Agents for the repigmentation of keratin fibers, especially human hair

Abstract

Cosmetic formulation containing a dye precursor selected from the group consisting of indoline derivatives and indole derivatives and at least one direct dye.

Description

[0001] The present invention relates to a cosmetic formulation comprising a dye precursor selected from the group consisting of indole derivatives and indoline derivatives, and a xanthine derivative.

[0002] A person's hair color depends on the amount of melanins, eumelanin and pheomelanin, contained in the hair fiber layer and produced by melanocytes in the hair follicles. As part of the normal aging process, but also due to certain medical conditions, stress, vitamin and mineral deficiencies, or excessive alcohol or nicotine consumption, melanin production can decrease, resulting in hypopigmentation. Such hair appears white or colorless to the observer. The visual appearance of gray hair results from the mixture of pigmented and apigmented hair.

[0003] The average life cycle of a hair is three to seven years. After that, the hair falls out and a new hair grows in its place. Gradually, the proportion of white or pigmentless hairs predominates, and the hair turns gray.

[0004] Changing hair color, and in particular the pigmentation or repigmentation of gray hair, represents an important area of ​​modern cosmetics. Good fastness properties, good gray coverage, and long-lasting coloring are particularly desirable.

[0005] For permanent, intensive dyeings with good fastness properties and good gray coverage, oxidation dyes are traditionally used. Such dyes typically contain oxidation dye precursors, so-called developer components, and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide or atmospheric oxygen, form the actual dyes, either with each other or by coupling with one or more coupler components.

[0006] However, the use of oxidative dyes is still associated with impairments or damage to the hair and especially its surface structure.

[0007] Alternatively, precursors of the natural hair pigment melanin can be applied to the hair, which, through oxidative processes in the hair, form virtually nature-identical pigments. Coloring can be achieved using atmospheric oxygen as the sole oxidizing agent, thus eliminating the need for additional oxidizing agents. One such process using 5,6-dihydroxyindoline as a dye precursor is described, for example, in EP 0 530 229 B1.

[0008] In contrast, direct dyes, also known as substantive dyes, are used for temporary coloring. These are dye molecules that absorb directly into the hair and no longer require an oxidative process to develop the color. Compared to oxidative hair coloring, the colors obtained with substantive dyes are less durable and wash out more quickly. Colorings with substantive dyes typically remain on the hair for between 5 and 20 washes.

[0009] WO 99 / 66890 describes a dye for dyeing keratin fibers containing a dye precursor, which may be an indoline or indole derivative, e.g., a derivative of 5,6-dihydroxyindoline or 5,6-dihydroxyindole, and an amino acid or oligopeptide. The color can be formed by air oxidation.

[0010] DE 10 2018 127 182 A1 relates to a two-component system for artificial hair coloring, comprising, separately, an anhydrous carrier medium comprising an alkane, a fatty alcohol, and an alcohol, as well as an aqueous phase containing hydrogen peroxide. An organosilicon compound from the silane group may be included for hair protection and care.

[0011] DE 10 2007 038 484 A1 describes a hair treatment product for protection against external influences, wherein the hair treatment product contains bacterial ferment(s) from Thermus thermophilus.

[0012] WO 2005 / 007615 A1 relates to 2-(amino- or substituted amino)-5-(substituted oxymethyl)-phenol compounds and compositions for the oxidative dyeing of keratin fibers.

[0013] However, the formulations known in the state of the art do not allow sufficiently satisfactory results to be achieved in terms of quality, intensity and duration of the colouring performance while at the same time causing as little impairment or damage to the hair structure as possible.

[0014] For example, the precursors of the natural hair pigment melanin take a significant time to form, making it difficult to control the color tones. Furthermore, the intermediate shades often turn out unnaturally violet. Another disadvantage is the unpigmented hairline that appears as the hair grows back.

[0015] In summary, there is still room for improvement, particularly in terms of fastness properties, grey coverage and the duration of dyeing performance.

[0016] Based on this, the object of the present invention was to provide a cosmetic formulation suitable for pigmenting or repigmenting keratin fibers, especially human hair, and in particular offering improved fastness properties of the pigmented or repigmented keratin fibers as well as improved gray coverage. Furthermore, this cosmetic formulation should have improved properties compared to prior art formulations with regard to the quality, intensity, and duration of the coloring performance.

[0017] This object was surprisingly achieved by the formulation according to claim 1. Preferred embodiments emerge from the dependent claims.

[0018] According to the invention, the object is achieved by providing a cosmetic formulation which contains a dye precursor selected from the group consisting of indole derivatives and indoline derivatives.

[0019] Surprisingly, it was found that the contrast to the regrowing hair (hairline) is significantly lower, as the natural pigment formation in the hair root is stimulated, while at the same time the already grown-out hair darkens.

[0020] Overall, the hair gradually becomes darker, with the color effect building up subtly, gray hair being clearly covered, and the overall impression of the hair color appearing significantly darker.

[0021] Thus, the cosmetic formulation according to the invention achieves good gray coverage and excellent fastness properties with long-lasting coloring performance and reduced graying of the hairline.

[0022] The xanthine derivative contained in the formulation according to the invention, together with the dye precursor, stimulates the keratinocytes in the hair roots, causing them to produce more natural pigment. Furthermore, the xanthine derivative causes the hair to stay on the head longer. This delays the loss of still-pigmented hair and contributes to the natural repigmentation of hair that is already poorly pigmented or lacks pigment. For the purposes of the present invention, the terms "pigmentation" and "repigmentation" are used interchangeably.

[0023] The dye precursor contained in the formulation according to the invention, which is an indole derivative and / or indoline derivative, is preferably an indole derivative and / or indoline derivative that has a hydroxyl or amino group, preferably as a substituent on the six-membered ring. These groups can bear further substituents, e.g., in the form of an etherification or esterification of the hydroxyl group or an alkylation of the amino group. Compounds with two of these groups, in particular two hydroxyl groups, one or both of which can be etherified or esterified, are particularly preferred.

[0024] In a preferred embodiment of the invention, the dye precursor is an indole derivative.

[0025] According to the invention, the dye precursor is preferably a derivative of 5,6-dihydroxyindole of the formula (I), wherein, in each case independently of one another, R 1represents hydrogen, a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, R 2 hydrogen or a-COOH group, where the-COOH group can also be present as a salt with a physiologically acceptable cation, R 3 represents hydrogen or a C1-C4 alkyl group, R 4 Hydrogen, a C1-C4 alkyl group, an amino group or a group -CO-R 6 means in the R 6 a C1-C4 alkyl group, and R 5 one of the under R 4 mentioned groups means or a physiologically acceptable salt of these compounds with an organic or inorganic acid.

[0026] Preferred representatives according to the invention are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole.

[0027] In a particularly preferred embodiment, the compound of formula (I) is selected from 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole and their physiologically acceptable salts.

[0028] Most preferably, the dye precursor used in the formulation according to the invention is 5,6-dihydroxyindole.

[0029] In a further preferred embodiment of the invention, the dye precursor is an indoline derivative.

[0030] According to the invention, the dye precursor is preferably a derivative of 5,6-dihydroxyindoline of the formula (II), wherein, in each case independently of one another, R 1 represents hydrogen, a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, R 2 hydrogen or a-COOH group, where the-COOH group can also be present as a salt with a physiologically acceptable cation, R 3represents hydrogen or a C1-C4 alkyl group, R 4 Hydrogen, a C1-C4 alkyl group, an amino group or a group -CO-R 6 means in the R 6 a C1-C4 alkyl group, and R 5 one of the under R 4 mentioned groups means or a physiologically acceptable salt of these compounds with an organic or inorganic acid.

[0031] Preferred representatives according to the invention are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindole.

[0032] In a particularly preferred embodiment, the compound of formula (II) is selected from 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline and their physiologically acceptable salts.

[0033] Most preferably, the dye precursor used in the formulation according to the invention is 5,6-dihydroxyindoline.

[0034] In a further particularly preferred embodiment, the dye precursor used in the formulation according to the invention is dihydroxyindoline hydrobromide (2,3-dihydro-1H-indole-5,6-diol hydrobromide).

[0035] The indole and indoline derivatives contained in the compositions according to the invention can be used both as free bases and in the form of their physiologically acceptable salts with inorganic or organic acids, e.g., hydrochlorides, sulfates, and hydrobromides.

[0036] The indole or indoline derivative is usually present in the formulation according to the invention in an amount of 0.001-5 wt.%, preferably 0.005-2 wt.%, preferably 0.01-2 wt.%, preferably 0.01-1.5 wt.%, preferably in an amount of about 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1.5 wt.%, in each case based on the total weight of the formulation.

[0037] In a particularly preferred embodiment, the dye precursor is an indole derivative, preferably 5,6-dihydroxyindole, which is present in the formulation according to the invention in an amount of 0.01-2 wt.%, preferably 0.05-0.6 wt.%, preferably in an amount of 0.08-0.5 wt.%, preferably in an amount of about 0.1-0.5 wt.%, in each case based on the total weight of the formulation.

[0038] In a further particularly preferred embodiment, the dye precursor is an indoline derivative, preferably dihydroxyindoline hydrobromide (2,3-dihydro-1H-indole-5,6-diol hydrobromide), which is contained in the formulation according to the invention in an amount of 0.01-4.0 wt.%, preferably 0.05-2.0 wt.%, preferably in an amount of 0.08-1.0 wt.%, preferably in an amount of about 0.1-0.5 wt.%, in each case based on the total weight of the formulation.

[0039] The formulation according to the invention may also contain more than one indole or indoline derivative or mixtures of indole and indoline derivatives.

[0040] The formation of the pigment from the dye precursor, i.e. the indole or indoline derivative, occurs by reaction with atmospheric oxygen; no additional oxidizing agent is required.

[0041] The formulation according to the invention can contain a xanthine derivative. The xanthine derivative then contained in the cosmetic formulation, together with the dye precursor, leads in particular to the stimulation of the keratinocytes in the hair roots to produce more natural pigment again. Furthermore, the xanthine derivative causes the hair to remain on the head longer, which, on the one hand, delays the loss of still-pigmented hair and, on the other hand, contributes to the natural repigmentation of hair that is already poorly pigmented or lacks pigment.

[0042] The preferred xanthine derivative according to the invention is caffeine.

[0043] The IUPAC name for caffeine is 1,3,7-trimethyl-3,7-dihydro-1H-purine-2,6-dione. Alternatively, caffeine is also known as 1,3,7-trimethylxanthine. Caffeine is represented by the following chemical formula (III). Caffeine is a methylxanthine alkaloid belonging to the class of methylxanthines. It is a bitter crystalline substance, can be considered a purine derivative, and is chemically related to the adenine and guanine bases of deoxyribonucleic and ribonucleic acids.

[0044] The xanthine derivative is usually present in the formulation according to the invention in an amount of 0.0001-10 wt.%, preferably 0.01-5 wt.%, preferably 0.05-2 wt.%, preferably 0.1-1.5 wt.%, preferably in an amount of about 0.0001 wt.%, 0.05 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.5 wt.%, 0.7 wt.%, 1.0 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, in each case based on the total weight of the formulation.

[0045] Formulations according to the invention further contain at least one direct dye.

[0046] Surprisingly, it was discovered that the color effect of a formulation containing a direct dye in addition to the indole or indoline-type dye precursor and the xanthine derivative is more intense than would have been expected based on the color effects of the individual components, the indole or indoline-type dye precursor and the direct dye. The darkening effects (repigmentation) are synergistically enhanced by the combination with direct dyes in terms of the speed of color onset and color depth.

[0047] In the presence of a combination of indole or indoline type dye precursor and direct dye, a synergistic effect occurs.

[0048] Thus, with the cosmetic formulation according to the invention containing a dye precursor of the indole or indoline type, a xanthine derivative and a direct dye, a particularly intensive color effect is advantageously achieved, with excellent gray coverage and excellent fastness properties, ie a highly natural color tone with a long-lasting coloring result, being achieved.

[0049] As mentioned at the beginning, direct dyes are dye molecules that are absorbed directly onto the hair and no longer require an oxidative process to develop the color.

[0050] Preferred direct dyes include nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones and indophenols and are preferably selected from the group of dyes known under the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, Basic Yellow 57, Basic Yellow 87, HC Orange 1, Disperse Orange 3, Acid Orange 7, Basic Orange 31, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, Acid Red 33, Acid Red 52, Pigment Red 57:1, Basic Red 51, Basic Red 76, HC Blue 2, HC Blue 12, HC Blue 16, Disperse Blue 3, Acid Blue 7, Basic Blue 99, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, Acid Black 52, Basic Brown 16 and Basic Brown 17 as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-Bis-(β-hydroxyethyl)-amino-2-nitrobenzene,3-Nitro-4-(β-hydroxyethyl)-aminophenol, 2-(2-Hydroxyethyl)amino-4,6-dinitrophenol, 1-(2'-Hydroxyethyl)amino-4-methyl-2-nitrobenzol, 1-Amino-4-(2-hydroxyethyl)-amino-5-chlor-2-nitrobenzol, 4-Amino-3-nitrophenol, 1-(2-Ureidoethyl)amino-4-nitrobenzol, 4-Amino-2-nitrodiphenylamin-2'-carbonsäure, 6-Nitro-1,2,3,4-tetrahydrochinoxalin, 2-Hydroxy-1,4-naphthochinon, Hydroxyethyl-2-nitro-toluidin, Pikraminsäure und deren Salze, 2-Amino-6-chlor-4-nitrophenol, 4-Ethylamino-3-nitrobenzoesäure und 2-Chlor-6-ethylamino-1-hydroxy-4-nitrobenzol.,

[0051] The direct dye is usually present in the formulation according to the invention in an amount of 0.001-5 wt.%, preferably 0.05-3 wt.%, preferably 0.1-2 wt.%, preferably 0.1-1.2 wt.%, preferably in an amount of about 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2.0 wt.%, in each case based on the total weight of the formulation.

[0052] In a preferred embodiment, the direct dye is selected from the group consisting of 2-amino-6-chloro-4-nitrophenol, 1,4-bis-(β-hydroxyethyl)-amino-2-nitrobenzene, Basic Yellow 57, Basic Red 76, Basic Brown 16, Basic Brown 17, Basic Blue 99, HC Blue 2, HC Blue 12, HC Blue 16 and Acid Violet 43.

[0053] In a particularly preferred embodiment of the invention, the direct dye is HC Blue 2.

[0054] In a particularly preferred embodiment, the formulation according to the invention contains 5,6-dihydroxyindole as a dye precursor and caffeine as a xanthine derivative. 5,6-dihydroxyindole is present in an amount of 0.05-0.6 wt.% and caffeine in an amount of 0.8-1.2 wt.%, each based on the total weight of the formulation.

[0055] In another particularly preferred embodiment, the formulation according to the invention contains 5,6-dihydroxyindole as a dye precursor, caffeine as a xanthine derivative, and HC Blue 2 as a direct dye. 5,6-dihydroxyindole is present in an amount of 0.05-0.6 wt. %, caffeine in an amount of 0.8-1.2 wt. %, and the direct dye in an amount of 0.1-1.2 wt. %, each based on the total weight of the formulation.

[0056] Furthermore, the cosmetic formulation according to the invention can contain all additives known in such preparations (ie active ingredients, additives and auxiliaries).

[0057] In one embodiment, the cosmetic formulation comprises a surfactant. The surfactant can be an anionic, non-ionic, cationic or zwitterionic surfactant. The surfactant is preferably an anionic or non-ionic surfactant, in particular an anionic or non-ionic surfactant that is as mild as possible (i.e., particularly skin-compatible). Non-ionic surfactants are used according to the invention in particular because of their very good emulsification properties and their excellent skin care properties. Anionic surfactants are preferred because they have a particularly high cleaning performance. They are therefore particularly suitable in cleaning formulations such as shampoos. Cationic surfactants have excellent hair care properties and are used according to the invention in particular in hair care formulations such as conditioners, shampoos and treatments.

[0058] The formulation according to the invention preferably contains surfactants in an amount of 2 to 40 wt.%, in particular 5 to 30 wt.%, preferably 7 to 20 wt.%, particularly preferably 10 to 17 wt.%, based in each case on the total weight of the formulation. Suitable amounts of surfactant are: 8 wt.%; 9 wt.%; 10 wt.%; 11 wt.%; 12 wt.%; 13 wt.%; 14 wt.%; 15 wt.%; 16 wt.%; 17 wt.%; 18 wt.%; 19 wt.%; 20 wt.%; 21 wt.%; 22 wt.%; 23 wt.%; 24 wt.%; 25 wt.%, based in each case on the total weight of the formulation. The cosmetic formulation of the invention particularly preferably contains one or more anionic surfactants in an amount of 0.1 to 20 wt.%, preferably 1 to 17 wt.%, and particularly preferably 5 to 15 wt.%, based in each case on the total weight of the formulation. Suitable amounts of anionic surfactant are: 1 wt.%; 2 wt.%; 3 wt.%; 4 wt.%; 5 wt.%; 6 wt.%; 7 wt.%; 8 wt.%; 9 wt.%; 10 wt.%; 11 wt.%; 12 wt.%.-%; 13 wt.%; 14 wt.%; 15 wt.%; 16 wt.%; 17 wt.%; 18 wt.%, 19 wt.%, 20 wt.%, each based on the total weight of the formulation. In these amounts, the surfactants exhibit particularly high cleaning performance and are extremely well tolerated by skin, scalp, and hair.

[0059] The surfactants of the present invention are described, among others, in the book “Surfactants and interfacial phenomena”, by Milton Rosen and Joy Kunjappu, John Wiley & Sons, Inc.-Verlag, 2012, 4th edition.

[0060] In a preferred embodiment, the surfactant is an anionic surfactant selected from alkyl carboxylates, alkyl sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl phosphates, alkyl sarcosinates, alkyl taurates, amino acid surfactants, and mixtures thereof. Particularly preferably, the surfactant is selected from alkyl carboxylates, alkyl sulfates, alkyl sarcosinates, alkyl taurates, alkyl glutamate, such as sodium cocoyl glutamate / disodium cocoyl glutamate, alkyl glucinate, alkyl alaninate, such as sodium cocoyl alaninate, and mixtures thereof. Also preferred due to their cleaning performance are fatty alcohol polyglycerol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, and α-olefin sulfonates.

[0061] Alkyl carboxylates have the generic formula RCO2M, alkyl sulfates have the generic formula ROSO3M, alkyl sarcosinates have the generic formula RC(O)N(CH3)CH2CO2M, and alkyl taurates have the generic formula RC(O)N(CH3)CH2CH2SO3M, where R is a C4-C26 -alkyl or C4-C 26 -alkenyl and M is a water-soluble cation such as ammonium, sodium or potassium. Preferably, M is a sodium cation. Preferably, R is a C 12 -C 16 -alkyl or a C 12 -C 18 -Alkyl.

[0062] In one embodiment, the surfactant is a nonionic surfactant (also referred to as a nonionic emulsifier). Non-limiting examples include glycerol fatty acid esters, fatty alcohols, polyoxyethylene ethers of one or more fatty alcohols, alkoxylated fatty acid alkyl esters, polyglycerol ethers of fatty alcohols, polyglycerol esters of fatty acids, polyethylene glycol and / or polypropylene glycol ethers, fatty acid amides, alkylphenol polyglycol ethers, amine oxides, and alkyl polyglucosides.

[0063] In one embodiment, the surfactant is selected from the group of glycerol fatty acid esters, fatty alcohols, polyoxyethylene ethers of one or more fatty alcohols, polyglycerol ethers of fatty alcohols, polyglycerol esters of fatty acids and mixtures thereof.

[0064] In the present invention, the term "glycerol fatty acid ester" refers to a glycerol mono- or glycerol difatty acid ester. Glycerol difatty acid esters have the formula R 3 -COO-(CH2CH(OH)CH2)-OOR 4 or R 3 -COO-(CH2CH(OOR 4 )CH2)-OH. Glycerol monofatty acid esters have the formula R 3 -COO-(CH2CH(OH)CH2)-OH or HO-(CH2CH(OOR 3 )CH2)-OH. R 3 and R 4 independently from C6-C 28 -alkyl and C6-C 28-Alkenyl. Glycerol monofatty acid esters contain a glycerol group bound to a single fatty acid via an ester bond. Examples are glycerol monostearate, glycerol monobehenate, glycerol monocaprylate, glycerol monocaprate, and glycerol monolaurate.

[0065] Fatty alcohols (saturated) are compounds of the formula H3C-(CH2) n -CH2-OH, where n is an integer between 4 and 20, preferably an integer between 6 and 16.

[0066] Polyoxyethylene ethers are compounds of the formula R 5 (OC2H3) n OH, where R 5 is selected from C6-C 28 -Alkyl, C6-C 28-alkenyl, substituted and unsubstituted phenoxy groups; and n is an integer greater than 1. Preferably, the polyoxyethylene ether of one or more fatty alcohols is selected from the group consisting of steareth-2, steareth-21, macrogol cetostearyl ether 12, ceteareth-25, macrogol cetostearyl ether 20, and mixtures of the aforementioned compounds. Even more preferably, the polyoxyethylene ether is a compound selected from the group consisting of ceteareth-25, macrogol cetostearyl ether 20, and mixtures of the aforementioned compounds.

[0067] The term “polyglycerol ethers of fatty alcohols” refers to a compound of the formula R 6 O-(C3H6O2) n -H, where R 6 a branched or linear C6-C 28 -alkyl or C6-C 28-alkenyl and n is an integer greater than 1, preferably an integer from 2 to 10. It is preferred that the formulation contains 0.01 to 15.0 wt.%, 0.1 to 10.0 wt.%, or 1 to 5.0 wt.% polyglycerol ether.

[0068] The term “polyglycerol esters of fatty acids” refers to compounds containing both a polyglycerol unit and at least one C6-C 26 -alkyl or C6-C 26 -alkenylcarboxylic acid unit. These compounds may have the formula R 7 -R 8 -(C3H6O2) n -H, where R 7 a C6-C 26 -alkanoate- or C6-C 26 -alkenoate residue and R 8 a suitable connecting molecule or a direct bond. Thus, the polyglycerol unit and the C6-C 26 -alkyl or C6-C 26-Alkenylcarboxylic acid unit may be directly linked by an ester bond or contain a linking unit connecting these two units. Non-limiting examples of this group are polyglyceryl-3 methylglucose distearate, polyglycerol polycrinoleate, polyglyceryl dimerate isostearate, polyglyceryl-2 laurate, polyglyceryl-2 sesquiisostearate, polyglyceryl-3 distearate (Cremophor GS 32), polyglyceryl-3 oleate, polyglyceryl-3 methylglycose distearate, polyglyceryl-4 caprate (Polyglycerol Caprate T2010190), polyglyceryl-4 diisostearate / polyhydroxystearate / sebacate (Isolan GPS), and polyglyceryl-4 isostearate.

[0069] In one embodiment, the surfactant comprises a cationic surfactant, such as a quaternary surfactant. Quaternary surfactants contain at least one nitrogen atom covalently bonded to four alkyl or aryl groups. This results in a positive charge, regardless of pH. Alkyl betaine, alkylamidopropyl betaine, and alkylamidopropyl hydroxysulfaine are advantageous.The cationic surfactants used according to the invention can also preferably be selected from the group of quaternary ammonium compounds, in particular benzyltrialkylammonium chlorides or bromides, such as benzyldimethylstearylammonium chloride, and alkyltrialkylammonium salts, for example cetyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium chlorides or bromides, dialkyldimethylammonium chlorides or bromides, alkylamideethyltrimethylammonium ether sulfates, alkylpyridinium salts, for example lauryl- or cetylpyrimidinium chloride, imidazoline derivatives, and compounds with cationic character, such as amine oxides, for example alkyldimethylamine oxides or alkylaminoethyldimethylamine oxides. Cetyltrimethylammonium salts are particularly advantageous.

[0070] In a further embodiment, the formulation according to the invention contains at least one additive. Preference is given to additives that are typically used in shampoos, conditioners, and emulsions for treating the skin, scalp, and hair. The at least one additive can be present in a proportion of 0.01 wt.% to 12.0 wt.%, more preferably from 0.25 wt.% to 10.0 wt.%, in particular from 1.0 to 7.0 wt.%.

[0071] The at least one additive may further be selected from the group consisting of hair conditioning agents, refatting agents, preservatives, stabilizers, fragrances, antioxidants, rheology modifiers, thickeners, care agents, dyes, pearlizing agents, lightening agents, solvents, setting compounds, anti-dandruff agents, vitamins, alkalizing agents or pH adjusters and combinations thereof.

[0072] Hair conditioners can reduce static electricity in the hair by neutralizing electrical charges on its surface. Examples of hair conditioners include quaternary ammonium compounds.

[0073] Refatting agents, also called refatting or superfatting agents, are lipophilic substances that can prevent disruptive effects on the epidermal barrier function. Examples of refatting agents include lanolin, squalene, liquid paraffin, vegetable oils, silicones, and cetyl palmitate.

[0074] Preservatives are substances used for preservation by killing and / or inhibiting the growth of microorganisms that degrade the formulation. The preservatives can preferably be selected from the group consisting of benzoic acid, benzoic acid derivatives, sorbic acid, sorbic acid derivatives, salicylic acid, salicylic acid derivatives, phenoxyethanol, parabens, and combinations thereof. In a preferred embodiment, sodium benzoate and / or potassium sorbate are used as preservatives in the formulation according to the invention. In a slightly acidic environment, sodium benzoate releases benzoic acid, and potassium sorbate releases sorbic acid. Both acids are said to have an antimicrobial effect.

[0075] Stabilizers can protect light-sensitive components against radiation and are preferably UV absorbers such as benzophenone derivatives.

[0076] The addition of fragrances can provide a pleasant smell to the formulation. Examples include perfumes, which are familiar to those in the art.

[0077] An antioxidant is a chemical compound that slows down or completely prevents the oxidation of other components in the formulation according to the invention. Examples of suitable antioxidants include citric acid, ascorbic acid, sodium sulfite, and butylhydroxyanisole.

[0078] Rheology modifiers and thickeners can help improve the application properties of the formulation according to the invention. The addition of table salt (sodium chloride) can be considered as a rheology modifier and thickener. By adding table salt, the flowability of the formulation according to the invention can be influenced within certain limits and adjusted to the required level. Naturally occurring gelling agents can also be used as thickeners, preferably selected from agar, xanthan gum, cellulose and / or cellulose derivatives, or alginic acid.

[0079] For the purposes of the application, care products are understood to be substances that condition the hair and / or scalp. Hydrolyzed wheat protein, panthenol, and allantoin have a conditioning effect on the scalp and hair. Hydrolyzed wheat protein has primarily moisturizing properties.

[0080] The formulation according to the invention may contain additional colorants, for example, to impart a visually appealing color to the formulation. For example, CI 47005 may be included in the formulation according to the invention as a suitable colorant.

[0081] A solvent or solvent mixture commonly known to those skilled in the art can be used as the solvent. Preferred solvents are ethanol or butylene glycol, especially 1,4-butylene glycol, propylene glycol, and isopropyl alcohol. Ethanol or propylene glycol is preferred. These solvents can preferably be present in the formulation according to the invention in an amount of 0.1 to 70 wt.%. They are most preferably present in an amount of 0.1 to 5.0 wt.%.

[0082] Strengthening compounds are preferably selected from the group consisting of waxes, synthetic polymers, and mixtures thereof. Suitable strengthening compounds are known to the person skilled in the art and are described, for example, in Goddard, E. Desmond; Gruber, James V. (1999), "Principles of polymer science and technology in cosmetics and personal care", Series: Cosmetic science and technology series : v. 22., New York (Marcel Dekker, INC.); Schrader, Karlheinz (1989), "Grundlagen und Rezepturen der Kosmetika" (2nd edition), Chapter 3.7, Heidelberg (Hüthig); and Scott, Richard (2017), "Ingredients focus: cosmetic waxes and butters", Personal Care Europe 10(3), 46-47.

[0083] Antidandruff agents are used to control excessive dandruff formation on the scalp. Suitable antidandruff agents are known to those skilled in the art and are described, for example, in Trüeb, RM (2009). "Treating head dandruff successfully." Akt Dermatol 35(01 / 02): 19-24; Trueb, RM (2007). "Shampoos: ingredients, efficacy and adverse effects." J. Dtsch. Dermatol. Ges. 5(5): 356-365; Sanfilippo, A. and J. English (2006). "An overview of medicated shampoos used in dandruff treatment." P AND T 31(7): 396; and Futterer, E. (1981). "Evaluation of efficacy of antidandruff agents." J Soc Cosmet Chem 32: 327-338.

[0084] Vitamins and minerals such as niacinamide (vitamin B3), vitamin E, or zinc are used to achieve a positive effect on hair growth and repair damaged hair. Suitable vitamins and minerals are known to those skilled in the art and are described, for example, in Pietrzik K, Golly I, Loew D, Handbook of Vitamins, Elsevier GmbH, Urban & Fischer Verlag, Munich 2008; H. Lautenschläger, Vitamins in Cosmetics, medical Beauty Forum 2020 (3), 14-17; and Martini MC, Chivot M, Peyrefitte G, Textbook of Cosmetics: Fundamentals - Basic Substances - Basic Techniques, Hogrefe AG, Bern 2001.

[0085] Alkalizing agents or pH adjusters are used to adjust the pH of the formulation to a desired range. Suitable alkalizing agents or pH adjusters include sodium hydroxide, monoethanolamine 0.1-5%, phosphoric acid, and citric acid.

[0086] Example compositions are shown in the following table: ingredient Amount in wt% Aqua [water] to 100 Sodium lauryl ether sulfate 5-15 Sodium myreth sulfate 0-5 Sodium cocoamphoacetate 0-5 Laureth-2 0-5 Cocoamidopropyl betaine 0-5 Disodium lauryl sulfosuccinate 0-5 Sodium lauroyl glutamate 0-5 Panthenol 0-5 caffeine 0,1-5 Sodium chloride 0-5 Phenoxyethanol 0-5 Wheat protein hydrolysate 0-3 Cocoglucoside 0-3 Glyceryl oleate 0-3 Phosphoric acid 0-3 Sodium benzoate 0-3 PEG-120 Methylglucose dioleate 0-3 Potassium sorbate 0-3 HC Blue 2 0,1-2 Allantoin 0-3 PEG-40 hydrogenated castor oil 0-3 menthol 0-2 Polyquaternium-7 0-2 Sodium hydroxide 0-2 Disodium EDTA 0-2 Dihydroxyindol 0,01-2 Tocopherol 0-2 citric acid 0-2 Niacinamide 0-2 Zinc PCA 0-2 Dye / staining agent 0-2

[0087] According to the invention, the composition is applied topically. Topical application is understood to mean external application, in particular local, external application. Compositions according to the invention are preferably hair care products (i.e., treatment agents such as shampoos, conditioners, or treatments).

[0088] In a preferred embodiment, the formulation according to the invention is present as a shampoo, conditioner, treatment or color treatment, in particular as a shampoo or color treatment.

[0089] The cosmetic formulation of the present invention is particularly suitable for pigmenting and / or repigmenting keratin fibers.

[0090] For the purposes of the present invention, "keratin fibers" are understood to mean hair, especially human hair. The term "human hair" includes, in particular, head hair and beard hair.

[0091] The cosmetic formulation according to the invention for the pigmentation and / or repigmentation of keratin fibers, in particular human hair, ensures that the hair is slowly and gently colored permanently and, at the same time, the keratinocytes in the hair roots are stimulated so that they produce more natural pigment again.

[0092] The use of the cosmetic formulation for the pigmentation and / or repigmentation of human hair is also described, whereby the hair is slowly and gently colored permanently and at the same time the keratinocytes in the hair roots are stimulated so that they produce more natural pigment again.

[0093] The following formulations are intended to clarify the invention without, however, wishing to restrict it to the specific examples. Character description Fig. 1 Comparison photos of strands washed with example recipe 2 (D1 / D2) or comparison recipe (E1 / E2) Fig. 2 Comparison of the color preview for the two shampoos used Example recipe 2 or comparison recipe Fig. 3 Change in color depth when using the shampoos example recipe 2 or comparison recipe as absolute values ​​dL* Fig. 4 Total color change dE* when using the shampoos example recipe 2 or comparison recipe Fig. 5 Change in color depth when washing with color shampoo (5 washes) or washing out with neutral formula (14 washes) Fig.6 Change in color depth when washing with color shampoo (10 washes) or washing out with neutral formula (15 washes) Fig. 7 Change in color depth when washing with color shampoo (15 washes) or washing out with neutral formula (15 washes) Fig. 8 Comparison of the color change for the two shampoos used on a single strand of hair after 15 wash cycles, followed by 15 rinse cycles Fig. 9 Comparison of the color preview for the shampoos used Example Recipe 1 or Example Recipe 2 or Comparison Recipe on a single strand each with 15 wash cycles Figure 10 Change in color depth when using the shampoos Example Recipe 1 or Example Recipe 2 or Comparison Recipe as absolute values ​​dL* Fig. 11 Total color change dE* when using the shampoos Example Recipe 1 or Example Recipe 2 or Comparison Recipe Experimental PartRecipes

[0094] The following recipes were prepared using methods known to those skilled in the art. Comparison recipe

[0095] The comparison formulation contains caffeine as a xanthine derivative and HC Blue 2 as a direct dye. ingredient Amount in wt.% Aqua [water] to 100 Sodium lauryl ether sulfate 11,5 Sodium cocoamphoacetate 3 Cocamidopropyl betaine 1,7 caffeine 1,1 Panthenol 0,92 Sodium chloride 1 Phenoxyethanol 0,7 Cocoglucoside 0,5 Glyceryl oleate 0,5 Phosphoric acid 0,4 PEG-120 Methylglucose dioleate 0,3 HC Blue 2 0,22 menthol 0,2 Polyquaternium-7 0,2 Sodium hydroxide 0,15 Niacinamide 0,1 Zinc PCA 0,1 Dye / dyeing agent 0,1 citric acid 0,06 Example recipe 1

[0096] Example formulation 1 contains dihydroxyindole and caffeine as a xanthine derivative. ingredient Amount in wt.% Aqua [water] to 100 Sodium lauryl ether sulfate 8,0 Sodium myreth sulfate 2,5 Laureth-2 2 Panthenol 1,7 Sodium chloride 1,65 Disodium lauryl sulfosuccinate 1,5 Sodium lauroyl glutamate 1,3 caffeine 1,1 PEG-120 Methylglucose dioleate 0,75 Wheat protein hydrolysate 0,7 Dihydroxyindol 0,49 Allantoin 0,4 citric acid 0,38 Sodium benzoate 0,36 Propylene glycol 0,3 Potassium sorbate 0,3 PEG-40 hydrogenated castor oil 0,18 Cocoglucoside 0,18 Glyceryl oleate 0,17 Polyquaternium-7 0,17 Disodium EDTA 0,15 Zinc PCA 0,1 Niacinamide 0,1 Tocopherol 0,06 Example recipe 2

[0097] Example formulation 2 contains dihydroxyindole, caffeine as a xanthine derivative and HC Blue 2 as a direct dye. ingredient Amount in wt.% Aqua [water] to 100 Sodium lauryl ether sulfate 11,5 Sodium cocoamphoacetate 3 Cocamidopropyl betaine 1,7 caffeine 1,1 Panthenol 0,92 Sodium chloride 1 Phenoxyethanol 0,7 Cocoglucoside 0,5 Glyceryl oleate 0,5 Phosphoric acid 0,4 PEG-120 Methylglucose dioleate 0,3 HC Blue 2 0,22 menthol 0,2 Polyquaternium-7 0,2 Sodium hydroxide 0,15 Dihydroxyindol 0,2 Niacinamide 0,1 Zinc PCA 0,1 Dye / dyeing agent 0,1 citric acid 0,06 Example recipe 3

[0098] Example formulation 3 contains dihydroxyindole, caffeine as a xanthine derivative and HC Blue 2 as a direct dye. ingredient Amount in wt.% Aqua [water] to 100 Sodium lauryl ether sulfate 9 Sodium myreth sulfate 3 Sodium cocoamphoacetate 1 Laureth-2 2 Disodium lauryl sulfosuccinate 1 Sodium lauroyl glutamate 2 caffeine 0,9 Sodium chloride 1 Wheat protein hydrolysate 0,7 Phosphoric acid 0,3 Sodium benzoate 0,5 Potassium sorbate 0,2 HC Blue 2 1 Allantoin 0,4 PEG-40 hydrogenated castor oil 0,4 Polyquaternium-7 0,2 Disodium EDTA 0,2 Dihydroxyindol 0,3 Tocopherol 0,02 Example recipe 4

[0099] Example formulation 4 contains dihydroxyindole, caffeine as a xanthine derivative and HC Blue 2 as a direct dye. ingredient Amount in wt.% Aqua [water] to 100 Sodium lauryl ether sulfate 11 Sodium myreth sulfate 2 Laureth-2 3 Cocoamidopropyl betaine 2 Disodium lauryl sulfosuccinate 1 Sodium lauroyl glutamate 1 Panthenol 0,5 caffeine 1 Sodium chloride 0,9 Phenoxyethanol 0,5 Wheat protein hydrolysate 0,5 Cocoglucoside 0,3 Glyceryl oleate 0,4 Phosphoric acid 0,25 Sodium benzoate 0,2 PEG-120 Methylglucose dioleate 0,1 Potassium sorbate 0,5 HC Blue 2 0,8 Allantoin 0,1 PEG-40 hydrogenated castor oil 0,2 menthol 0,2 Sodium hydroxide 0,1 Disodium EDTA 0,2 Dihydroxyindol 0,1 citric acid 0,03 Niacinamide 0,2 Zinc PCA 0,2 Dye / dyeing agent 0,1 Example recipe 5

[0100] Example formulation 5 contains dihydroxyindole and caffeine as a xanthine derivative. ingredient Amount in wt.% Aqua [water] to 100 Sodium lauryl ether sulfate 12 Sodium cocoamphoacetate 2 Cocoamidopropyl betaine 2 Panthenol 1 caffeine 1,1 Sodium chloride 0,9 Phenoxyethanol 0,8 Cocoglucoside 0,4 Glyceryl oleate 0,3 Phosphoric acid 0,3 PEG-120 Methylglucose dioleate 0,2 menthol 0,2 Polyquaternium-7 0,1 Sodium hydroxide 0,2 Disodium EDTA 0,1 Dihydroxyindol 0,2 citric acid 0,06 Niacinamide 0,2 Zinc PCA 0,2 Dye / dyeing agent 0,5 Neutral recipe

[0101] The neutral formula contains neither caffeine nor DHI nor HC Blue 2. ingredient Amount in wt.% Aqua [water] to 100 Sodium lauryl ether sulfate 10 Laureth-2 1,9 Disodium lauryl sulfosuccinate 1,5 Sodium chloride 1,3 Sodium lauroyl glutamate 1,3 Panthenol 1,2 PEG-120 Methylglucose dioleate 0,5 Wheat protein hydrolysate 0,49 citric acid 0,4 Sodium citrate 0,35 Propylene glycol 0,2 menthol 0,2 PEG-40 hydrogenated castor oil 0,2 Potassium sorbate 0,19 Polyquaternium-7 0,17 Disodium EDTA 0,11 Sodium benzoate 0,1 Zinc PCA 0,06 Niacinamide 0,055 Tocopherol 0,032 Dye / staining agent 0,0005 Application examples

[0102] To evaluate the dyeing performance in terms of quality, intensity and duration, the following washing tests (wash-up and wash-out tests) were carried out. Application example 1

[0103] Kerling strands were subjected to a wash-up test with a shampoo containing 5,6-DHI, caffeine, and HC Blue 2 (example formulation 2) or with a shampoo containing HC Blue 2 and caffeine (comparison formulation) to investigate the coloring performance in terms of quality and intensity.

[0104] Washing protocol: - Moisten strands with lukewarm water for 30 seconds, then smooth out excess water between two fingers - Massage in a total of 5 g of shampoo for 1 minute per 5 strands - Leave on for a total of 5 minutes - Rinse with lukewarm water for 1 minute, then squeeze out in kitchen paper - Comb, spread out individually and let air dry - The next day, scan the strands with the Konica (Konica-Minolta Spectrophotometer CM600d, measuring geometry d / 8°, Specular Component Excluded (SCE), standard illuminant D65, field of view 10°) (photograph sample strands every 5 wash cycles); then repeat the wash cycle

[0105] Hair strands used: Kerling white selected, adhesive braid 2 cm wide, 12 cm long, 3 g / pc., Ch. 1719

[0106] Shampoos used: Example recipe 2 strands D1-D5 Comparison recipe strands E1-E5 5 strands were used per product and 28 washes were carried out.

[0107] Fig. Figure 1 shows a comparison of strands D1 / D2 treated with example recipe 2 with strands E1 / E2 treated with the comparison recipe.

[0108] The comparison of the color preview for the two shampoos used is in Fig. 2. The Fig. 3 and Fig. 4 show the change in color depth as absolute values ​​dL* ( Fig. 3) or as total color change dE* ( Fig. 4). The figures show the gradual build-up of the color effect with repeated application, as well as the improved coloring result compared to the reference formulation. Application example 2

[0109] Kerling strands were subjected to a wash-on and wash-out test with a shampoo containing 5,6-DHI, caffeine, and HC Blue 2 (example formulation 2) or with a shampoo containing HC Blue 2 and caffeine (comparison formulation) to investigate the coloring performance in terms of quality, intensity, and duration.

[0110] Washing protocol: - Moisten strands with lukewarm water for 30 seconds, then smooth out excess water between two fingers - Massage in a total of 5 g of shampoo for 1 minute per 5 strands - Leave on for a total of 5 minutes - Rinse with lukewarm water for 1 minute, then squeeze out in kitchen paper - Comb, spread out individually and let air dry - The next day, scan the strands with the Konica (Konica-Minolta Spectrophotometer CM600d, measuring geometry d / 8°, Specular Component Excluded (SCE), standard illuminant D65, field of view 10°), photograph them; then repeat the wash cycle

[0111] Hair strands used: Kerling white selected, adhesive braid 2cm wide, 12cm long

[0112] Coloring shampoos used: Example recipe 2 strands B1-B15 Comparison recipe highlights C1-C15

[0113] The neutral recipe was used for washing out.

[0114] For each product, 15 strands were treated in portions of 5 each.

[0115] The color change was monitored over the following wash-up and wash-out cycles: - 5 washes each with coloring shampoo, followed by 14 washes with neutral formula ( Fig. 5) - 10 washes each with coloring shampoo, followed by 15 washes with neutral formula ( Fig. 6) - 15 washes each with coloring shampoo, followed by 15 washes with neutral formula ( Fig. 7).

[0116] The Fig.Figures 5-7 show the change in color depth when washing with color shampoo or washing out with a neutral formula according to the protocols given above. Fig. Figure 8 shows the comparison of the color change for the two shampoos used on a single strand of hair after 15 wash-ins followed by 15 wash-outs, measured with the Konica measuring instrument (Konica-Minolta Spectrophotometer CM600d, measurement geometry d / 8°, Specular Component Excluded (SCE), standard illuminant D65, field of view 10°). The figures demonstrate the gradual buildup of the color effect with repeated use, as well as the improved coloring result compared to the comparison formulation. After discontinuing treatment with the shampoo according to the invention, the color effect also lasts longer than when using the comparison formulation. Application example 3

[0117] White Virgin strands (Imhair) were subjected to a wash-up test with a shampoo containing 5,6-DHI and caffeine (example formulation 1) or with a shampoo containing 5,6-DHI, caffeine, and HC Blue 2 (example formulation 2) or with a shampoo containing HC Blue 2 and caffeine (comparison formulation) to investigate the coloring performance in terms of quality and intensity.

[0118] Washing protocol: - Moisten strands with lukewarm water for 30 seconds, then smooth out excess water between two fingers - Massage 2 g of shampoo into each of the 3 strands for 30 seconds - Leave on for a total of 5 minutes - Rinse with lukewarm water for 1 minute - Comb, air dry - The next day, scan strands with the Konica, photograph them; then repeat the wash cycle

[0119] Hair strands used: White Virgin (Imhair) Shampoos used: Example recipe 1 strands 1-3 Example recipe 2 strands 4-6 Comparison recipe strands 7-9

[0120] Three strands were used per product and 15 washes were carried out.

[0121] The comparison of the color preview for the shampoos used is for a single strand of hair in Fig. 9. The Fig. 10 and Fig. 11 show the change in color depth as absolute values ​​dL* ( Fig. 10) or as total color change dE* ( Fig. 11). The figures show the gradual build-up of the color effect with repeated application as well as the improved coloring result compared to the comparison formulation. Application example 4

[0122] To examine the final shade over time, the Kerling white and Imhair bleached strands were dyed for 15 minutes with 10 g of Sample Formula 2, rinsed for 1 minute, and air-dried for 1.5 hours (residual moisture was then blow-dried). Measurements were taken on the day of treatment, after 15 minutes of exposure time (initial shade), and after 1, 2, 3, 8, 9, 10, 11, 14, and 15 days. L*(D65) a*(D65) b*(D65) dL*(D65) there*(D65) db*(D65) dE*ab(D65) Streak Kerling, white 76,58 2,15 21 - - - - Initial shade (after 15 min exposure time) 62,32 1,58 5,02 -14,27 -0,57 -15,98 21,43 read after 1d 62,11 2,05 5,23 -14,48 -0,1 -15,77 21,41 read after 2d 63,06 2,22 4,59 -13,52 0,07 -16,42 21,27 read in 3d 63,02 2,44 5,09 -13,56 0,29 -15,91 20,91 read after 8 days 62,95 2,53 5,57 -13,64 0,38 -15,44 20,6 read after 9 days 62,86 2,35 5,5 -13,73 0,21 -15,51 20,71 read after 10 days 62,63 2,57 5,87 -13,95 0,42 -15,13 20,58 read after 11d 62,59 2,61 5,47 -14 0,46 -15,53 20,91 read after 14 days 63,16 3,1 6,34 -13,43 0,95 -14,67 19,91 read after 15 days 63,59 3,16 6,26 -12,99 1,02 -14,74 19,68 L*(D65) a*(D65) b*(D65) dL*(D65) there*(D65) db*(D65) dE*ab(E65) strand Imhair, bleached 76,9 3,5 24,61 - - - - Initial shade (after 15 min exposure time) 51,51 1,01 2,73 -25,38 -2,49 -21,88 33,61 read after 1d 51,71 1,6 2,8 -25,19 -1,9 -21,82 33,38 read after 2d 52,11 1,61 2,79 -24,78 -1,89 -21,82 33,08 read in 3d 51,57 2,06 3,23 -25,33 -1,43 -21,38 33,17 read after 8 days 52,21 2,22 3,78 -24,68 -1,28 -20,84 32,33 read after 9 days 51,98 2,13 3,84 -24,92 -1,36 -20,78 32,47 read after 10 days 52 2,29 4,16 -24,9 -1,21 -20,46 32,24 read after 11d 52,11 2,29 4,16 -24,79 -1,21 -20,46 32,16 read after 14 days 52,69 2,65 4,86 -24,21 -0,84 -19,75 31,25 read after 15 days 53,23 2,68 5,01 -23,67 -0,82 -19,61 30,74

[0123] The measured values ​​demonstrate a - also visually perceptible - shift in nuance from the original graphite to a more natural, brownish color. QUOTES CONTAINED IN THE DESCRIPTION

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

[0000] EP 0 530 229 B1

[0007] WO 99 / 66890

[0009] DE 10 2018 127 182 A1

[0010] DE 10 2007 038 484 A1

[0011] WO 2005 / 007615 A1

[0012] Cited non-patent literature

[0000] Milton Rosen and Joy Kunjappu, John Wiley & Sons, Inc.-Verlag, 2012, 4

[0059] Goddard, E. Desmond; Gruber, James V. (1999), "Principles of polymer science and technology in cosmetics and personal care", Series: Cosmetic science and technology series : v. 22., New York (Marcel Dekker, INC.); Schrader, Karlheinz (1989), "Fundamentals and formulations of cosmetics" (2nd edition), Chapter 3.7, Heidelberg (Hüthig); and Scott, Richard (2017), "Ingredients focus: cosmetic waxes and butters", Personal Care Europe 10(3), 46-47

[0082] Trüeb, RM (2009). “Successfully treating dandruff.” Akt Dermatol 35(01 / 02): 19-24; Trueb, RM (2007). “Shampoos: ingredients, efficacy, and adverse effects.” J. Dtsch. Dermatol. Ges. 5(5): 356-365; Sanfilippo, A. and J. English (2006). “An overview of medicated shampoos used in dandruff treatment.” P AND T 31(7): 396; and Futterer, E. (1981). “Evaluation of efficacy of antidandruff agents.” J Soc Cosmet Chem 32: 327-338

[0083] Pietrzik K, Golly I, Loew D, Handbook of Vitamins, Elsevier GmbH, Urban & Fischer Verlag, Munich 2008; H. Lautenschläger, Vitamins in Cosmetics, Medical Beauty Forum 2020 (3), 14-17; and Martini MC, Chivot M, Peyrefitte G, Textbook of Cosmetics: Fundamentals - Basic Ingredients - Basic Techniques, Hogrefe AG, Bern 2001

[0084]

Claims

[1] Cosmetic formulation containing a dye precursor selected from the group consisting of indoline derivatives and indole derivatives and at least one direct dye. [2] Cosmetic formulation according to claim 1, wherein the dye precursor is an indole derivative. [3] Cosmetic formulation according to claim 1 or claim 2, wherein the dye precursor is a derivative of 5,6-dihydroxyindole of formula (I), wherein, in each case independently of one another, R 1 represents hydrogen, a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, R 2 hydrogen or a-COOH group, where the-COOH group can also be present as a salt with a physiologically acceptable cation, R 3 represents hydrogen or a C1-C4 alkyl group, R 4 Hydrogen, a C1-C4 alkyl group, an amino group or a group -CO-R 6 means in the R6 a C1-C4 alkyl group, and R 5 one of the under R 4 mentioned groups means or a physiologically acceptable salt of these compounds with an organic or inorganic acid. [4] Cosmetic formulation according to claim 3, wherein the compound of formula (I) is selected from 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole and their physiologically acceptable salts. [5] Cosmetic formulation according to any one of claims 1-4, wherein the dye precursor is an indoline derivative. [6] Cosmetic formulation according to any one of claims 1-5, wherein the dye precursor is a derivative of 5,6-dihydroxyindoline of formula (II), wherein, in each case independently of one another, R 1 represents hydrogen, a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group, R 2hydrogen or a-COOH group, where the-COOH group can also be present as a salt with a physiologically acceptable cation, R 3 represents hydrogen or a C1-C4 alkyl group, R 4 Hydrogen, a C1-C4 alkyl group, an amino group or a group -CO-R 6 means in the R 6 a C1-C4 alkyl group, and R 5 one of the under R 4 mentioned groups means or a physiologically acceptable salt of these compounds with an organic or inorganic acid. [7] Cosmetic formulation according to claim 6, wherein the compound of formula (II) is selected from 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline and their physiologically acceptable salts. [8] Cosmetic formulation according to any one of claims 1-7, wherein the direct dye is selected from the group consisting of 2-amino-6-chloro-4-nitrophenol, 1,4-bis-(β-hydroxyethyl)-amino-2-nitrobenzene, Basic Yellow 57, Basic Red 76, Basic Brown 16, Basic Brown 17, Basic Blue 99, HC Blue 2, HC Blue 12, HC Blue 16 and Acid Violet 43, preferably HC Blue 2.

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