains an average of 8 ethylene glycol units (x1 = 8), has an average molecular weight of 400 g / mol, and bears the CAS number 25322-68-3. PEG-8 is also known as PEG 400 and is commercially available, for example, from APS.

[0053] Other suitable low molecular weight polyethylene glycols include PEG-6, PEG-7, PEG-9 and PEG-10.

[0054] Another suitable polyethylene glycol is PEG-32. PEG-32 comprises 32 ethylene glycol units (x1 = 32), has an average molecular weight of 1500 g / mol, and bears the CAS number 25322-68-3. PEG-32 is also known as PEG 1500 and can be purchased commercially, for example, from Clariant. Furthermore, the use of high-molecular-weight polyethylene glycols has also proven well-suited for solving the problem of the invention.

[0055] High molecular weight polyethylene glycols in the sense of the present invention can be represented by the formula (EG-2), where the index number x2 stands for an integer from 101 to 10000 (EG-2).

[0056] In the case of particularly suitable high molecular weight polyethylene glycols, x2 represents an integer from 101 to 1000, preferably an integer from 105 to 800, more preferably an integer from 107 to 600, even more preferably an integer from 109 to 400 and most preferably an integer from 110 to 200.

[0057] In a further particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) contains at least one ethylene glycol of the formula (EG-2), where x2 represents an integer from 101 to 1000, preferably an integer from 105 to 800, more preferably an integer from 107 to 600, even more preferably an integer from 109 to 400 and most preferably an integer from 110 to 200.

[0058] 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, corresponding to a x2 value of 136 to 171.

[0059] Another suitable polyethylene glycol is PEG 12000, which is marketed commercially by CG Chemikalien, for example, under the trade name Polyethylene Glycol 12000 S (or PEG 12000 S). The molecular weight of PEG 12000 is stated to be between 10500 and 15000 g / mol, corresponding to a x2 value of 238 to 341. 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 20000 g / mol, corresponding to a x2 value of 454.

[0060] Surprisingly, it was found that pretreatment agents containing both a low molecular weight polyethylene glycol and a high molecular weight polyethylene glycol provided particularly good results, as these agents have both very good cleaning properties and are optimized with regard to their rheological profile.

[0061] The (poly)alkylene glycol(s), in particular the (poly)ethylene glycol(s) of formula (EG), are preferably used in the pretreatment agent (V) in specific quantity ranges. The pretreatment agent (V) preferably contains—based on the total weight of the pretreatment agent (V)—one or more ethylene glycols of formula (EG) in a total amount of 10.0 to 99.0 wt.%, preferably 25.0 to 95.0 wt.%, more preferably 40.0 to 90.0 wt.%, and most preferably 60.0 to 85.0 wt.%.

[0062] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains one or more ethylene glycols of the formula (EG) in a total amount of 10.0 to 99.0 wt.%, preferably 25.0 to 95.0 wt.%, more preferably 40.0 to 90.0 wt.% and very particularly preferably 60.0 to 85.0 wt.%.

[0063] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains one or more ethylene glycols of the formula (EG-1) in a total amount of 20.0 to 99.0 wt.%, preferably from 40.0 to 95.0 wt.%, particularly preferably from 50.0 to 70.0 wt.%, and / or it contains one or more ethylene glycols of the formula (EG-2) in a total amount of 1.0 to 35.0 wt.%, preferably from 3.0 to 25.0 wt.%, particularly preferably from 4.0 to 15.0 wt.%.

[0064] Instead of or in addition to the alkylene glycols, the pretreatment agent (V) may also contain one or more solvents. Solvents from the group consisting of glycerin, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, ethanol, isopropanol, dipropylene glycol, diethylene glycol monoethyl ether, phenoxyethanol, benzyl alcohol, poly-Ci-Cs-alkylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, and glycerol carbonate have proven particularly suitable.In a further preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) contains at least one solvent from the group consisting of glycerol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, ethanol, isopropanol, dipropylene glycol, diethylene glycol monoethyl ether, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-alkylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate.

[0065] The pretreatment agent (V) preferably contains - based on the total weight of the pretreatment agent (V) - one or more solvents from the group consisting of ethanol, isopropanol, glycerol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-ethylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate in a total amount of 3.0 to 80% by weight, preferably from 5.0 to 60.0% by weight, more preferably from 9.0 to 40.0% by weight and very particularly preferably from 12.0 to 25.0% by weight.

[0066] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains one or more solvents from the group consisting of ethanol, isopropanol, glycerol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-ethylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate in a total amount of 3.0 to 80 wt.%, preferably from 5.0 to 60.0 wt.%, more preferably from 9.0 to 40.0 wt.% and very particularly preferably from 12.0 to 25.0 wt.%.

[0067] The pretreatment agent (V) preferably contains - based on the total weight of the pretreatment agent (V) - 9.0 to 40.0 wt.% and particularly preferably 12.0 to 25.0 wt.% ethanol.

[0068] In addition to increasing the content of alkylene glycols and / or solvents in the pretreatment agent (V), it has also proven particularly advantageous to adjust the water content in the pretreatment agent to a medium to low range. It is therefore particularly advantageous if the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains 1.0 to 70.0 wt. %, preferably 2.0 to 50.0 wt. %, more preferably 3.0 to 40.0 wt. % and very particularly preferably 4.0 to 20.0 wt. % water. In a further very particularly preferred embodiment, a process according to the invention is characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains 1.0 to 70.0 wt. %, preferably 2.0 to 50.0 wt. %, more preferably 3.0 to 40.0 wt. % and very particularly preferably 4.0 to 20.0 wt. % water.

[0069] Dye (F)

[0070] Following the application of the pretreatment agent (V), the colorant (F) is then applied to the keratin material in the process according to the invention. The colorant (F) contains, in a cosmetic carrier, at least one chitosan and / or a chitosan derivative (F-1) and (F-2) at least one colorant compound from the group of pigments and direct dyes.

[0071] Cosmetic carrier of the colorant (F)

[0072] As a cosmetic carrier for the colorant (F), for example, a suitable aqueous, alcoholic or aqueous-alcoholic carrier can be used. For the purpose of hair coloring, such carriers are, for example, creams, emulsions, gels, pastes or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations suitable for application to the hair. The cosmetic carrier for the colorant is particularly preferably a water-rich carrier, i.e. the colorant (F) preferably has a high water content. It has been found that colorants (F) which contain - based on the total weight of the pretreatment agent (V) - 50.0 to 99.0 wt. %, preferably 60.0 to 99.0 wt. %, more preferably 70.0 to 99.0 wt. % and very particularly preferably 80.0 to 99.0 wt. % water are particularly suitable for use in the process according to the invention.

[0073] In one embodiment, a process according to the invention is characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains 50.0 to 99.0 wt.%, preferably 60.0 to 99.0 wt.%, more preferably 70.0 to 99.0 wt.% and most preferably 80.0 to 99.0 wt.% of water.

[0074] Chitosans (F-1) in the dye (F)

[0075] Chitosan, also known as polyglusam, poly-D-glucosamine, or polyglucosamine, is a naturally occurring biopolymer derived from chitin, which is composed of ß-1,4-glycosidically linked N-acetylglucosamine residues (more precisely, 2-acetamido-2-deoxy-ß-D-glucopyranose residues), and is thus, like chitin, a polyaminosaccharide. To produce chitosan, chitin is deacetylated, so that the molecule ultimately consists of only approximately 2,000 linearly linked 2-amino-2-deoxy-ß-D-glucopyranose or glucosamine monomers. Chitosan has the CAS number 9012-76-4. Chitosan is preferably produced from the chitin found in shellfish or crustaceans. Chitosan is technically obtained from chitin by deacetylation. This can be achieved, for example, with (hot) caustic soda or enzymatically. Both processes are used industrially, but in terms of quantity, the alkaline procedure is clearly the most important.The degree of resulting deacetylation can vary considerably: Deacetylation can be complete or partial, resulting in a distribution of highly deacetylated regions alongside less deacetylated regions, or a homogeneous deacetylation distribution. At the same time, this chemical intervention can lead to a decrease in the chain length of the polymer (depolymerization). The molecular weight of chitosan can vary over a wide range, for example, from 20,000 to approximately 5 million g / mol.

[0076] Chitosan derivatives are compounds with a chitosan base structure in which at least some of the functional groups present have been chemically modified. Chitosan derivatives are also based on a poly-D-glucosamine or polyglucosamine structure.

[0077] For example, a chitosan with a molecular weight of 20,000 to 800,000 g / mol, preferably 50,000 to 600,000 g / mol, more preferably 80,000 to 450,000 g / mol and most preferably 100,000 to 300,000 g / mol is very suitable.

[0078] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one chitosan and / or a chitosan derivative (F-1) with a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and very particularly preferably of 100,000 to 300,000 g / mol.

[0079] In a further very particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one chitosan (F-1) having a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and very particularly preferably of 100,000 to 300,000 g / mol.

[0080] Chitosan with a molecular weight of 100,000 to 300,000 g / mol can be purchased commercially from Sigma Aldrich, for example.

[0081] A chitosan with a lower molecular weight of 10,000 to 30,000 g / mol (or Daltons) is commercially available in pharmaceutical grade from BioLog Heppe (Kraeber), for example. The degree of deacetylation of this chitosan is 88-95%. Chitosan in the form of its hydrochloride can be obtained as vegan chitosan from Sandream Impact. The hydrochloride of the chitosan is a chitosan derivative according to the invention.

[0082] Chitosan 027 is a suitable high molecular weight chitosan from Polymar, which has a molecular weight of 100,000 - 2,000,000 g / mol.

[0083] It has proven particularly advantageous if the colorant according to the invention contains the chitosan(s) and / or chitosan derivative(s) (F-1) in specific quantity ranges. Particularly good results were obtained when the colorant—based on the total weight of the colorant—contained one or more chitosans and / or chitosan derivatives in a total amount of 0.1 to 10.0 wt.%, preferably 0.2 to 8.0 wt.%, more preferably 0.5 to 6.0 wt.%, and most preferably 0.7 to 2.0 wt.%.

[0084] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) - based on the total weight of the colorant - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.1 to 10.0 wt.%, preferably 0.2 to 8.0 wt.%, more preferably 0.5 to 6.0 wt.% and most preferably 0.7 to 2.0 wt.%.

[0085] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains one or more chitosans in a total amount of 0.1 to 10.0 wt. %, preferably 0.2 to 8.0 wt. %, more preferably 0.5 to 6.0 wt. %, and most preferably 0.7 to 2.0 wt. %, based on the total weight of the colorant. Coloring compounds (F-2) in the colorant (F)

[0086] As a second essential component, the colorant (F) used in the subsequent step of the process according to the invention contains at least one color-providing compound (F-2) from the group of pigments and direct dyes.

[0087] Pigments in the sense of the present invention are understood to be color-imparting 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 pigment remains on the filter paper, the solubility of the pigment is below 0.5 g / L.

[0088] Suitable color pigments can be of inorganic and / or organic origin. In a preferred embodiment, a method according to the invention is characterized in that the aftertreatment agent is applied to keratin material that has been colored by applying at least one inorganic and / or organic pigment.

[0089] 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.

[0090] 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).

[0091] Also particularly preferred color pigments according to the invention are colored pearlescent pigments. These are typically based on mica and / or mica and can be coated with one or more metal oxides. Mica belongs to the class of layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite, and margarite. To produce pearlescent pigments in combination with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide.

[0092] 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).

[0093] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least inorganic pigment (F-2), 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.

[0094] In a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one pigment (f2) which is selected from mica- or mica-based pigments coated with one or more metal oxides from the group consisting of titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and / or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarines (sodium aluminum sulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and / or iron blue (ferric ferrocyanide, CI 77510).

[0095] 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.

[0096] Particularly preferred color pigments with the trade name Colorona® are, for example:

[0097] Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)

[0098] Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina

[0099] Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0100] Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE)

[0101] Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)

[0102] Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE

[0103] Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA

[0104] Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0105] Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA

[0106] Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)

[0107] Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)

[0108] Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES)

[0109] 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)

[0110] Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (Cl 77510) Colorona Red Gold, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON OXIDES)

[0111] Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (Cl 77891), IRON OXIDES (Cl 77491)

[0112] Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE

[0113] Colorona Blackstar Green, Merck, MICA, Cl 77499 (IRON OXIDES)

[0114] Colorona Bordeaux, Merck, MICA, Cl 77491 (IRON OXIDES)

[0115] Colorona Bronze, Merck, MICA, Cl 77491 (IRON OXIDES)

[0116] Colorona Bronze Fine, Merck, MICA, Cl 77491 (IRON OXIDES)

[0117] Colorona Fine Gold MP 20, Merck, MICA, Cl 77891 (TITANIUM DIOXIDE), Cl 77491 (IRON

[0118] OXIDES)

[0119] Colorona Sienna Fine, Merck, Cl 77491 (IRON OXIDES), MICA

[0120] Colorona Sienna, Merck, MICA, Cl 77491 (IRON OXIDES)

[0121] Colorona Precious Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Silica, Cl 77491 (Iron oxides), Tin oxide

[0122] Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, Cl 77891 , Cl 77491 (EU)

[0123] Colorona Mica Black, Merck, Cl 77499 (Iron oxides), Mica, Cl 77891 (Titanium dioxide)

[0124] Colorona Bright Gold, Merck, Mica, Cl 77891 (Titanium dioxide), Cl 77491 (Iron oxides)

[0125] Colorona Blackstar Gold, Merck, MICA, Cl 77499 (IRON OXIDES)

[0126] Weiterhin besonders bevorzugte Farbpigmente mit der Handelsbezeichnung Xirona® sind beispielsweise:

[0127] Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0128] Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide

[0129] Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide

[0130] Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

[0131] In addition, particularly preferred color pigments with the trade name Unipure® are, for example:

[0132] Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica

[0133] Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica

[0134] Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

[0135] In a further embodiment, the applied colorant may also contain one or more organic pigments.

[0136] 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.

[0137] Particularly suitable organic pigments are, for example, carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the color index numbers CI 61565, CI 61570, CI 74260, orange pigments with the color index numbers CI 1 1725, CI 15510, CI 45370, CI 71105, red pigments with the color index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and / or CI 75470.

[0138] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one organic pigment (F-2) 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 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.

[0139] The organic pigment can also be a colored lake. For the purposes of the invention, the term colored lake refers to particles comprising a layer of absorbed dyes, the particle-dye unit being insoluble under the aforementioned conditions. The particles can be, for example, inorganic substrates, which can be aluminum, silica, calcium borosilicate, calcium aluminum borosilicate, or even aluminum.

[0140] Alizarin lake, for example, can be used as a colored varnish.

[0141] 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 platelet can be used. Furthermore, coloring based on a substrate platelet comprising a vacuum-metallized pigment is also possible. Within the scope of a further preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one pigment (F-2) selected from the group of pigments based on a lamellar substrate platelet, pigments based on a lenticular substrate platelet, and vacuum-metallized pigments.

[0142] 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.

[0143] 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.

[0144] The size of the substrate platelet can be tailored to the specific application, especially the desired effect on the keratin material. Typically, the substrate platelets have an average diameter of approximately 2 to 200 pm, particularly approximately 5 to 100 pm.

[0145] In a preferred embodiment, the aspect ratio, expressed as the ratio of the mean 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 mean size of the uncoated substrate platelets is understood to be the d50 value of the uncoated substrate platelets. Unless otherwise stated, the d50 value was determined using a Sympatec Heios device with Quixel wet dispersion. For sample preparation, the sample to be tested was predispersed in isopropanol for 3 minutes.

[0146] The substrate platelets can be made of any material that can be formed into platelets. 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.

[0147] 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.

[0148] Lamellar substrate platelets are characterized by an irregularly structured edge and are also called "cornflakes" due to their appearance.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] The substrate platelets made of metal or metal alloy can be passivated, for example, by anodizing (oxide layer) or chromating. Uncoated lamellar, lenticular, and / or VPM substrate platelets, especially those made of metal or metal alloy, reflect incident light to a high degree and create a light-dark flop. These have proven particularly preferred for use in the colorant.

[0153] Suitable pigments based on a lamellar substrate platelet include, for example, the pigments of the VISIONAIRE series from Eckart.

[0154] Pigments based on a lenticular substrate platelet are available, for example, under the name Alegrace® Gorgeous from Schlenk Metallic Pigments GmbH.

[0155] 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.

[0156] Due to their excellent light and temperature stability, the use of the aforementioned pigments in the agent according to the invention is very particularly preferred. Furthermore, it is preferred if the pigments used have a specific particle size. It is therefore advantageous according to the invention if the at least one pigment has an average particle size D50 of 1.0 to 50 pm, preferably of 5.0 to 45 pm, more preferably of 10 to 40 pm, in particular of 14 to 30 pm. The average particle size D50 can be determined, for example, using dynamic light scattering (DLS).

[0157] The coloring agent (F) can also contain at least one direct dye as the coloring compound (F-2). Direct dyes are dyes that are absorbed directly into the hair and do not require an oxidative process to develop the color. Direct dyes are typically nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes, or indophenols.

[0158] Direct dyes can be nonionic, cationic, or anionic. It is particularly preferred if the colorant (F) contains at least one anionic direct dye, which can alternatively also be referred to as an acid dye.

[0159] Anionic direct dyes are also known as acid dyes. Acid dyes are defined as direct dyes that contain at least one carboxylic acid group (-COOH) and / or one sulfonic acid group (-SO3H) and / or one sulfate group (-OSO3H). Depending on the pH, the profaned forms (-COOH, -SO3H) of the carboxylic acid or sulfonic acid groups are in equilibrium with their deprotonated forms (-COO-, -SOs, or -OSOs-). As the pH decreases, the proportion of profaned forms increases. If direct dyes are used in the form of their salts, the carboxylic acid 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.

[0160] 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.

[0161] 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.

[0162] Als Beispiele für Säurefarbstoffe können 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 (C1 18965), Acid Yellow 23 (COLIPA n° C 29, Covacap Jaune W 1 100 (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, C1 15510, D&C Orange 4, COLIPA n° C015), Acid Orange 10 (C.l. 16230; Orange G sodium salt), Acid Orange 11 (Cl 45370), Acid Orange 15 (Cl 50120), Acid Orange 20 (Cl 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.1.14720), Acid Red 18 (E124, Red 18; Cl 16255), Acid Red 27 (E 123, Cl 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, Cl 17200), Acid Red 35 (Cl C.l.18065), Acid Red 51 (Cl 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, lodeosin), Acid Red 52 (Cl 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (Cl 27290), Acid Red 87 (Eosin, Cl 45380), Acid Red 92 (COLIPA n° C53, Cl 45410), Acid Red 95 (Cl 45425, Erythtosine.Simacid Erythrosine Y), Acid Red 184 (Cl 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet n° 2, C.l. 60730, COLIPA n° C063), Acid Violet 49 (Cl 42640), Acid Violet 50 (Cl 50325), Acid Blue 1 (Patent Blue, Cl 42045), Acid Blue 3 (Patent Blau V, Cl 42051), Acid Blue 7 (Cl 42080), Acid Blue 104 (Cl 42735), Acid Blue 9 (E 133, Patentblau AE, Amidoblau AE, Erioglaucin A, Cl 42090, C.l.Food Blue 2), Acid Blue 62 (Cl 62045), Acid Blue 74 (E 132, Cl 73015), Acid Blue 80 (Cl 61585), Acid Green 3 (Cl 42085, Foodgreenl), Acid Green 5 (Cl 42095), Acid Green 9 (C.1.42100), Acid Green 22 (C.1.42170), Acid Green 25 (Cl 61570, Japan Green 201 , D&C Green No. 5), Acid Green 50 (Brillantsäuregrün BS, C.l. 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n° 401 , Naphthalene Black 10B, Amido Black 10B, Cl 20 470, COLIPA n° B15), Acid Black 52 (Cl 15711), Food Yellow 8 (Cl 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 .

[0163] In a further embodiment, an inventive method is characterized in that the dye (F) contains at least one acid dye (F-2), which is selected from the group consisting of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red 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 .,

[0164] 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 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.

[0165] Like pigments, acid dyes are primarily designed not to diffuse into the keratin fibers, but rather to deposit on the surface of the keratin fibers embedded in the chitosan film. For this reason, acid dyes are particularly preferred. Although their solubility is so high that they are no longer classified as organic pigments, they nevertheless have relatively poor solubility.

[0166] For this reason, acid dyes which have a solubility in water at 25 °C of less than 20 g / L, preferably less than 18 g / L, even more preferably less than 15 g / L and very particularly preferably less than 12 g / L are very particularly preferably used as organic coloring compounds (F-2).

[0167] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) contains, as organic coloring compound (F-2), at least one acid dye which has a solubility in water at 25 °C of less than 20 g / L, preferably less than 18 g / L, even more preferably less than 15 g / L and very particularly preferably less than 12 g / L.

[0168] 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 added. 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 assessed visually 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.

[0169] 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).

[0170] 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).

[0171] 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).

[0172] Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)- 1 H-pyrazole-3-carboxylic acid and is readily soluble in water at 25 °C.

[0173] 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).

[0174] 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%.

[0175] 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).

[0176] 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).

[0177] Brilliant Blue FCF, alternatively known as Food Blue 2 or Acid Blue 9, is known as disodium salt disodium 2-[(Z)-{4-[ethyl(3-sulfonatobenzyl)amino]phenyl}{(4Z)-4-[ethyl(3-sulfonatobenzyl)iminio]-2,5-cyclohexadien-1-ylidene}methyl]benzenesulfonate 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).

[0178] Acid Blue 74 is also alternatively 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.

[0179] The color-providing compound(s) (F-2) represent(s) the second essential constituent of the colorant (F) according to the invention and are preferably used in the composition in specific quantity ranges. Particularly good results were obtained when the colorant (F) contained one or more color-providing compounds (F-2) 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.

[0180] In a further very particularly preferred embodiment, a process (F) according to the invention is characterized in that the colorant (F) contains - based on the total weight of the colorant - one or more color-providing compounds from the group of pigments and direct dyes (F-2) 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 very particularly preferably 0.25 to 1.5 wt. % organic and / or inorganic acids (F-3) in the colorant

[0181] As an optional component, the agent (F) or the colorant (F) may contain at least one organic and / or inorganic acid (F-3).

[0182] By using one or more acids, the pH of the colorant (F) can be lowered, whereby the chitosan is completely or partially profaned and dissolves more easily. Macroscopically, the protonation of the chitosan in water is perceived as swelling, from which, when the preferred or particularly preferred pH value is adjusted, a particularly uniform and thin film is deposited on the keratin fibers. It has been shown that the durability of the film is better the more even the film forms on the hair. By forming a particularly uniform film, colorations with particularly good washfastness could also be achieved. In addition, the presence of the acid(s) (F-3) in the colorant also means that the chitosan can form a particularly thin film on the hair.Comparative studies have shown that a uniformly thin film offers better resistance to external mechanical influences. Particularly suitable organic acids include acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid, and benzoic acid.

[0183] Other suitable acids are formic acid and propanoic acid.

[0184] In a further particularly preferred embodiment, a process according to the invention is characterized in that the colorant (F) contains at least one organic acid (F-3) from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

[0185] Acetic acid dissolves chitosan particularly well and leads to particularly thin and uniform films, therefore a dye (F) containing acetic acid is particularly preferred.

[0186] In a further explicitly particularly preferred embodiment, a colorant (F) according to the invention is therefore characterized in that it contains acetic acid (F-3).

[0187] It is assumed that lowering the pH shifts the equilibrium reaction in the coloring compounds (F-2), which contain at least one acid group, more strongly toward the profaned acid side, thereby further reducing the solubility of the acid dyes and allowing the coloring compounds to integrate even better into the chitosan film. Therefore, the lower the pH of the colorant, the better the color absorption and washfastness of the dyes. However, for reasons of skin compatibility, the pH should not be lowered too much. Even if the colorant is designed as a leave-on product, for example, and is intended to remain on the hair without being washed out, the pH values ​​should not be chosen too low.

[0188] By using the acid(s) in appropriate amounts, the pH of the colorant can be adjusted to the desired pH range. In this context, it has also proven particularly preferable to adjust the pH of the agent (F) to a range from 1.0 to 7.5, preferably from 1.5 to 7.0, more preferably from 2.0 to 6.5, and most preferably from 2.0 to 6.0. To enable the pH of the agent (F) to be measured, the agent additionally contains water (F-4).

[0189] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) contains water (F-4) and has a pH of 1.0 to 7.5, preferably 1.5 to 7.0, more preferably 2.0 to 6.5, and most preferably 2.0 to 6.0. The proportion of the components (F-1), (F-2), (F-3), and (F-4) in the colorant

[0190] As part of the work leading to this invention, microscopic images were taken that showed that a thin, uniform film on the keratin fibers exhibits particularly good resistance to external influences such as mechanical friction or hair washing. The smoother and more cohesive the film, the less surface area it has to resist external forces. Once the film is broken at one point, it is quickly and completely detached due to the constant movement of the keratin fibers.

[0191] It was found that the films produced with the colorant (F) were particularly thin, uniform, and stable when the colorant consisted largely of the components (F-1), (F-2), (F-3), and (F-4). It is suspected that additional components could disrupt the film's uniformity by integrating into the film, weakening it at this point, or forming a surface vulnerable to external forces. For this reason, it is particularly preferred when the components (F-1), (F-2), (F-

[0192] 3) and (F-4) together are present in the colorant (F) in a proportion of at least 90.0 wt.%, preferably at least 93 wt.%, more preferably at least 96 wt.% and most preferably at least 99 wt.%.

[0193] If the components (F-1), (F-2), (F-3) and (F-4) are contained together in a proportion of at least 90.0 wt.% in the colorant, then the colorant consists of at least 90 wt.% of the components (F-1), (F-2), (F-3) and (F-4) based on its total weight. In other words, in this case, other substances or ingredients that are listed from (F-1) to (F-

[0194] 4) are different, are contained in the colorant (F) only in a maximum proportion of 10 wt.%, but preferably in even smaller proportions.

[0195] In a further particularly preferred embodiment, a process according to the invention is characterized in that the components (F-1), (F-2), (F-3) and (F-4) are contained together in the colorant (F) in a proportion of at least 90.0 wt.%, preferably of at least 93 wt.%, more preferably of at least 96 wt.% and most preferably of at least 99 wt.%.

[0196] Furthermore, it has also proven preferable if no solvents other than water are used in the colorant (F). Here, too, it was observed that the film produced on the keratin fibers was very thin and uniform when the colorant contained virtually no solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerin, 1-butanol, and / or polyethylene glycols.

[0197] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) is substantially free of solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and / or polyethylene glycols.

[0198] In this embodiment, the colorant (F) is characterized in that it is substantially free of solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerin, 1-butanol, phenoxyethanol, and benzyl alcohol. This means that none of the solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerin, 1-butanol, phenoxyethanol, and benzyl alcohol are intentionally added to the agent.

[0199] Some raw materials may contain one or more of the above-mentioned solvents in small amounts as a minor component, so that when this raw material is used, marginal amounts of this solvent are introduced. However, it has been found that the presence of such small amounts of solvent does not unduly increase skin staining.

[0200] In summary, a colorant (F) which is substantially free of the solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol and benzyl alcohol is understood to mean an agent which - based on its total weight - contains the above-mentioned solvents in a total amount of less than 0.2 wt.%, preferably less than 0.1 wt.%, even more preferably less than 0.05 wt.% and very particularly preferably less than 0.01 wt.%.

[0201] Most preferably, the colorant (F) is free from solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol and benzyl alcohol, ie the agent contains these solvents in a total amount of 0 wt.%.

[0202] In a further particularly preferred embodiment, a process according to the invention is therefore characterized in that the colorant (F) is free from solvents from the group consisting of ethanol, isopropanol, 1,2-propylene glycol, 1,3-propanediol, glycerol, 1-butanol, phenoxyethanol, benzyl alcohol and polyethylene glycols.

[0203] Ethanol has the Cas number 64-17-5.

[0204] Isopropanol is also known as 2-propanol and has the CAS number 67-63-0.

[0205] 1,2-Propylene glycol is alternatively also called 1,2-propanediol and has the CAS numbers 57-55-6 [(RS)-1,2-dihydroxypropane], 4254-14-2 [(R)-1,2-dihydroxypropane] and 4254-15-3 [(S)-1,2-dihydroxypropane],

[0206] 1,3-Propanediol or 1,3-Dihydroxypropane has the CAS number 504-63-2.

[0207] Glycerin is also known as 1,2,3-propanetriol and has the CAS number 56-81-5. 1-Butanol can also be known as n-butanol or butyl alcohol and has the CAS number 71-36-3.

[0208] Phenoxyethanol has the Cas number 122-99-6.

[0209] Benzyl alcohol is also known as phenylmethanol and has the CAS number 100-51-6.

[0210] Polyethylene glycols in the sense of the present invention are liquid polymers at room temperature (25 °C) of the general molecular formula C2nH4n+2O n +i. The repeating unit of the linear polymer is (-CH2-CH2-O-), with a molar mass of about 44 g mol -1 Chemically, it is a polyether. Polyethylene glycols are therefore ethylene glycols of the formula (EG) where x is an integer from 2 to 10000.

[0211] Pretreatment agents (V) and colorants (F)

[0212] In the process according to the invention, a pretreatment agent (V) and a colorant (F) are applied to the keratin fibers, wherein the pretreatment agent (V) and colorant (F) are different formulations.

[0213] Pretreatment agents (V) and colorants (F) are used for different purposes and contain different ingredients due to their different intended use.

[0214] The pretreatment agent (V) is intended to achieve a basic cleaning or preparation of the keratin fiber, for which purpose the pretreatment agent contains the alkalizing agent(s) (V-1).

[0215] The dye (F) is intended to achieve the coloring of the keratin fibers, so that the dye contains the chitosans (F-1) responsible for film formation and the pigments or direct dyes (F-2) responsible for coloring.

[0216] The coloring agent (F) according to the invention is therefore preferably characterized in that it either contains no alkalizing agents or contains them in smaller total amounts than the pretreatment agent (V), the reference point for the quantity being the total weight of the respective agent.

[0217] The pretreatment agent (V) according to the invention is preferably characterized in that it contains no pigments and no direct dyes. Sequence of process steps

[0218] As already described above, the pretreatment agent (V) is applied before the application of the coloring agent (F). In one embodiment, it may be preferable to apply the pretreatment agent (V) to the keratin material, allow it to act for a certain period of time, and then rinse it off with water.

[0219] Therefore, a method for coloring keratin fibers, in particular human hair, comprising the following steps in the given order is preferred:

[0220] (1) Applying the pretreatment agent (V) to the keratin fibers,

[0221] (2) allowing the pretreatment agent (V) applied in step (1) to act on the keratin fibres for a period of 1 to 45 minutes, preferably 5 to 30 minutes and particularly preferably 10 to 15 minutes,

[0222] (3) if necessary, rinsing out the pretreatment agent (V) with water or with the aid of water and a shampoo,

[0223] (4) if necessary, drying the keratin fibres,

[0224] (5) Applying the colorant (F) to the keratin fibers.

[0225] (6) Action of the colorant (F) on the keratin fibers, and

[0226] (7) if necessary, rinsing out the dye (F).

[0227] However, to ensure the most comprehensive pre-cleaning possible, it has proven particularly preferable to foam the pre-treatment agent (V) still present on the keratin fibers with a surfactant-containing solution and only then to rinse the fibers.

[0228] A particularly preferred method for dyeing keratin fibers, in particular human hair, is therefore a method comprising the following steps in the order given:

[0229] (1) Applying the pretreatment agent (V) to the keratin fibers,

[0230] (2) allowing the pretreatment agent (V) applied in step (1) to act on the keratin fibres for a period of 1 to 45 minutes, preferably 5 to 30 minutes and particularly preferably 10 to 15 minutes,

[0231] (3a) Applying a surfactant-containing solution to the keratin fibres still covered with the pretreatment agent (V),

[0232] (3b) joint washing out of the pretreatment agent (V) and the surfactant-containing solution from the keratin fibres,

[0233] (4) if necessary, drying the keratin fibres,

[0234] (5) Applying the colorant (F) to the keratin fibers.

[0235] (6) Action of the colorant (F) on the keratin fibers, and

[0236] (7) optionally rinsing out the coloring agent (F). In step (1) of the process according to the invention, a pretreatment agent (V) containing at least one alkalizing agent (V-1) is applied to the hair.

[0237] In the next step, the previously applied pretreatment agent (V) is allowed to act on the keratin fibers. Various exposure times are possible, ranging from 2 to 45 minutes, preferably from 2 to 30 minutes, and particularly preferably from 2 to 20 minutes.

[0238] After the pretreatment agent (V) has acted on the keratin fibers, it can now either be rinsed out with water or water and shampoo (step 3) or first mixed or foamed with a surfactant-containing solution on the keratin fibers (step 3a) and this mixture can then be rinsed off the keratin fibers with water (step 3b).

[0239] Anionic surfactants, for example, are very suitable as surfactants in step (3a).

[0240] In principle, any anionic surface-active substance suitable for use on the human body is suitable as anionic surfactants. These are characterized by a water-solubilizing anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group with approximately 8 to 30 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups.Typical examples of anionic surfactants are alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, a-methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, acyl lactylates, acyl tartrates, acyl glutamates, acylaspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrowed homolog distribution.Examples of particularly suitable anionic surfactants are, in the form of sodium, potassium and ammonium as well as mono-, di- and trialkanolammonium salts with 2 to 4 C atoms in the alkanol group, linear and branched fatty acids with 8 to 30 C atoms (soaps).

[0241] Ethercarboxylic acids of the formula RO-(CH2-CH2O)x-CH2-COOH, in which R is a linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 16,

[0242] Acylsarcosides with 8 to 24 C atoms in the acyl group,

[0243] Acyltaurides with 8 to 24 C atoms in the acyl group, and acyl isethionates with 8 to 24 C atoms in the acyl group, are long-known, skin-friendly surfactants that are obtainable by esterifying fatty acids with the sodium salt of 2-hydroxyethanesulfonic acid (isethionic acid). If fatty acids with 8 to 24 C atoms, such as lauric, myristic, palimitic, or stearic acid, or even technical fatty acid fractions, such as the C12-cis fatty acid fraction obtainable from coconut fatty acid, are used for this esterification, the C12-cis acyl isethionates that are preferably suitable according to the invention are obtained. It is known that the sodium salts of C12-cis-acylisethionates can be molded into a suitable form for transport and application by kneading, piling, extruding, cutting, and bar pressing, similar to fatty acid-based soaps. In this way, needles, granules, noodles, or bars can be produced.Acyl isethionates are used in toilet soap bars and syndets, sulfosuccinic acid mono- and dialkyl esters with 8 to 24 C atoms in the alkyl group, and sulfosuccinic acid monoalkylpolyoxyethyl esters with 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups. The sulfosuccinic acid monoalkyl (C8-C24) ester disodium salts are produced by known processes, e.g., by reacting maleic anhydride with a fatty alcohol with 8-24 C atoms to form the maleic acid monoester of the fatty alcohol, and then sulfiting this with sodium sulfite to form the sulfosuccinic acid ester. Particularly suitable sulfosuccinic acid esters are derived from fatty alcohol fractions with 12-18 C atoms, such as those found, for example, in fatty alcohols. B. are accessible from coconut fatty acid or coconut fatty acid methyl ester by hydrogenation, linear alkanesulfonates with 8 to 24 C atoms, linear alpha-olefinsulfonates with 8 to 24 C atoms,.

[0244] Alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 C atoms,

[0245] Alkyl sulfates and alkyl polyglycol ether sulfates of the formula RO(CH2-CH2O)x-OSC>3H, in which R is a preferably linear alkyl group having 8 to 30 C atoms and x = 0 or 1 to 12, hydroxysulfonates essentially corresponding to at least one of the two following formulas or mixtures thereof and salts thereof, CH3-(CH2)y-CHOH-(CH2)p-(CH-SO3M)-(CH2)z-CH2-O-(CnH2nO)xH, and / or

[0246] CH3-(CH2)y-(CH-SO3M)-(CH2)p-CHOH-(CH2)z- CH2-O-(CnH2nO)xH where in both formulas y and z = 0 or integers from 1 to 18, p = 0, 1 or 2 and the sum (y+z+p) is a number from 12 to 18, x = 0 or a number from 1 to 30 and n is an integer from 2 to 4 and M = H or alkali metal, in particular sodium, potassium, lithium, alkaline earth metal, in particular magnesium, calcium, zinc and / or an ammonium ion, which may optionally be substituted, in particular mono-, di-, tri- or tetraammonium ions with C1 to C4 alkyl, alkenyl or aryl radicals, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylenepropylene glycol ethers of the formula R 1 - (CHOSO3M)-CHR 3 -(OCHR 4 -CH2)n-OR 2 with R 1 , a linear alkyl radical with 1 to 24 C atoms, R 2 represents a linear or branched, saturated alkyl radical having 1 to 24 C atoms, R 3 represents hydrogen or a linear alkyl radical having 1 to 24 C atoms, R 4represents hydrogen or a methyl radical and M represents hydrogen, ammonium, alkylammonium, alkanolammonium, wherein the alkyl and alkanol radicals each have 1 to 4 C atoms, or a metal atom selected from lithium, sodium, potassium, calcium or magnesium and n represents a number in the range from 0 to 12 and furthermore the total number of radicals in R 1 and R 3 contained C atoms is 2 to 44, sulfonates of unsaturated fatty acids with 8 to 24 C atoms and 1 to 6 double bonds,

[0247] Esters of tartaric acid and citric acid with alcohols, which are addition products of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 C atoms, alkyl and / or alkenyl ether phosphates of the formula,

[0248] R 1 (OCH2CH2)nO-(PO-OX)-OR 2 , in the R 1 preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R 2 for hydrogen, a residue (CH2CH2O)n R 2 orX, n is a number from 1 to 10 and X is hydrogen, an alkali or alkaline earth metal or NR 3 R 4 R 5 R e , with R 3 to R e independently of one another standing for hydrogen or a Ci to C4 hydrocarbon radical, sulfated fatty acid alkylene glycol esters of the formula RCO(AlkO) n SC>3M in which RCO- is a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk is CH2CH2, CHCH3CH2 and / or CH2CHCH3, n is a number from 0.5 to 5 and M is a metal, such as alkali metal, in particular sodium, potassium, lithium, alkaline earth metal, in particular magnesium, calcium, zinc, or ammonium ion, such as + NR 3 R 4 R 5 R e , with R 3 to R e independently of each other standing for hydrogen or a C1 to C4 hydrocarbon radical,

[0249] Monoglyceride sulfates and monoglyceride ether sulfates of the formula R 8 OC-(OCH2CH2)x-OCH2-[CHO(CH2CH2O) y H]-CH2O(CH2CH2O)z-SO3X, in which R 8 CO represents a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total represent 0 or numbers from 1 to 30, preferably 2 to 10, and X represents an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Monoglyceride sulfates are preferably used in which R 8 CO represents a linear acyl radical with 8 to 18 carbon atoms,

[0250] Amide ether carboxylic acids, R 1 -CO-NR 2 -CH2CH2-O-(CH2CH2O) nCH2COOM, with R 1 as a straight-chain or branched alkyl or alkenyl radical with a number of carbon atoms in the chain from 2 to 30, n stands for an integer from 1 to 20 and R 2 represents hydrogen, a methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl or iso-butyl radical and M represents hydrogen or a metal such as alkali metal, in particular sodium, potassium, lithium, alkaline earth metal, in particular magnesium, calcium, zinc, or an ammonium ion, such as + NR 3 R 4 R 5 R e , with R 3 to R e independently of each other, represent hydrogen or a C1 to C4 hydrocarbon residue. Such products are available, for example, from Chem-Y under the product name Akypo®.

[0251] Acylglutamates of the formula XOOC-CH2CH2CH(C(NH)OR)-COOX, in which RCO represents a linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2, or 3 double bonds, and X represents hydrogen, an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium, or glucammonium, condensation products of a water-soluble salt of a water-soluble protein hydrolyzate-fatty acid condensation product. These are produced by condensing C8-C30 fatty acids, preferably fatty acids with 12-18 carbon atoms, with amino acids, mono-, di-, and water-soluble oligopeptides, and mixtures of such products, as arise from the hydrolysis of proteins. These protein hydrolysate-fatty acid condensation products are neutralized with a base and are then preferably present as alkali, ammonium, mono-, di- or trialkanolammonium salts.Such products have long been commercially available under the trademarks Lamepon®, Maypon®, Gluadin®, Hostapon® KCG or Amisoft®.

[0252] In principle, the user can freely choose the period between the application of the two agents (V) and (F).

[0253] However, it may be preferable that no further products, such as other conditioners or styling products, are applied between the application of the two products (V) and (F). In this way, the maximum period between the application of the two products (V) and (F) is preferably limited to a maximum 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 pretreatment agent (V) and the application of a coloring agent (F) to the keratin fibers.

[0255] In a further particularly preferred embodiment, a process according to the invention is characterized in that 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 pretreatment agent (V) and the subsequent application of the colorant (F).

[0256] In a further preferred embodiment, a method according to the invention is characterized in that a period of a maximum of 24 hours, preferably a maximum of 12 hours, more preferably a maximum of 6 hours, and most preferably a maximum of 3 hours, lies between steps (3) and (4) (or (3b) and (4)). Following the washing out of the pretreatment agent, the colorant (F) is then applied to the keratin fibers (step (5)).

[0257] The action of the colorant (F) on the keratin fibers in step (6) 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.

[0258] After applying or allowing the colorant (F) to work, it can be rinsed out again in a subsequent step. Rinsing can be done with or without the aid of a shampoo or conditioner, for example.

[0259] Particularly good results were obtained, however, when the inventive coloring process was designed as a leave-on process. This means that in this case, the colorant (F) was not immediately rinsed out after application, but rather the keratin fibers still coated with the colorant (F) were dried. The drying of the keratin fibers can take place at room temperature or be assisted by an external heat source.

[0260] Heat treatment involves bringing the keratin fibers into contact with a heated device, or applying this heated device to or on the keratin fibers. Furthermore, the keratin fibers can also be exposed to warm / hot air for heat treatment. Devices such as a hairdryer, a blow dryer, a thermal cap, a flat iron, a curling iron, or an infrared lamp can be used.

[0261] It has been found that it is preferred if the treatment temperature during the heat treatment is between 40°C and 210°C, preferably from 50°C to 190°C, more preferably from 50°C to 170°C, even more preferably from 50°C to 150°C, and most preferably from 50°C to 100°C. In other words, it has proven particularly preferred if the heat treatment is carried out using a device that is heated to a temperature of 40°C to 210°C, preferably from 50°C to 190°C, more preferably from 50°C to 170°C, even more preferably from 50°C to 150°C, and most preferably from 50°C to 100°C.

[0262] In a particularly preferred embodiment, a method according to the invention is characterized in that the heat treatment is carried out using a device which is heated to a temperature of 40 °C to 210 °C, preferably from 50 °C to 190 °C, more preferably from 50 °C to 170 °C, even more preferably from 40 °C to 100 °C and most preferably from 40 °C to 80 °C. In a particularly preferred embodiment, a method according to the invention is characterized by drying the keratin fibers still coated with the colorant (F), preferably drying the hair still coated with the colorant (F) under the action of heat at a temperature of 40 °C to 210 °C, preferably from 40 °C to 190 °C, more preferably from 40 °C to 170 °C, even more preferably from 40 °C to 100 °C and most preferably from 40 °C to 80 °C.

[0263] For example, the keratin fibers or the hair can be treated with a hairdryer that blows warm or hot air onto the keratin material. This air is particularly preferably between 40 and 100°C, or even more preferably between 40 and 80°C. Alternatively, the keratin material or the hair can be held under an infrared lamp, which is particularly preferably set to a temperature of 40 to 100°C. For the purpose of heat treatment, hair can also be pressed between two appropriately temperature-controlled plates of a straightening iron, with the plates simultaneously moving along the fiber. The plates of the straightening iron can, for example, be set to a temperature of up to 210°C.

[0264] The duration of the heat treatment can be adapted to the selected temperature range. For example, a heat treatment can be carried out for a duration of 5 seconds to 60 minutes, preferably from 15 seconds to 45 minutes, more preferably from 15 seconds to 30 minutes, and most preferably from 15 seconds to 15 minutes.

[0265] Multi-component packaging unit

[0266] 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).

[0267] A second subject of the present invention is therefore a multi-component packaging unit (kit-of-parts) for coloring keratin fibers, in particular human hair, comprising a first container with a pretreatment agent (V) and a second container with a coloring agent (F) separately packaged from one another, wherein the pretreatment agent (V) and the coloring agent (F) have already been disclosed in detail in the description of the first subject of the invention.

[0268] The multi-component packaging unit (kit-of-parts) may also include one or more additional containers with additional formulations.

[0269] Improved color retention

[0270] For the purposes of the present invention, an improvement in color retention is understood in particular to mean an improvement in washfastness, i.e., with the application of the method according to the invention, fewer pigments / dyes are removed from the hair during subsequent washes. Color retention can be quantified, for example, by colorimetric measurements (measurement of the L, a, b values) and calculation of the color difference. The smaller the color difference between washed and unwashed hair, the better the washfastness or color retention. Color retention or washfastness can also be assessed visually.

[0271] A third subject matter of the present application is the use of a pretreatment agent (V) for improving the color retention of a colorant (F) on keratin fibers, in particular human hair, wherein the colorant (F) and the pretreatment agent (V) have already been disclosed in detail in the description of the first subject matter of the invention.

[0272] Regarding the further preferred embodiments of the multi-component packaging unit (kit of parts) according to the invention and use, what has been said regarding the methods according to the invention applies mutatis mutantis.

[0273] Examples

[0274] 1 . Formulations

[0275] The following formulations were prepared (all data in wt.% unless otherwise stated):

[0276] 2. Application to strands

[0277] The pretreatment agent (V) was applied to hair strands (Kerling 9-0). 1.0 g of pretreatment agent (V) per gram of hair was applied to the strands, massaged in, and left to act at room temperature for 30 minutes.

[0278] Next, 0.25 g of a 28% solution of sodium laureth sulfate (2EO) in water (Texapon N28, BASF) was applied to the hair strands and massaged in. The pretreatment agent and the surfactant solution were then rinsed out together with water. The colorant (F) was then immediately applied to the still-damp hair. 2.0 g of colorant (F) per gram of hair strand was massaged in and left on for 1 minute. The strands still coated with the colorant were then dried with a standard hairdryer. The colored strands were visually assessed by a trained person under a daylight lamp.

[0279] Reference strands were treated directly with the respective colorant (F) without the use of the pretreatment agent (V). Before applying the colorant (F), the reference strands were moistened only with water, then the colorant was applied according to the procedure described above. These strands were also visually assessed by a trained person under a daylight lamp.

[0280] Following the coloring process, each colored strand underwent five manual hair washes. 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 each wash, the strand was visually assessed again under a daylight lamp.

[0281] The hair strands were assessed for their color intensity using a scale from 1 (very low color intensity) to 5 (very high color intensity).

[0282] Comparison = without pretreatment

[0283] Invention = successive application of pretreatment agent (V) and colorant (F)

[0284] 0 HW = Color result directly after coloring

[0285] 5 = high intensity 1 = low intensity

[0286]

[0287] 5 = high intensity 1 = low intensity

[0288] The strands dyed by the process (V) / (F1) and (V) / (F2) according to the invention showed improved wash fastness compared to the corresponding dyeing without pretreatment (V).

Claims

Patent claims 1. A process for dyeing keratin fibers, in particular human hair, comprising the following steps: - application of a pretreatment agent (V) to the keratin fibres, wherein the pretreatment agent (V-1) contains at least one alkalizing agent, and - application of a coloring agent (F) to the keratin fibers, wherein the coloring agent is contained in a cosmetic carrier (F-1) at least one chitosan and / or a chitosan derivative, and (F-2) contains at least one coloring compound from the group of pigments and direct dyes.

2. Process according to claim 1, characterized in that the pretreatment agent (V) contains at least one inorganic alkalizing agent (V-1) from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, potassium carbonate and / or ammonia, very particularly preferably potassium hydroxide.

3. Process according to one of claims 1 to 2, characterized in that the pretreatment agent (V) contains at least one organic alkalizing agent (V-1) from the group consisting of alkali metal salts of Cs-Cso fatty acids, alkaline earth metal salts of Cs-Cso fatty acids, ammonium salts of Cs-Cso fatty acids, Ci-Ce alkanolamines and / or basic amino acids.

4. Method according to one of claims 1 to 3, characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - one or more alkalizing agents (V-1) in a total amount of 0.1 to 10.0% by weight, preferably 0.2 to 7.5% by weight, more preferably 0.5 to 5.0% by weight and particularly preferably 1.0 to 3.5% by weight.

5. Process according to one of claims 1 to 4, characterized in that the pretreatment agent (V) contains at least one ethylene glycol (V-2) of the formula (EG), where x represents 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.

6. The method according to claim 5, characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains one or more ethylene glycols of the formula (EG) in a total amount of 10.0 to 99.0 wt.%, preferably 25.0 to 95.0 wt.%, more preferably 40.0 to 90.0 wt.% and most preferably 60.0 to 85.0 wt.%.

7. The method according to any one of claims 1 to 6, characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains one or more solvents from the group consisting of ethanol, isopropanol, glycerol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethylene glycol monoethyl ether, phenoxyethanol, benzyl alcohol, poly-Ci-Ce-ethylene glycols, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and glycerol carbonate in a total amount of 3.0 to 80% by weight, preferably 5.0 to 60.0% by weight, more preferably 9.0 to 40.0% by weight and most preferably 12.0 to 25.0% by weight.

8. The method according to any one of claims 1 to 7, characterized in that the pretreatment agent (V) - based on the total weight of the pretreatment agent (V) - contains 1.0 to 70.0 wt.%, preferably 2.0 to 50.0 wt.%, more preferably 3.0 to 40.0 wt.% and most preferably 4.0 to 20.0 wt.% water.

9. The method according to any one of claims 1 to 8, characterized in that the colorant (F) contains at least one chitosan and / or a chitosan derivative (F-1) having a molecular weight of 20,000 to 800,000 g / mol, preferably of 50,000 to 600,000 g / mol, more preferably of 80,000 to 450,000 g / mol and most preferably of 100,000 to 300,000 g / mol.

10. The method according to any one of claims 1 to 9, characterized in that the colorant (F) - based on the total weight of the colorant (F) - contains one or more chitosans and / or chitosan derivatives in a total amount of 0.1 to 10.0 wt.%, preferably 0.2 to 8.0 wt.%, more preferably 0.5 to 6.0 wt.% and most preferably 0.7 to 2.0 wt.%. 11 . Method according to one of claims 1 to 10, characterized in that the coloring agent (F) - based on the total weight of the coloring agent (F) - one or more coloring Compounds from the group of pigments and direct dyes (F-2) 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.%.

12. The method according to any one of claims 1 to 11, characterized in that the coloring agent (F) contains one or more organic acids (F-3) from the group consisting of acetic acid, citric acid, succinic acid, tartaric acid, lactic acid, malic acid, malonic acid, maleic acid and benzoic acid.

13. A method according to any one of claims 1 to 12, comprising the following steps in the order given: (1) Applying the pretreatment agent (V) to the keratin fibers, (2) allowing the pretreatment agent (V) applied in step (1) to act on the keratin fibres for a period of 1 to 45 minutes, preferably 5 to 30 minutes and particularly preferably 10 to 15 minutes, (3) if necessary, rinsing out the pretreatment agent (V) with water or with the aid of water and a shampoo, (4) if necessary, drying the keratin fibres, (5) Applying the colorant (F) to the keratin fibers. (6) Action of the colorant (F) on the keratin fibers, and (7) if necessary, rinsing out the dye (F).

14. The method according to any one of claims 1 to 13, characterized in that between the application of the pretreatment agent (V) and the subsequent application of the colorant (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.

15. Multi-component packaging unit (kit-of-parts) for coloring keratin fibers, in particular human hair, comprising a first container with a pretreatment agent (V) and a second container with a coloring agent (F) separately packaged from one another, wherein the pretreatment agent (V) and the coloring agent (F) are defined in claims 1 to 12.

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