Recoloring agent for keratin fibers, especially human hair

Abstract

The present invention relates to a cosmetic formulation containing a colorant precursor selected from the group consisting of indole derivatives and indoline derivatives, and a xanthine derivative. The present invention also relates to the use of the cosmetic formulation for recoloring keratin fibers, in particular human hair.

Description

[Technical Field]

[0001] The present invention relates to a cosmetic preparation containing a dye precursor selected from the group consisting of indole derivatives and indoline derivatives, and a xanthine derivative. The present invention further relates to the use of the cosmetic preparation for recoloring keratin fibers, in particular human hair.

[0002] Human hair color depends on the amount of melanin, known as eumelanin and pheomelanin. Eumelanin and pheomelanin are contained in the hair fiber layer and are produced by melanocytes within the hair follicle. As part of normal aging, as well as certain diseases, stress, vitamin and mineral deficiencies, and excessive alcohol and nicotine intake, melanin production decreases, resulting in depigmentation. Such hair appears white or colorless to the observer. The optical impression of gray hair results from the mixture of pigmented and non-pigmented hair.

[0003] The average lifespan of a hair is 3 to 7 years, after which it falls out and is replaced by new hair. Gradually, the proportion of white or unpigmented hair increases, and hair turns gray.

[0004] Hair color change, especially coloring or recoloring gray hair, is an important part of modern cosmetics. In particular, good fastness and good gray coverage, as well as long-lasting color payoff, are desired.

[0005] For permanent, intensive dyeing with good fastness properties and good gray coverage, oxidation dyes have traditionally been used. Such dyes usually contain oxidation dye precursors, so-called developer and coupler components, which, under the influence of an oxidizing agent such as hydrogen peroxide or atmospheric oxygen, couple with each other or with one or more coupler components to form the actual dye.

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

[0007] Alternatively, a precursor to the natural hair dye melanin can be applied to hair, which forms a substantially natural dye as part of the hair's oxidation process. Color development can occur using atmospheric oxygen as the only oxidizing agent, so no additional oxidizing agent is required. Such a method, using 5,6-dihydroxyindoline as a dye precursor, is described, for example, in EP 0 530 229 B1.

[0008] Direct dyes, also known as solid dyes, are used for temporary dyes. They apply dye molecules directly to the hair, eliminating the need for an oxidation step to create color. Compared to oxidation dyes, direct dyes are less durable and wash out more quickly. Direct dye color typically lasts for 5-20 washes.

[0009] WO 99 / 66890 describes dyes for dyeing keratin fibers, which contain an indoline or indole derivative, such as a derivative of 5,6-dihydroxyindoline or 5,6-dihydroxyindole, and a dye precursor, which may be an amino acid or an oligopeptide, and 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, which comprises, separately from each other, an anhydrous carrier medium containing an alkane, a fatty alcohol, and an alcohol, and an aqueous phase containing hydrogen peroxide. For hair protection and care, the system may contain organosilicon compounds from the silane group.

[0011] DE 10 2007 038 484 A1 describes a hair treatment agent for protection against external influences, which comprises a bacterial fermentation product from Thermus thermophilus.

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

[0013] However, with the formulations known in the art, it is not possible to achieve fully satisfactory results in terms of quality, intensity and duration of color performance while at the same time leaving the hair structure as intact or damaged as possible.

[0014] Thus, with the precursors of natural hair dye melanin, the resulting color bodies are formed after a significant time delay, making it difficult to control the color shade. Furthermore, intermediate shades often have an unnatural purple hue. Another drawback is the appearance of a non-pigmented hairline as the hair grows longer.

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

[0016] Based on this, the problem underlying the present invention was to provide a cosmetic formulation suitable for coloring or recoloring keratin fibers, in particular human hair, and which in particular provides improved fastness properties of the colored or recolored keratin fibers and improved gray coverage. Furthermore, this cosmetic formulation should have improved properties in terms of quality, intensity and duration of coloring performance compared to formulations known from the prior art.

[0017] This problem has surprisingly been solved by the formulation according to claim 1 and its use according to claim 11. Preferred embodiments are set out in the dependent claims.

[0018] According to the present invention, this problem is solved by providing a cosmetic preparation containing a dye precursor selected from the group consisting of indole derivatives and indoline derivatives, and a xanthine derivative.

[0019] Surprisingly, it was found that while the natural pigmentation of the hair roots was stimulated, the existing hairs darkened, resulting in a much lower contrast with the regenerating hair (at the hairline).

[0020] The hair gradually darkens overall, allowing the color effect to build up gradually, clearly covering the gray hair and making the overall impression of the hair color appear significantly darker.

[0021] The cosmetic formulation according to the invention therefore achieves good grey coverage and excellent fastness properties, while at the same time providing long-lasting colour performance and reducing grey hair at the hairline.

[0022] The xanthine derivatives contained in the formulations according to the present invention, together with the dye precursors, stimulate the keratinocytes in the hair roots to produce more natural pigment again. Furthermore, the xanthine derivatives allow the hair to remain on the scalp longer. This slows down the loss of still pigmented hair and also contributes to the natural re-coloring of already poorly pigmented or unpigmented hair. In the context of the present invention, the terms coloring and re-coloring are used interchangeably.

[0023] The dye precursors contained in the formulations according to the present invention, which are indole and / or indoline derivatives, are preferably indole and / or indoline derivatives having a hydroxyl or amino group as a substituent on the six-membered ring. These groups can have further substituents, for example, in the form of etherification or esterification of the hydroxyl group or alkylation of the amino group. Compounds having two of these groups, especially compounds having two hydroxyl groups, one or both of which may be etherified or esterified, are particularly preferred.

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

[0025] According to the present invention, the dye precursor preferably has formula (I):

[0026] [ka]

[0027] (where, independently of each other, R 1 is hydrogen, a C1-C4-alkyl group or a C1-C4-hydroxyalkyl group, R 2 is hydrogen or a -COOH group, which may also exist as a salt with a physiologically acceptable cation, R 3 is hydrogen or a C1-C4-alkyl group, R 4 is hydrogen, a C1-C4 alkyl group, an amino group, or R 6 is a C1-C4-alkyl group -CO-R 6 and R 5 is R 4 or physiologically acceptable salts of these compounds with organic or inorganic acids.

[0028] 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.

[0029] In one particularly preferred embodiment, the compound of formula (I) is selected from 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole and physiologically acceptable salts thereof.

[0030] Particularly preferably, the dye precursor used in the formulation according to the invention is 5,6-dihydroxyindole.

[0031] In a further preferred embodiment of the present invention, the dye precursor is an indoline derivative.

[0032] According to the present invention, the dye precursor preferably has formula (II):

[0033] [ka]

[0034] (where, independently of each other, R 1 is hydrogen, a C1-C4-alkyl group or a C1-C4-hydroxyalkyl group, R 2 is hydrogen or a -COOH group, which may also exist as a salt with a physiologically acceptable cation, R 3 is hydrogen or a C1-C4-alkyl group, R 4 is hydrogen, a C1-C4 alkyl group, an amino group, or R 6 is a C1-C4-alkyl group -CO-R 6 and R 5 is R 4 or physiologically acceptable salts of these compounds with organic or inorganic acids.

[0035] Preferred representatives according to the invention are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindole.

[0036] In one particularly preferred embodiment, the compound of formula (II) is selected from 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline and physiologically acceptable salts thereof.

[0037] Particularly preferably, the dye precursor used in the formulations according to the invention is 5,6-dihydroxyindoline.

[0038] In another particularly preferred embodiment, the dye precursor used in the formulations according to the invention is dihydroxyindoline hydrobromide (2,3-dihydro-1H-indole-5,6-diol hydrobromide).

[0039] The indole and indoline derivatives contained in the agents according to the invention can be used either as a free base or in the form of a physiologically acceptable salt with an inorganic or organic acid, such as a hydrochloride, sulfate or hydrobromide.

[0040] In the formulations according to the invention, the indole or indoline derivative is usually present in an amount of 0.001 to 5% by weight, preferably 0.005 to 2% by weight, preferably 0.01 to 2% by weight, preferably 0.01 to 1.5% by weight, preferably about 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.5% by weight, in each case based on the total weight of the formulation.

[0041] In a particularly preferred embodiment, the dye precursor is an indole derivative, preferably 5,6-dihydroxyindole, which is present in the formulations according to the invention in an amount of 0.01 to 2% by weight, preferably 0.05 to 0.6% by weight, preferably 0.08 to 0.5% by weight, preferably about 0.1 to 0.5% by weight, in each case based on the total weight of the formulation.

[0042] 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 present in the formulations according to the invention in an amount of in each case about 0.01 to 4.0% by weight, preferably 0.05 to 2.0% by weight, preferably about 0.08 to 1.0% by weight, preferably about 0.1 to 0.5% by weight, based on the total weight of the formulation.

[0043] Formulations according to the invention may also contain one or more indole or indoline derivatives or mixtures of indole and indoline derivatives.

[0044] The pigments are produced from dye precursors, i.e., indole or indoline derivatives, by reaction with atmospheric oxygen: no additional oxidizing agent is required.

[0045] The xanthine derivatives contained in cosmetic formulations, together with dye precursors, stimulate keratinocytes, especially in the hair root, to produce more natural pigment again. Furthermore, the xanthine derivatives help hair to stay longer on the scalp, slow down the loss of hair that still has pigment, and contribute to the natural re-coloring of hair that is already low in pigment or has a pigment deficiency.

[0046] A preferred xanthine derivative according to the present invention is caffeine.

[0047] The IUPAC name for caffeine is 1,3,7-trimethyl-3,7-dihydro-1H-purine-2,6-dione. Alternatively, caffeine is known as 1,3,7-trimethylxanthine. Caffeine has the following chemical formula (III):

[0048] [ka]

[0049] Caffeine is an alkaloid belonging to the methylxanthine family. It is a bitter-tasting crystalline substance that can be considered a purine derivative, chemically related to the adenine and guanine bases of deoxyribonucleic and ribonucleic acids.

[0050] In the formulations according to the invention, the xanthine derivatives are usually present in an amount of 0.0001 to 10% by weight, preferably 0.01 to 5% by weight, preferably 0.05 to 2% by weight, preferably 0.1 to 1.5% by weight, preferably about 0.0001% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.5% by weight, 0.7% by weight, 1.0% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, in each case based on the total weight of the formulation.

[0051] In one preferred embodiment, the formulation according to the invention further comprises at least one direct dye.

[0052] Surprisingly, it has been found that the color effect of formulations containing indole or indoline-type dye precursors and xanthine derivatives as well as direct dyes is stronger than would be expected based on the color effects of the individual components, the indole or indoline-type dye precursors and the direct dyes. The darkening effect (recolorization) is synergistically enhanced in terms of color penetration rate and color strength in combination with the direct dye.

[0053] Thus, in the presence of a combination of an indole or indoline type dye precursor and a direct dye, a synergistic effect occurs, as a result of which the cosmetic preparation according to the invention comprising an indole or indoline type dye precursor, a xanthine derivative and a direct dye advantageously achieves particularly strong color effects with excellent gray coverage and good fastness properties, i.e., highly natural shades with long-lasting dyeing results.

[0054] As mentioned at the beginning, direct dyes apply dye molecules directly to the hair and do not require an oxidation process to form color.

[0055] Preferred direct dyes include nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones and indophenols, preferably those having 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 Dyes known as Black 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-nitrobenzene, 1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene 4-amino-3-nitrophenol, 1-(2-ureidoethyl)amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, hydroxyethyl-2-nitro-toluidine, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

[0056] In general, the direct dyes are contained in an amount of 0.001 to 5% by weight, preferably 0.05 to 3% by weight, preferably 0.1 to 2% by weight, preferably 0.1 to 1.2% by weight, preferably about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% by weight, in each case based on the total weight of the formulation.

[0057] 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.

[0058] In one particularly preferred embodiment of the invention, the direct dye is HC Blue 2.

[0059] In a particularly preferred embodiment, the formulation according to the invention contains 5,6-dihydroxyindole as the dye precursor and caffeine as the xanthine derivative, wherein 5,6-dihydroxyindole is contained in an amount of 0.05 to 0.6% by weight in each case, based on the total weight of the formulation, and caffeine is contained in an amount of 0.8 to 1.2% by weight in each case, based on the total weight of the formulation.

[0060] In a further particularly preferred embodiment, the formulation according to the invention contains 5,6-dihydroxyindole as dye precursor, caffeine as xanthine derivative and additionally HC Blue 2 as direct dye, wherein 5,6-dihydroxyindole is contained in an amount of 0.05 to 0.6% by weight, caffeine is contained in an amount of 0.8 to 1.2% by weight and the direct dye is contained in an amount of 0.1 to 1.2% by weight, in each case based on the total weight of the formulation.

[0061] Furthermore, the cosmetic preparation according to the invention may contain any additives (ie active ingredients, additives and excipients) known in such preparations.

[0062] In one embodiment, the cosmetic formulation comprises a surfactant. The surfactant may be an anionic, nonionic, cationic, or zwitterionic surfactant. Preferably, the surfactant is an anionic or nonionic surfactant, and in particular an anionic or nonionic surfactant that is as mild as possible (i.e., particularly well tolerated by the skin). According to the present invention, nonionic surfactants are particularly used due to their very good emulsifying properties and their excellent skin care properties. Anionic surfactants are preferred because they have particularly high cleansing performance. Therefore, they are particularly suitable for cleansing formulations such as shampoos. Cationic surfactants have excellent hair care properties and are used according to the present invention, especially in hair care formulations such as conditioners, shampoos, and treatments.

[0063] The formulations according to the invention preferably contain surfactants in an amount of 2 to 40% by weight, in particular 5 to 30% by weight, preferably 7 to 20% by weight, and particularly preferably 10 to 17% by weight, in each case based on the total weight of the formulation. Suitable amounts of surfactants are as follows: 8% by weight; 9% by weight; 10% by weight; 11% by weight; 12% by weight; 13% by weight; 14% by weight; 15% by weight; 16% by weight; 17% by weight; 18% by weight; 19% by weight; 20% by weight; 21% by weight; 22% by weight; 23% by weight; 24% by weight; and 25% by weight, in each case based on the total weight of the formulation. Particularly preferably, the cosmetic formulations according to the invention contain one or more anionic surfactants in an amount of 0.1 to 20% by weight, preferably 1 to 17% by weight, and particularly preferably 5 to 15% by weight, in each case based on the total weight of the formulation. Suitable amounts of anionic surfactants are as follows: 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, based on the total weight of the formulation. At these amounts, the surfactants have particularly high cleansing performance and are very well tolerated by the skin, scalp and hair.

[0064] The surfactants of the present invention are described in particular in "Surfactants and interfacial phenomena" by Milton Rosen and Joy Kunjappu, John Wiley & Sons, Inc., 2012, 4th edition.

[0065] 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 preferred surfactants are selected from alkyl carboxylates, alkyl sulfates, alkyl sarcosinates, alkyl taurates, alkyl glutamates (e.g., sodium cocoyl glutamate / disodium cocoyl glutamate), alkyl glycinates, alkyl alanines (e.g., sodium cocoyl alanine), and mixtures thereof.Similarly, fatty alcohol polyglycerol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, and α-olefin sulfonates are also preferred due to their cleaning performance.

[0066] Alkyl carboxylates have the general formula RCO2M, alkyl sulfates have the general formula ROSO3M, alkyl sarcosinates have the general formula RC(O)N(CH3)CH2CO2M, and alkyl taurates have the general formula RC(O)N(CH3)CH2SO3M, where R is each C4-C 26 -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 C 12 -C 16 -Alkyl or C 12 -C 18 - alkyl.

[0067] In one embodiment, the surfactant is a nonionic surfactant (also called 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.

[0068] 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.

[0069] In the present invention, the term "glycerol fatty acid ester" refers to a glycerol mono-fatty acid ester or a glycerol di-fatty acid ester. A glycerol di-fatty acid ester is represented by the formula R 3 -COO-(CH2CH(OH)CH2)-OOR 4 or R 3 -COO-(CH2CH(OOR 4 )CH2)—OH. Glycerol mono-fatty acid esters have the formula R 3 -COO-(CH2CH(OH)CH2)-OH or HO-(CH2CH(OOR 3 )CH2)—OH, where R 3 and R 4 independently, C6-C 28 -Alkyl and C6-C 28 -alkenyl. Glycerol mono fatty acid esters contain a glycerol group linked to a single fatty acid via an ester bond. Examples are glycerol monostearate, glycerol monobehenate, glycerol monocaprylate, glycerol monocaprate, and glycerol monolaurate.

[0070] Fatty alcohols (saturated) have the formula H3C-(CH2) n In the compound of formula —CH2—OH, n is an integer from 4 to 20, preferably from 6 to 16.

[0071] Polyoxyethylene ethers are those of the formula R 5 (OC2H3) n OH, where R 5 is C6-C 28 -Alkyl, C6-C 28 -alkenyl, substituted and unsubstituted phenoxy groups; n is an integer greater than 1. Preferably, the one or more polyoxyethylene ethers of fatty alcohols are selected from the group of steareth-2, steareth-21, macrogolcetostearyl ether 12, ceteareth-25, macrogolcetostearyl ether 20 and mixtures of the aforementioned compounds. Even more preferably, the polyoxyethylene ether is a compound selected from the group of ceteareth-25, macrogolcetostearyl ether 20 and mixtures of the aforementioned compounds.

[0072] The term "polyglycerol ether of a fatty alcohol" refers to a compound of formula R 6 O-(C3H6O2) n -H, where R 6 is a branched or linear C6-C 28 -Alkyl or C6-C 28 -alkenyl, where n is an integer greater than 1, preferably an integer from 2 to 10. Preferably, the formulation comprises 0.01 to 15.0 wt. %, 0.1 to 10.0 wt. % or 1 to 5.0 wt. % of the polyglycerol ether.

[0073] The term "polyglycerol ester of fatty acids" refers to a polyglycerol ester of fatty acids containing a polyglycerol unit and at least one C6-C 26 -Alkyl or C6-C 26 -alkenyl carboxylic acid units. These compounds have the formula R 7 -R 8 -(C3H6O2) n -H, where R7 is C6-C 26 -Alkanoates or C6-C 26 -alkenoate residue, R 8 is a suitable linking molecule or direct bond. Thus, the polyglycerol moiety and the C6-C 26 -Alkyl or C6-C 26 The -alkenyl carboxylic acid moieties may be directly linked by an ester bond or may contain a linker moiety connecting the two moieties to each other. Non-limiting examples of this group are polyglyceryl-3-methylglucose distearate, polyglycerol polycrylolate, 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.

[0074] In one embodiment, the surfactant includes a cationic surfactant, such as a quaternary surfactant. Quaternary surfactants contain at least one N atom covalently bonded to four alkyl or aryl groups. This results in a positive charge regardless of the pH value. Alkyl betaine, alkylamidopropyl betaine, and alkylamidopropyl hydroxysulfine are preferred. Cationic surfactants used in accordance with the present invention are also preferably cationic compounds, such as quaternary ammonium compounds, especially benzyltrialkylammonium chloride or bromide, such as benzyldimethylstearylammonium chloride, and alkyltrialkylammonium salts, such as cetyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium chloride or bromide, dialkyldimethylammonium chloride or bromide, alkylamidoethyltrimethylammonium ether sulfate, alkylpyridinium salts, such as lauryl or cetylpyrimidinium chloride, imidazoline derivatives, and amine oxides, such as alkyldimethylamine oxide or alkylaminoethyldimethylamine oxide. The use of cetyltrimethylammonium salts is particularly preferred.

[0075] In a further embodiment, the formulation according to the invention comprises at least one additive, preferably an additive typically used in shampoos, conditioners and emulsions for treating the skin, scalp and hair. The at least one additive may be present in a proportion of 0.01 to 12.0% by weight, more preferably 0.25 to 10.0% by weight, and in particular 1.0 to 7.0% by weight.

[0076] The at least one additive may further be selected from the group consisting of hair conditioning agents, moisturizers, preservatives, stabilizers, fragrances, antioxidants, rheology modifiers, thickeners, care agents, dyes, pearlizing agents, gloss agents, solvents, solidifying compounds, anti-dandruff agents, vitamins, alkalizing agents or pH adjusters and combinations thereof.

[0077] Hair conditioning agents can reduce static electricity on hair by neutralizing the charge on the hair surface. Examples of hair conditioning agents are quaternary ammonium compounds.

[0078] Moisturizers, also known as moisturizers or superfatting agents, are lipophilic substances that prevent the destructive effects of the epidermal barrier function. Examples of moisturizers include lanolin, squalene, liquid paraffin, vegetable oils, silicones, and cetyl palmitate.

[0079] Preservatives are substances used to preserve formulations by killing and / or inhibiting the growth of microorganisms that degrade them. Preferably, the preservative may 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 formulations according to the present invention. Sodium benzoate releases benzoic acid, and potassium sorbate releases sorbic acid in a weakly acidic environment. Both acids are said to have antibacterial effects.

[0080] The stabilizer can protect the photosensitive component from radiation and is preferably a UV absorber such as a benzophenone derivative.

[0081] Flavorings can be added to give the formulation a pleasant odor, examples being flavors known to the expert.

[0082] Antioxidants or antioxidants are chemical compounds that slow or completely prevent the oxidation of other ingredients in the formulations according to the invention. Examples of antioxidants include citric acid, ascorbic acid, sodium sulfite, and butylated hydroxyanisole.

[0083] Rheology modifiers and thickeners can help improve the application properties of the formulations according to the present invention. The addition of common salts (sodium chloride) can be considered as rheology modifiers and thickeners. The addition of common salts can affect the flowability of the formulations according to the present invention within a certain range and adjust it to the required level. Naturally occurring gelling agents can also be used as thickeners, and are preferably selected from agar, xanthan gum, cellulose and / or cellulose derivatives, or alginic acid.

[0084] In the context of this application, care agents are understood as substances that provide care to the hair and / or scalp. Hydrolyzed wheat protein, panthenol and allantoin have a nourishing effect on the scalp and hair. Hydrolyzed wheat protein primarily has moisturizing properties.

[0085] As an additional dye, the formulations according to the invention can contain colorants, for example to give the formulations an optically attractive color. The formulations according to the invention can contain, for example, CI 47005 as a suitable colorant.

[0086] The solvent used may be any solvent or solvent mixture commonly used by those skilled in the art. Preferred solvents are ethanol or butylene glycol, particularly 1,4-butylene glycol, propylene glycol, and isopropyl alcohol. Ethanol or propylene glycol is preferred. These solvents may be present in the formulation according to the present invention in an amount of 0.1 to 70% by weight. Most preferably, they are present in an amount of 0.1 to 5.0% by weight.

[0087] Solidifying compound is preferably selected from the group consisting of wax, synthetic polymer and their mixture.Suitable solidifying compound is known to those skilled in the art, and can be 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 (Huthig); and Scott, Richard (2017), "ingredients focus: cosmetic waxes and butters" Personal Care Europe 10(3), 46-47.

[0088] Antidandruff agents are used to suppress excessive formation of dandruff on scalp.Suitable antidandruff agents are known to those skilled in the art, and can be found in, for example, Trueb, RM (2009) "Kopfschuppen erfolgreich behandeln" 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: 327-33.

[0089] Vitamins and minerals such as niacinamide (vitamin B3), vitamin E or zinc are used to achieve a favorable effect on the growth and repair of 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, Handbuch Vitamine, Elsevier GmbH, Urban & Fischer Verlag, Munich 2008; H. Lautenschlager, Vitamine in der Kosmetik, medical Beauty Forum 2020 (3), 14-17; and Martini MC, Chivot M., Peyrefitte G., Lehrbuch Kosmetik: Grundlagen - Grundstoffe - Grundtechniken, Hogrefe AG, Bern 2001.

[0090] The alkalizing agent or pH adjuster is used to adjust the pH value of the formulation to the desired range. Suitable alkalizing agents or pH adjusters include sodium hydroxide, monoethanolamine 0.1-5%, phosphoric acid, and citric acid, among others.

[0091] Examples of compositions are shown in the table below:

[0092] [Table 1]

[0093] According to the present invention, the composition is applied topically. By topical application, it is meant external application, in particular topical external application. The composition according to the present invention is preferably a hair care product (i.e., a treatment composition such as a shampoo, conditioner or treatment).

[0094] In one 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.

[0095] The cosmetic preparations according to the invention are particularly suitable for colouring and / or recolouring keratin fibres.

[0096] Therefore, in a further embodiment, the present invention relates to the use of a cosmetic formulation containing a dye precursor selected from the group consisting of indoline and indole derivatives and a xanthine derivative as a bioactive agent for coloring and / or recoloring keratin fibers.

[0097] For the purposes of the present invention, "keratinous fibers" means hair, in particular human hair. In this context, the term "human hair" includes in particular scalp and facial hair.

[0098] In one preferred embodiment, the present invention relates to the use of a cosmetic preparation for coloring and / or recoloring human hair.

[0099] The formulation is preferably dispensed onto wet or dry hair and rinsed off after a residence time of 1 to 30 minutes.

[0100] The cosmetic preparations according to the invention for colouring and / or recolouring keratin fibres, in particular human hair, have the effect that the hair is permanently coloured in a slow and gentle way, while stimulating the keratinocytes in the hair roots to produce more natural pigment again.

[0101] Therefore, in a further embodiment, the present invention relates to the use of a cosmetic preparation for coloring and / or recoloring human hair, in which the hair is permanently colored in a slow and gentle manner and at the same time the keratinocytes in the hair root are stimulated to produce more natural pigment again.

[0102] In a further embodiment, the present invention relates to a method for coloring and / or recoloring keratin fibers, in particular human hair, comprising applying a cosmetic preparation according to the invention to the hair and then coloring, wherein the coloring is carried out solely by atmospheric oxygen, without the need for any additional oxidizing agent.

[0103] The following formulations are intended to illustrate the invention but are not intended to be limiting to the specific examples. Text description of the illustration image022.gif. [Brief explanation of the drawings]

[0104] [Figure 1] Comparative photographs of strands washed with Example Formulation 2 (D1 / D2) and Comparative Formulation (E1 / E2) [Figure 2] Comparison of color previews of the two shampoos used, Example Formulation 2 (D1 / D2) and the comparative formulation [Figure 3] Change in color intensity (as absolute value dL*) when using shampoos containing Example Formulation 2 and Comparative Formulation [Figure 4] Total color change dE* when using the shampoo of Example 2 and the comparative example, respectively [Figure 5] The change in color intensity when washed with a color shampoo (5 washes) and when washed with a neutral shampoo (14 washes). [Figure 6] Change in color intensity when washed with color shampoo (10 washes) and when washed with neutral shampoo (15 washes) [Figure 7] Change in color intensity when washed with color shampoo (15 washes) and when washed with neutral shampoo (15 washes) [Figure 8] Comparison of color change after 15 wash-on cycles and 15 wash-out cycles using two shampoos on one strand. [Figure 9] Comparison of color previews for Example Formulation 1, Example Formulation 2 and Comparative Formulation, using shampoo, when 15 wash-on cycles were performed on one strand in each case. [Figure 10] Change in color intensity (as absolute value dL*) when using Example Formulation 1, Example Formulation 2, and the shampoo of the comparative formulation, respectively. [Figure 11] Total change in color dE* when using Example Formulation 1, Example Formulation 2, and the comparative formulation shampoo, respectively. [Figure 12] Comparison of color previews for the shampoos used in Example Formulation 6, Example Formulation 7 and Example Formulation 8, in each case on one strand after 15 wash-on cycles. [Figure 13] Change in color intensity (as absolute value dL*) when using shampoo with Example Formulation 6, Example Formulation 7 or Example Formulation 8. [Figure 14] Total change in color dE* when using shampoos of Example Formulation 6, Example Formulation 7 and Example Formulation 8, respectively. [Figure 15] Comparative photographs of strands washed with Example Formulation 6 ("DHI-B"), Example Formulation 7 ("Combi-B"), and Example Formulation 8 ("Blue-B"), respectively (Strand B used as an example).

[0105] Experimental Part formulation The following formulations were prepared by methods known to those skilled in the art.

[0106] Comparative formulation The comparative formulation contains caffeine as the xanthine derivative and HC Blue 2 as the direct dye.

[0107] [Table 2]

[0108] Example Formulation 1 Example formulation 1 contains dihydroxyindole and caffeine as a xanthine derivative.

[0109] [Table 3]

[0110] Example Formulation 2 Example formulation 2 contains dihydroxyindole, caffeine as a xanthine derivative, and HC Blue 2 as a direct dye.

[0111] [Table 4]

[0112] Example Formulation 3 Example formulation 3 contains dihydroxyindole, caffeine as a xanthine derivative, and HC Blue 2 as a direct dye.

[0113] [Table 5]

[0114] Example Formulation 4 Example formulation 4 contains dihydroxyindole, caffeine as a xanthine derivative, and HC Blue 2 as a direct dye.

[0115] [Table 6]

[0116] Example Formulation 5 Example formulation 5 contains dihydroxyindole and caffeine as the xanthine derivative.

[0117] [Table 7]

[0118] Example formulations 6 to 8 In contrast to Example Formulation 2, additional dyes for coloring the formulation were completely omitted in Example Formulations 6 to 8. Example Formulation 6 contains dihydroxyindole and caffeine as a xanthine derivative, Example Formulation 7 contains dihydroxyindole, caffeine as a xanthine derivative, and HC Blue 2 as a direct dye, and Example Formulation 8 contains caffeine as a xanthine derivative and HC Blue 2 as a direct dye.

[0119] [Table 8]

[0120] Neutral preparation The neutral formulation contains no caffeine, DHI or HC Blue 2.

[0121] [Table 9]

[0122] Application Examples To evaluate the color performance in terms of quality, intensity, and duration, the following wash-on and wash-out tests were performed.

[0123] Application example 1 To examine color performance in terms of quality and strength, Kerling strands were subjected to wash-on tests using a shampoo containing 5,6-DHI, caffeine, and HC Blue 2 (Example Formulation 2) and a shampoo containing HC Blue 2 and caffeine (Comparative Formulation).

[0124] Washing Protocol: - Dampen your strands with warm water for 30 seconds and then use two fingers to remove excess water. -Massage a total of 5g of shampoo into 5 strands for 1 minute. - Leave it on for a total of 5 minutes - Rinse with warm water for 1 minute and squeeze with kitchen roll. -Comb them and spread them out to air dry The next day, scan the strands (photograph a sample strand every 5 washes) using a Konica Minolta spectrophotometer CM600d, measurement geometry d / 8°, specular reflection included (SCE), standard illuminance D65, field of view 10°). Then repeat the wash cycle.

[0125] Use hair strands: Kerling White Selection, adhesive braid, width 2cm, length 12cm, 3g / pc Use shampoo: Example Formulation 2 Strands D1-D5 Comparative formulations: Strand E1-E5

[0126] For each product, 5 strands were used and 28 washes were performed.

[0127] FIG. 1 shows a comparison between strands D1 / D2 treated with Example Formulation 2 and strands E1 / E2 treated with the comparative formulation.

[0128] A comparison of the color previews of the two shampoos used is shown in Figure 2. Figures 3 and 4 show the change in color intensity in absolute values ​​(dL). * (Figure 3) and total color change dE * (Figure 4) which shows that with repeated use, the color benefit gradually builds up, improving the color results compared to the comparative formulation.

[0129] Application example 2 To examine color performance in terms of quality, strength, and duration, Kerling strands were subjected to wash-on and wash-out tests using a shampoo containing 5,6-DHI, caffeine, and HC Blue 2 (Example Formulation 2), and a shampoo containing HC Blue 2 and caffeine (Comparative Formulation), respectively.

[0130] Washing Protocol: - Wet your strands with warm water for 30 seconds, then use two fingers to remove excess water. -Massage a total of 5g of shampoo into 5 strands for 1 minute. - Leave it on for a total of 5 minutes - Rinse with warm water for 1 minute and squeeze with kitchen roll. -Comb them and spread them out to air dry The next day, the strands are scanned and photographed with a Konica Minolta spectrophotometer CM600d, measurement geometry d / 8°, specular reflection included (SCE), standard illuminance D65, field of view 10°; then the washing cycle is repeated.

[0131] Use hair strands: Kerling White Selection, adhesive braid, 2cm wide, 12cm long Use color shampoo: Example 2 Strands B1-B15 Comparative formulations Strand C1-C15

[0132] A neutral formulation was used for washout.

[0133] For each product, 15 strands were processed in 5 pieces.

[0134] The color change was monitored throughout the subsequent wash-on and wash-out cycles: - Wash five times with color shampoo, then wash 14 times with a neutral formula (Figure 5) -Wash 10 times with color shampoo, then wash 15 times with a neutral formula (Figure 6) -Wash 15 times with color shampoo, then wash 15 times with a neutral formula (Figure 7).

[0135] Figures 5-7 show the change in color intensity when hair is washed with a color shampoo and a neutral formulation, respectively, according to the protocol described above. Figure 8 compares the color change of two shampoos applied to one strand over 15 wash-on cycles followed by 15 wash-out cycles, as measured with a Konica Minolta spectrophotometer CM600d, measurement geometry d / 8°, specular reflection included (SCE), standard illuminance D65, field of view 10°. The figure shows that the color effect gradually builds with repeated application, improving dyeing results compared to the comparative formulation. The color effect persists longer after treatment with the shampoo according to the present invention than with the comparative formulation.

[0136] Application example 3 White Virgin strands (Imhair) were subjected to wash-on tests using a shampoo containing 5,6-DHI and caffeine (Example Formulation 1), a shampoo containing 5,6-DHI, caffeine and HC Blue 2 (Example Formulation 2), and a shampoo containing HC Blue 2 and caffeine (Comparative Formulation) to examine color performance in terms of quality and strength.

[0137] Washing Protocol: - Wet your strands with warm water for 30 seconds, then use two fingers to remove excess water. - Massage 5g of shampoo into each of your three strands for 30 seconds. - Leave it on for a total of 5 minutes -Rinse with warm water for 1 minute -Comb and let air dry -The next day, scan and photograph the strands with the Konica; then repeat the wash cycle.

[0138] Use hair strands: White Virgin (Imhair) Use shampoo: Example Formulation 1 Strands 1-3 Example Formulation 2 Strands 4-6 Comparative formulation: Strand 7-9

[0139] Three strands of each product were used and each was subjected to 15 wash cycles.

[0140] A comparison of the color previews of the shampoos used is shown on one strand of hair in Figure 9. Figures 10 and 11 show the change in color intensity in absolute values ​​dL * (Figure 10) and total color change dE * (Figure 11) which shows that repeated applications gradually build up color benefits, improving staining results compared to the comparative formulation.

[0141] Application example 4 To determine dye shade over time, white strands of Kerling and bleached strands of Imhair were dyed with 10 g of Example Formulation 2 for 15 minutes, rinsed for 1 minute, and air-dried for 1.5 hours (after which residual moisture was blow-dried). Measurements were taken on the day of treatment, after the 15-minute exposure time (initial shade), and after 1, 2, 3, 8, 9, 10, 11, 14, and 15 days.

[0142] [Table 10]

[0143] The measurements show a visually noticeable shift in hue from the original graphite color to a more natural, brownish color.

[0144] Application example 5 Kerling strands were subjected to wash-on tests using a shampoo containing 5,6-DHI and caffeine (Example Formulation 6), a shampoo containing 5,6-DHI, caffeine and HC Blue 2 (Example Formulation 7), and a shampoo containing HC Blue 2 and caffeine (Example Formulation 8) to examine color performance in terms of quality and strength.

[0145] Washing Protocol: - Wet 5 strands with warm water for 30 seconds, then squeeze out excess water using two fingers. -Massage a total of 5g of shampoo into 5 strands for 1 minute. - Leave it on for a total of 5 minutes - Rinse with warm water for 1 minute and squeeze with kitchen roll. -Comb them and spread them out to air dry The next day, the strands are scanned and photographed with a Konica Minolta spectrophotometer CM600d, measurement geometry d / 8°, specular reflection included (SCE), standard illuminance D65, field of view 10°; the washing cycle is then repeated.

[0146] Use hair strands: Kerling white selection, adhesive braid width 2cm, length 12cm, 3g / pc, Use coloring shampoo: Example Formulation 6 Strand DHI-A to E Example Formulation 7 Strand Combi A to E Example Formulation 8 Strand Blue A-E

[0147] Five strands were used per product, and each was washed 15 times.

[0148] A comparison of the color previews of the shampoos used is shown on one strand of hair in Figure 12.

[0149] Figures 13 and 14 show the change in color intensity in absolute value dL * (Figure 13) and total color change dE * (Figure 14).

[0150] In Figures 12-14, the term "DHI only" refers to a test using a shampoo containing 5,6-DHI and caffeine (Example Formulation 6), the term "DHI / Blue 2" refers to a test using a shampoo containing 5,6-DHI, caffeine, and HC Blue 2 (Example Formulation 7), and the designation "Blue 2 only" refers to a test using a shampoo containing Blue 2 and caffeine (Example Formulation 8).

[0151] FIG. 15 shows a comparison of strands washed with Example Formulation 6 ("DHI-B"), Example Formulation 7 ("Combi-B") and Example Formulation 8 ("Blue-B"), using Strand B as an example.

[0152] The figure shows that repeated applications result in improved color results with a gradual buildup of color benefit compared to a comparative formulation containing only HC Blue 2 and caffeine (Example Formulation 8).

Claims

1. A cosmetic formulation comprising a dye precursor selected from the group consisting of indoline derivatives and indole derivatives, and a xanthine derivative as a physiologically active ingredient.

2. The cosmetic formulation according to claim 1, wherein the dye precursor is an indole derivative.

3. The dye precursor is given by formula (I), 【Chemistry 1】 (Independent of each other, R １ is hydrogen, C １ -C ４ - Alkyl alkyl group or C １ -C ４ -Hydroxyalkyl groups, R ２ This is either hydrogen or a -COOH group, and the -COOH group can also exist as a salt with a physiologically acceptable cation. R ３ is hydrogen or C １ -C ４ -alkyl group, R ４ is hydrogen, C １ -C ４ - Alkyl group, amino group, or R ６ C １ -C ４ -Alkyl group-CO-R ６ And, R ５ is R ４ The cosmetic formulation according to claim 2, which is a derivative of 5,6-dihydroxyindole (one of the groups described above), or a physiologically acceptable salt of these compounds with an organic acid or an inorganic acid.

4. The cosmetic formulation according to claim 3, wherein the compound of formula (I) is selected from 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, and physiologically acceptable salts thereof.

5. The cosmetic formulation according to claim 1, wherein the dye precursor is an indoline derivative.

6. The dye precursor is given by formula (II), 【Chemistry 2】 (Independent of each other, R １ is hydrogen, C １ -C ４ - Alkyl alkyl group or C １ -C ４ -Hydroxyalkyl groups, R ２ This is either hydrogen or a -COOH group, and the -COOH group can also exist as a salt with a physiologically acceptable cation. R ３ is hydrogen or C １ -C ４ - Alkyl alkyl group, R ４ is hydrogen, C １ -C ４ - Alkyl group, amino group, or R ６ C １ -C ４ - A group indicating an alkyl group - CO-R ６ And, R ５ is R ４ The cosmetic formulation according to claim 5, which is a derivative of 5,6-dihydroxyindoline (one of the groups described above), or a physiologically acceptable salt of these compounds with an organic or inorganic acid.

7. The cosmetic formulation according to claim 6, wherein the compound of formula (II) is selected from 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline and physiologically acceptable salts thereof.

8. The cosmetic formulation according to claim 1, wherein the xanthine derivative is caffeine.

9. The cosmetic formulation according to claim 1, further comprising at least one direct dye.

10. The cosmetic formulation according to claim 9, 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, and preferably HC blue 2.

11. Use of the cosmetic formulation according to any one of claims 1 to 10 for the recoloring of keratin fibers, particularly human hair.

12. The use according to claim 11 for recoloring human hair, wherein the formulation is distributed to wet or dry hair and rinsed off again after a residence time of 1 to 30 minutes.

13. The use according to claim 11 for the recoloring of human hair, wherein the hair is permanently colored in a slow and gentle manner, and at the same time, the keratinocytes in the hair follicles are stimulated to produce more natural pigments again.

14. A method for recoloring keratin fibers, particularly human hair, comprising applying a cosmetic formulation according to any one of claims 1 to 10 to hair, and then coloring the hair.

Images