Dyeing method for keratin fibers comprising a direct azo-dye and an organic alkalizing agent, and kit-of-parts thereof

Abstract

This invention relates to a method for dyeing keratin fibers, preferably human keratin fibers, and more preferably human hair, comprising the following steps: i) mixing an aqueous dyeing composition A with a second aqueous composition C to produce a ready-to-use composition with a pH in the range of 7 to 12, wherein the aqueous dyeing composition A comprises: a) one or more anionic or nonionic azo dyes and / or their salts, and / or mixtures thereof; b) one or more alkalizing agents having at least one basic functional group, wherein the pKa value of the conjugate acid of the basic functional group is in the range of 6.0 to 8.0, the pKa being determined by measuring the pKa of the alkalizing agent in water at 20°C under atmospheric conditions with a pH of 0.1. The pH of the second aqueous composition C is determined by acid-base titration of solution M, which is in the range of 1 to 6 and contains one or more oxidants, preferably hydrogen peroxide, as appropriate; ii) the ready-to-use composition is applied to keratin fibers and left for a period of time ranging from 1 minute to 60 minutes; iii) the keratin fibers are rinsed and washed with shampoo as appropriate, wherein one or more of the compounds according to group b) are triethanolamine, 2-[4-(2-hydroxyethyl)-piperazine-1-yl]ethane-1-sulfonic acid, and / or its salts, and / or mixtures thereof.

Description

Technical Field

[0001] This invention relates to a dyeing method for keratin fibers comprising certain direct dyes and specific alkalizing agents, and a component kit. Prior Technology

[0002] Over the past decade, direct dyes have received particular attention from the cosmetics industry. Compared to their oxidizing counterparts, direct dyes are easier to apply to keratin fibers, but generally lack durability on keratin fibers. Furthermore, for gray hair, direct dyes typically lack color strength when used without oxidizing dyes.

[0003] The applicant has developed a novel direct dye (EP1366752) that complements the availability and color range of existing dyes. The aforementioned series of developed dyes includes HC Blue 18, HC Red 18, and HC Yellow 16.

[0004] EP2979683 discloses tris(hydroxymethyl)aminomethane as an alkalizing agent in oxidative dyeing compositions and broadly discloses its combination with direct dyes. It has been found that oxidative dyes can improve the uniformity of coloring.

[0005] However, prior art has not satisfactorily solved the problems of dyeing strength and durability of direct dyes, and therefore there is a real need to develop direct dyeing compositions for keratin fibers that have improved dyeing strength and durability, especially for hair that has previously been damaged. Summary of the Invention

[0006] Therefore, the first objective of this invention is a method for dyeing keratin fibers, preferably human keratin fibers, and more preferably human hair, comprising the following steps: i) An aqueous dyeing composition A containing the following: a) One or more anionic or nonionic azo dyes and / or their salts, and / or mixtures thereof (b) One or more alkalizing agents having at least one basic functional group, wherein the pKa value of the conjugate acid of the basic functional group is in the range of 6.0 to 8.0, determined by acid-base titration of a 0.1 M solution of the alkalizing agent in water at 20°C under atmospheric conditions. When mixed with a second aqueous composition C, which has a pH in the range of 1 to 6 and, where appropriate, contains one or more oxidants, preferably hydrogen peroxide, a ready-to-use composition with a pH in the range of 7 to 12 is produced. ii) Apply the ready-to-use composition to keratin fibers and leave it for a period ranging from 1 minute to 60 minutes. iii) Rinse the keratin fibers and wash them with shampoo if necessary. Wherein, one or more of the compounds in group b) are triethanolamine, 2-[4-(2-hydroxyethyl)-piperazine-1-yl]-ethane-1-sulfonic acid, and / or its salts, and / or mixtures thereof.

[0007] The second objective of this invention is a component set comprising... - As defined above, aqueous dyeing composition A, - Composition B, comprising one or more direct dyes selected from HC Yellow 1 and / or 2-amino-6-chloro-4-nitrophenol, and / or their salts, and / or mixtures thereof, and - As defined above, composition C has a pH in the range of 1 to 6 and, where appropriate, contains one or more oxidants, preferably hydrogen peroxide. Implementation

[0008] The inventors of this invention unexpectedly discovered that the dyeing strength, durability, and wash fastness of certain direct dyes are improved in the presence of certain organic alkalizing agents having at least one basic functional group, the pKa of which is the conjugate acid in the range of 6.0 to 8.0. Furthermore, such dyeing compositions of this invention improve the cosmetic properties of keratin fibers, such as hand feel, luster, and texture.

[0009] [Staining Method] [] This invention relates to a method for dyeing keratin fibers, preferably human keratin fibers, and more preferably human hair, comprising the following steps: [] i) An aqueous dyeing composition A containing the following a) One or more anionic or nonionic azo dyes and / or their salts, and / or mixtures thereof (b) One or more alkalizing agents having at least one basic functional group, wherein the pKa value of the conjugate acid of the basic functional group is in the range of 6.0 to 8.0, determined by acid-base titration of a 0.1 M solution of the alkalizing agent in water at 20°C under atmospheric conditions. When mixed with a second aqueous composition C having a pH in the range of 1 to 6 and, where appropriate, containing one or more oxidants, preferably hydrogen peroxide, a ready-to-use composition having a pH in the range of 7 to 12 is produced. ii) Apply the ready-to-use composition to keratin fibers and leave it for a period ranging from 1 minute to 60 minutes. iii) Rinse the keratin fibers and wash them with shampoo if necessary. Wherein, one or more of the compounds in group b) are triethanolamine, 2-[4-(2-hydroxyethyl)-piperazine-1-yl]-ethane-1-sulfonic acid, and / or its salts, and / or mixtures thereof.

[0010] Preferably, from the viewpoint of washing fastness, the dyes according to group a) are one or more anionic or nonionic azo dyes, namely HC Red 18, HC Blue 18, HC Yellow 16, Disperse Black 9, Acid Black 1, Disperse Orange 3, Disperse Red 17, Acid Black 52, Acid Red 14, Acid Orange 7, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 184, Acid Yellow 23, Acid Orange 24, Solvent Red 1, Curry Red, Acid Red 18, Pigment Red 57, and / or their salts, and / or mixtures thereof, preferably HC Red 18, HC Blue 18, HC Yellow 16, Disperse Black 9, and / or their salts, and / or mixtures thereof.

[0011] Preferably, from the viewpoint of dyeing intensity, the total concentration of the compound according to group a) is 0.001% by weight or higher, more preferably 0.002% by weight or higher, further preferably 0.05% by weight or higher, and even more preferably 0.1% by weight or higher, calculated based on the total weight of composition A.

[0012] Preferably, from the viewpoint of economic reasons and cosmetic safety, the total concentration of the compounds in composition a) is 10% by weight or less, more preferably 0.5% by weight or less, even more preferably 2% by weight or less, and even more preferably 1% by weight or less, calculated based on the total weight of composition A.

[0013] To achieve the above effects, preferably, the total concentration of the compounds in composition a) is in the range of 0.001% to 10% by weight, more preferably in the range of 0.002% to 5% by weight, even more preferably in the range of 0.05% to 2% by weight, and even more preferably in the range of 0.1% to 1% by weight, calculated based on the total weight of composition A.

[0014] Composition A comprises one or more alkalizing agents having at least one basic functional group, the pKa of which is the conjugate acid in the range of 6.0 to 8.0, determined by acid-base titration of a 0.1 M solution of the alkalizing agent in water at 20°C under atmospheric conditions. One or more alkalizing agents in Composition A are triethanolamine (pKa 7.7), 2-[4-(2-hydroxyethyl)-piperazine-1-yl]ethane-1-sulfonic acid (pKa 7.4), and / or its salts, and / or mixtures thereof.

[0015] Preferably, the pKa of the conjugate acid of at least one basic functional group is measured to be in the range of 7.0 to 8.0, as disclosed above.

[0016] Suitable acids for titration are strong acids with a pKa of 1 or less. Suitable strong acids include trifluoroacetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and / or perchloric acid. Titration is performed in water.

[0017] The appropriate detection method is an electrode, preferably a pH-sensitive electrode or an electrode that records changes in conductivity of the titration environment.

[0018] Suitable titrations of a 0.1 M alkalizing agent solution are performed in water at 20°C under atmospheric conditions. A suitable strong acid concentration is, for example, a 6 M hydrochloric acid solution.

[0019] Preferably, from the viewpoint of wash fastness, one or more of the compounds in group b) are selected from triethanolamine and / or its salts, more preferably one or more of the compounds in group b) are selected from triethanolamine and / or its inorganic salts, and even more preferably one or more of the compounds in group b) are selected from triethanolamine and / or its hydrochloride, sulfate, bisulfate, or nitrate.

[0020] Preferably, from the viewpoint of dyeing intensity, the total concentration of the compound according to composition b) is 0.1% by weight or higher, more preferably 0.25% by weight or higher, even more preferably 0.5% by weight or higher, even more preferably 0.75% by weight or higher, and even more preferably 1% by weight or higher, calculated based on the total weight of composition A.

[0021] Preferably, from the viewpoint of economic reasons and cosmetic safety, the total concentration of the compounds in composition b) is 40% by weight or less, more preferably 30% by weight or less, further preferably 20% by weight or less, and even more preferably 15% by weight or less, calculated based on the total weight of composition A.

[0022] To achieve the above effects, preferably, the total concentration of the compounds in composition b) is in the range of 0.1% to 40% by weight, more preferably in the range of 0.25% to 30% by weight, even more preferably in the range of 0.5% to 20% by weight, and even more preferably in the range of 0.75% to 15% by weight, calculated based on the total weight of composition A.

[0023] More preferably, from the viewpoint of staining intensity, the weight ratio of the compound according to group b) to the compound according to group a) in composition A is 0.1 or higher, more preferably 0.5 or higher, more preferably 1 or higher, even more preferably 1.5 or higher, even more preferably 5 or higher, even more preferably 10 or higher.

[0024] More preferably, from the viewpoint of dyeing strength, formulation stability and cosmetic safety, the weight ratio of the compound according to group b) to the compound according to group a) in composition A is 200 or less, more preferably 180 or less, even more preferably 150 or less, even more preferably 125 or less, even more preferably 100 or less, even more preferably 75 or less.

[0025] To achieve the above effects, preferably, the weight ratio of the compound according to group b) to the compound according to group a) in composition A is in the range of 0.1 to 200, more preferably in the range of 0.5 to 180, more preferably in the range of 1 to 150, even more preferably in the range of 1.5 to 125, even more preferably in the range of 5 to 100, and even more preferably in the range of 10 to 75.

[0026] [Composition] [A] [In the form of cosmetics] [] Composition A is an aqueous composition. The term "aqueous" means that composition A contains a majority of water, that is, from the viewpoint of achieving a cosmetically acceptable composition A, the composition preferably contains 50% or more by weight, more preferably 60% or more by weight, even more preferably 70% or more by weight, and even more preferably 80% or more by weight of water by weight.

[0027] More preferably, from the viewpoint of dyeing strength, composition A contains 98% by weight or less, more preferably 95% by weight or less, and more preferably 92% by weight or less of water, based on the total weight of composition A.

[0028] To achieve the above effects, preferably, the total concentration of water in composition A is in the range of 50% to 98% by weight, more preferably in the range of 60% to 95% by weight, even more preferably in the range of 70% to 92% by weight, and even more preferably in the range of 80% to 92% by weight.

[0029] Preferably, from the viewpoint of staining efficacy, the pH of composition A is 7 or greater, more preferably 7.5 or greater, even more preferably 8 or greater, and even more preferably 8.5 or greater.

[0030] Preferably, from the viewpoint of hair damage and dyeing efficacy, the pH of composition A is 12 or less, more preferably 11 or less, and even more preferably 10.5 or less.

[0031] To achieve the above effects, preferably, the pH of composition A is in the range of 7 to 12, more preferably in the range of 7.5 to 11, even more preferably in the range of 8 to 10.5, and even more preferably in the range of 8.5 to 10.5.

[0032] All pH values ​​were measured at 20°C under atmospheric conditions using suitable methods (such as pH-sensitive electrodes).

[0033] In one embodiment of the present invention, composition A may contain one or more organic solvents according to group c). For this embodiment, the suitable concentration of the compound according to group c) is in the range of 0.1% by weight to 10% by weight, based on the total weight of composition A. Suitable solvents are monovalent, divalent, and trivalent alcohols and / or mixtures thereof.

[0034] From the perspective of cosmetic safety and solubility, suitable monovalent, divalent and trivalent alcohols are ethanol, n-propanol, isopropanol, propylene glycol, ethylene glycol, benzyl alcohol, phenoxyethanol and glycerol and / or mixtures thereof.

[0035] [Based on group] [d)] [Of] [Lipophilic compounds] Preferably, from the viewpoint of further increasing the dyeing intensity, composition A contains one or more lipophilic compounds that are liquid at 25°C and atmospheric pressure as compounds according to group d).

[0036] Suitable compounds according to group d) are natural and / or vegetable oils, paraffin-based compounds, straight-chain or branched-chain, saturated or unsaturated C12 to C22 fatty alcohols, and fatty acid esters composed of straight-chain or branched-chain, saturated or unsaturated C12 to C22 fatty acids esterified from straight-chain or branched-chain C3 to C12 primary alcohols, and polysiloxanes.

[0037] Suitable natural and / or plant oils include olive oil, almond oil, avocado oil, wheat germ oil, and castor oil.

[0038] Suitable paraffin-based compounds are liquid paraffins, especially light liquid paraffins and sublime paraffins; and mineral oils, especially white mineral oils.

[0039] Suitable fatty compounds comprising lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, palmitol, heptadecanol, stearyl alcohol, nonadecanol, eicosyl alcohol, docosyl alcohol and / or mixtures thereof, such as cetearyl alcohol.

[0040] Suitable examples of fatty acid esters composed of straight or branched fatty acids, saturated or unsaturated, from C12 to C22, esterified from straight or branched primary alcohols of C3 to C18 are octyl palmitate, isocetyl palmitate, isopropyl palmitate, octyl stearate, oleate, and myristate, as well as mixtures thereof.

[0041] Suitablely, the composition may also contain lipophilic components, such as polysiloxanes, for example linear polysiloxanes, such as dimethyl polysiloxanes and dimethyl polysiloxane alcohols with different consistencies, amination polysiloxanes having primary, secondary, tertiary or quaternary ammonium groups, such as amino-terminated dimethyl polysiloxanes, polysiloxane 9 and quaternary ammonium salt 80, cyclic polysiloxanes, such as cyclomethicone polysiloxanes, aromatic polysiloxanes, such as phenyltrimethyl polysiloxanes; C10 to C36 fatty acid triglycerides, and mixtures thereof.

[0042] Furthermore, and more preferably, from the viewpoint of further increasing the staining intensity, composition A is an emulsion and contains one or more compounds according to group d), wherein the one or more compounds are selected from fatty alcohols having branched or straight chains, saturated or unsaturated carbon chain lengths in the range of C12 to C22; fatty acids having branched or straight chains, saturated or unsaturated carbon chain lengths in the range of C12 to C22; ester oils; vegetable oils; polysiloxane oils; and paraffin oils.

[0043] Based on the total weight of composition A, the suitable concentration of the compound according to d) in the emulsion is in the range of 0.5% to 20% by weight, preferably 1% to 10% by weight.

[0044] [Surfactants] Furthermore, from the viewpoint of composition stability and miscibility as well as the wettability of keratin fibers, composition A further comprises one or more surfactants as compounds according to f), preferably selected from nonionic, cationic, anionic, zwitterionic / amphoteric surfactants.

[0045] Suitable anionic surfactants are known in principle for self-cleaning compositions. These anionic surfactants are sulfate, sulfonate, carboxylate, and alkyl phosphate type anionic surfactants, such as known C10-C18 alkyl sulfates, and especially various ether sulfates, such as C12-C14 alkyl ether sulfates, lauryl ether sulfates (especially those having 1 to 4 ethylene oxide groups in the molecule), monoglyceride (ether) sulfates, fatty acid amide sulfates obtained by ethoxylation and subsequent sulfation of fatty acid alkylamines, their alkali metal salts, and salts of long-chain mono- and dialkyl phosphates. Preferred anionic surfactants are alkyl sulfate surfactants, especially lauryl sulfates and their salts.

[0046] Other suitable surfactants are nonionic surfactants. Non-limiting examples include long-chain fatty acid mono- and dialkyl alcohol amides, such as coconut oil fatty acid mono- or diethanolamide and myristic acid fatty acid mono- or diethanolamide, stearic acid mono- or diethanolamide; alkyl polyglucosides having 8 to 18 carbon atoms and 1 to 5 glucoside units; sorbitol esters, such as polyethylene glycol sorbitol stearic acid, palmitic acid, myristic acid, and laurate; fatty acid polyethylene glycol esters or condensates of ethylene oxide and propylene oxide, such as those sold under the trade name "Pluronics R"; and fatty alcohol ethoxides, C10-C10. 22 fatty alcohol ethoxides, known by the general terms “lauryl ether”, “myristyl ether”, “oleyl ether”, “cetyl ether”, “decyl ether”, “stearyl ether” and “cetosteryl ether” according to CTFA nomenclature, including the number of ethylene oxide molecules added, such as “lauryl ether-16”: therefore, the average degree of ethoxylation varies between about 2.5 and about 100, preferably between about 10 and about 30.

[0047] Suitable amphoteric / amphoionic surfactants are especially various known betaines, such as alkyl betaines, fatty acid amide alkyl betaines and sulfobetaines, such as lauryl hydroxysulfobetaine; long-chain alkyl amino acids, such as cocoaminoacetate, cocoaminopropionate and sodium cocoamphopropionate and sodium cocoamphoacetate are also suitable.

[0048] Typical cationic surfactants include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, dipalmityldimethylammonium chloride, distearatedimethylammonium chloride, stearylaminopropyltrimethylammonium chloride, dioleylethyldimethylmethylammonium sulfate, and dioleylethylhydroxyethylmethylmethylammonium sulfate.

[0049] Preferably, from the viewpoint of composition stability, wettability of keratin fibers and dispersibility of components, the total concentration of the compound according to f) in composition A, calculated by the total weight of composition A, is 0.1% by weight or more, more preferably 0.2% by weight or more, and even more preferably 0.25% by weight or more.

[0050] Preferably, from the viewpoint of composition stability, wettability of keratin fibers and dispersibility of components, the total concentration of the compound according to f) in composition A, calculated by the total weight of composition A, is 5% by weight or less, more preferably 4% by weight or less, and even more preferably 2.5% by weight or less.

[0051] To achieve the above effects, preferably, the total concentration of the compound according to f) in composition A is in the range of 0.1% to 5% by weight, more preferably in the range of 0.2% to 4% by weight, and even more preferably in the range of 0.2% to 2.5% by weight, calculated based on the total weight of composition A.

[0052] [Different from group] [b)] [Alkaliizing agent] Preferably, from the viewpoint of high pH staining, composition A comprises one or more alkalizing agents different from the compounds according to composition b), preferably selected from ammonia and / or its salts, organic alkyl and / or alkanolamines having at least one basic functional group, the pKa of the conjugate acid of the basic functional group being greater than 8.0, as determined by acid-base titration of a 0.1 M solution of the alkalizing agent in water at 20°C under atmospheric conditions, and / or its salts, and / or mixtures thereof.

[0053] Suitable organic alkyl and / or alkanolamines and / or their salts are based on the following general formula: R1, R2 and R3 are independently selected from H, straight-chain C1-C6 alkyl groups that may be substituted with a hydroxyl group, or branched-chain C3-C12 alkyl groups or alkanols, wherein at least one of R1, R2 or R3 is different from H, and / or its salts, and / or mixtures thereof.

[0054] Suitable for the purposes of providing alkalinity and cosmetic safety as well as low odor, one or more alkyl and / or alkanolamines and / or their salts are selected from monoethanolamine, diethanolamine, monoethanol methylamine, monoethanol dimethylamine, diethanol methylamine, monoethanol ethylamine, monoethanol diethylamine, diethanol ethylamine, monoethanol propylamine, monoethanol dipropylamine, diethanol propylamine, monoethanol butylamine, diethanol butylamine, trimethylamine, triethylamine, 2-amino-2-methylpropanol, and / or their salts, and / or mixtures thereof.

[0055] From the perspective of providing alkalinity and cosmetic safety, a preferred alkalizing agent, unlike the compound according to group b), is selected from ammonia, monoethanolamine, 2-amino-2-methylpropanol, and / or its salts, and / or mixtures thereof.

[0056] Preferably, from the viewpoint of providing alkalinity, the total concentration of the alkalizing agent, calculated based on the total weight of composition A, is 0.1% by weight or higher, more preferably 0.25% by weight or higher, and even more preferably 0.4% by weight or higher.

[0057] Preferably, from the viewpoint of providing alkalinity, hair damage and odor, the total concentration of the alkalizing agent, calculated by the total weight of composition A, is 40% by weight or less, more preferably 30% by weight or less, and even more preferably 25% by weight or less, different from the total concentration of the compound according to composition b).

[0058] To achieve the above effects, preferably, the total concentration of alkalizing agents in composition A that are different from the compounds according to group b) is in the range of 0.1% by weight to 40% by weight, more preferably in the range of 0.25% by weight to 30% by weight, and even more preferably in the range of 0.4% by weight to 25% by weight, calculated based on the total weight of composition A.

[0059] [Different from group] [a)] [Other direct dyes] In one embodiment of the present invention, composition A may contain one or more direct dyes different from the direct dyes according to group a).

[0060] Suitable direct dyes can be selected from cationic, anionic, and / or nonionic direct dyes.

[0061] From the viewpoint of improving the wash fastness of the composition, the best direct dye, other than the direct dye according to group a), is HC Yellow 1,2-amino-6-chloro-4-nitrophenol, and / or its salts, and / or mixtures thereof.

[0062] From the viewpoint of wash fastness, the total concentration of one or more direct dyes (if present) in composition A, excluding the direct dye in group a), is preferably 0.01% by weight or higher, more preferably 0.05% by weight or higher, and even more preferably 0.1% by weight or higher, calculated based on the total weight of composition A.

[0063] From the viewpoint of economic reasons and wash fastness, the total concentration of one or more direct dyes (if present) in composition A, excluding the direct dyes in groups a) and b), is preferably 10% by weight or less, more preferably 9% by weight or less, even more preferably 7.5% by weight or less, even more preferably 6% by weight or less, and even more preferably 4% by weight or less, calculated by the total weight of the composition.

[0064] To achieve the above effects, the total concentration of one or more direct dyes (if present) in composition A, excluding the direct dye in group a), is in the range of 0.01% to 10% by weight, more preferably in the range of 0.05% to 9% by weight, even more preferably in the range of 0.1% to 7.5% by weight, further preferably in the range of 0.1% to 6% by weight, and even more preferably in the range of 0.1% to 4% by weight, calculated based on the total weight of composition A.

[0065] [Oxidation dyes] Composition A may further comprise one or more oxidized dyes. Oxidized dyes are classified as oxidized dye coupling agents and oxidized dye precursors.

[0066] In the context of this invention, the term "precursor" refers to a compound that has been oxidized by an oxidant before reacting with at least one other compound, preferably with at least one other coupling agent compound.

[0067] In the context of this invention, the term "coupling agent" refers to a compound capable of reacting with an oxidizing precursor to form a dye intermediate. The coupling agent itself is not oxidized before reacting with the precursor.

[0068] Suitable precursors for oxidative dyes include p-phenylenediamine, p-aminophenol, and heterocyclic compounds such as diaminopyrazole and substituted pyrimidines, and suitable coupling agents include resorcinol, m-aminophenol, m-phenylenediamine, pyridine and substituted derivatives, and naphthol.

[0069] Suitable oxidative dye coupling agents include 5-amino-2-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 2,4-diaminophenoxyethanol, 2-amino-4-hydroxyethylaminoanisole, 2-methyl-5-amino-6-chlorophenol, 1,3-bis(2,4-diaminophenoxy)propane, 2-bis(2-hydroxyethyl)aminotoluene, 2-amino-5-methylphenol, resorcinol, 2-methyl-resorcinol, 4-chlororesorcinol, 2-amino-4-chlorophenol, 5-amino-4-methoxy-2-methylphenol, 2-aminophenol, 3-aminophenol, 1-methyl-2-hydroxy-4-aminobenzene, 3-N,N-dimethylaminophenol, 2,6-dihydroxy-3,5-dimethoxypyridine, 5- Amino-3-methylphenol, 6-amino-3-methylphenol, 1,3-diamino-benzene, 1-amino-3-(2'-hydroxyethylamino)benzene, 1-amino-3-[bis(2'-hydroxyethyl)amino]benzene, α-naphthol, 4,6-dichlororesorcinol, 1,3-diamine-toluene, 4-hydroxy-1,2-methylenedioxybenzene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-hydroxy-2-methylnaphthalene, 4-hydroxy-1,2-methyldioxybenzene, 2,4-diamine-3-chlorophenol, 5-amino-2-methoxyphenol and / or 1-methoxy-2-amino-4-(2'-hydroxyethylamino)benzene, and / or their salts, and / or mixtures thereof.

[0070] Composition A may contain an approximately equal molar proportion of oxidative dye, for example, in a total concentration ranging from 0.001% to 5% based on the total weight of composition A.

[0071] [Thickening Polymer] From the perspective of cosmetic safety, it is advantageous that composition A further comprises one or more thickening polymers.

[0072] Preferably, the thickening polymer is selected from polymers that produce an aqueous solution and / or an aqueous dispersion with a pH between 8 and 10, and has a viscosity of at least 5,000 mPa·s in water at 25°C at a polymer concentration of 1% by weight of the total weight of the composition, determined by measuring for 1 minute at 25°C with a Brookfield viscometer using a suitable rotor, such as at 10 rpm.

[0073] Suitable nonionic thickening polymers are cellulose-based polymers. Suitable examples of cellulose-based polymers are methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethyl-methylcellulose, and alkylated hydroxycellulose, such as (C2-C8) alkylcellulose or cetyl hydroxyethylcellulose.

[0074] Suitable anionic thickening polymer systems are selected from natural anionic polymers and / or synthetic anionic polymers.

[0075] Suitable natural anionic polymers may be selected from salicorn gum, dehydrosalicorn gum, hydroxypropyl salicorn gum, carboxymethyl cellulose, and starch-based polymers such as plant starch and / or its synthetically modified derivatives, such as hydroxypropyl starch phosphate. Alginic acid, sodium alginate, ammonium alginate, calcium alginate, gum arabic, and guar gum are also suitable.

[0076] From the viewpoint of biodegradability and low environmental impact, the preferred thickening polymer of the composition of the present invention is a natural anionic polymer, and more preferably, saffron gum and / or dehydrogenated saffron gum.

[0077] Preferably, from the viewpoint of providing sufficient viscosity to composition A, the total concentration of the thickening polymer in composition A, calculated by the total weight of the composition, is 0.1% by weight or higher, more preferably 0.25% by weight or higher, and more preferably 0.5% by weight or higher.

[0078] Preferably, from the viewpoint of providing sufficient viscosity to the composition and the cost of goods, the total concentration of the thickening polymer in composition A is 15% by weight or less, more preferably 12% by weight or more, and even more preferably 10% by weight or less, based on the total weight of composition A.

[0079] To achieve the above effects, preferably, the total concentration of the thickening polymer in composition A is in the range of 0.1% to 15% by weight, more preferably in the range of 0.25% to 12% by weight, and even more preferably in the range of 0.5% to 10% by weight, calculated based on the total weight of composition A.

[0080] [Two-component dyeing composition] In one embodiment of the present invention, the composition may be a part of a two-component dyeing composition, characterized in that the first part is composition A as defined above, and the second composition is an aqueous second composition C with a pH in the range of 1 to 6 and, where appropriate, contains one or more oxidizing agents.

[0081] The second aqueous composition C preferably contains hydrogen peroxide as an oxidant. The suitable concentration, calculated based on the total weight of the second aqueous composition C, is in the range of 0.1% to 20% by weight, preferably 0.25% to 15% by weight, and even more preferably 0.5% to 12% by weight.

[0082] The pH of the second aqueous composition C is preferably in the range of 1.5 to 5, and more preferably in the range of 2 to 4.5, by means of suitable acid and alkali adjustment.

[0083] Furthermore, and more preferably, from the viewpoint of miscibility with composition A, composition C comprises one or more lipophilic compounds according to e), as described above with respect to composition A. In this case, composition C is an emulsion and preferably also comprises one or more surfactants as compounds according to f), as described above with respect to composition A.

[0084] In this embodiment of the invention, compositions A and C are intended to be mixed directly before being applied to keratin fibers.

[0085] [Component Set] This invention also relates to a component kit comprising: - As defined above, aqueous dyeing composition A, - Composition B, comprising one or more direct dyes selected from HC Yellow 1 and / or 2-amino-6-chloro-4-nitrophenol, and / or their salts, and / or mixtures thereof, and - As defined above, composition C has a pH in the range of 1 to 6 and, where appropriate, contains one or more oxidants, preferably hydrogen peroxide.

[0086] Composition B may be a dyeing composition containing one or more alkalizing agents and having a pH in the range of 7 to 12.

[0087] However, composition B may also be a cleaning and / or conditioning composition for keratin fibers, preferably comprising one or more surfactants and one or more direct dyes selected from HC Yellow 1 and / or 2-amino-6-chloro-4-nitrophenol, and / or its salts, and / or mixtures thereof. Suitable concentrations of these dyes are explained above under the section on other direct dyes different from those in group a). For example, preferably, from the viewpoint of wash fastness, the total concentration of HC Yellow 1 and / or 2-amino-6-chloro-4-nitrophenol, and / or its salts, and / or mixtures thereof, calculated by the total weight of composition B, is in the range of 0.01% by weight to 10% by weight, more preferably in the range of 0.02% by weight to 5% by weight, and even more preferably in the range of 0.05% by weight to 2% by weight.

[0088] Preferably, from the viewpoint of color intensity, the pH of the ready-to-use composition as defined in step i) is in the range of 8 to 11, more preferably in the range of 8.5 to 10.5.

[0089] Further preferably, from the viewpoint of staining intensity and the economy of the staining method, the retention time as defined in step ii) is in the range of 2 minutes to 45 minutes, more preferably in the range of 5 minutes to 40 minutes, and even more preferably in the range of 10 minutes to 30 minutes.

[0090] [] [Example] [] [, , ] [] [surface] [1] [] [] [Element] [Example of the Invention] [1] [Example of the Invention] [2] [Example of the Invention] [3] [Comparison Examples] [1] [Comparison Examples] [2] [Comparison Examples] [3] [Comparison Examples] [4] [Composition] [A] a) HC Blue 18 0.135 0.135 - 0.135 0.135 0.135 - HC Red 18 0.015 0.015 - 0.015 0.015 0.015 - HC Yellow 16 0.25 0.1 - 0.25 0.25 0.25 - Dispersed Black 9 - 0.1 - - - - - Acid Red 14 - - 0.2 - - - 0.2 - Acid Yellow 1 - 0.5 - - - - - b) Triethanolamine (pKa 7.7) 5.0 4.0 5.0 - - - - - 2-Aminomethylpropanol (pKa 9.7) - - - 5.0 - - 5.0 - Ammonia 25% w / w (pKa 9.2) - 1.0 - - 2.0 - - - Sodium bicarbonate - - - - 3.4 - - - Sodium metasilicate - - - - - 4.9 - water Topping up to 100.0 [Evaluate] Immediate intensity after staining, ΔE * a,b 68.42 66.19 62.57 63.05 62.95 60.80 54.46 After washing, ΔE * a,b 68.03 63.50 38.64 54.80 59.67 48.59 24.24 Color loss / wash fastness, ΔΔE * a,b 0.39 2.69 23.92 8.25 3.28 12.21 30.22 The pH of the above composition is 9.5 ± 0.3. In the comparative examples, the amounts of sodium bicarbonate and sodium metasilicate are molar equivalents relative to other alkalizing agents. []

[0091] [] [Discussion of the Results] [] The examples in Table 1 illustrate that, compared to the comparative examples, the examples of the present invention achieve higher color rendering intensity (higher ΔE* a,b values). This is particularly relevant to Example 1 of the present invention and Comparative Example 2.

[0092] Compared to Comparative Example 1, which uses AMP instead of the same amount of triethanolamine, Example 1 of the present invention shows superior color strength and wash fastness (ΔΔE* a,b value).

[0093] Compared to Comparative Example 1, which uses ammonia to replace part of the triethanolamine, Example 2 of the present invention exhibits superior wash fastness.

[0094] The dyeing strength and wash fastness of the compositions of the present invention containing Acid Red 14 are improved.

[0095] [] [method] [] [Hair preparation] [] Commercially available goat hair (10 cm long, 2 g per bundle) was prewashed and blow-dried before any treatment. Commercial bleaching was performed; this was available under the trade names SilkLift Strong and Goldwell. The first step involved applying a reducing composition containing thioglycolic acid, leaving it on the hair for 20 minutes, then rinsing it off and applying an oxidizing composition containing hydrogen peroxide. The oxidizing composition was left on the hair for 15 minutes, followed by shampooing and blow-drying. Hair obtained using this method was used in dyeing experiments on permed hair.

[0096] [] [Hair dyeing] [] To prepare the ready-to-use composition, each of the above compositions was mixed with a second acidic composition C at a weight ratio of 1:1. 2 g of the resulting ready-to-use composition was applied to the hair prepared as described above and left at ambient temperature for 20 minutes. The hair was then rinsed with water and blow-dried.

[0097] Colorimetric measurements (Datacolor 45G, Datacolor AG Europe, Rotkreuz, Switzerland) were performed using a colorimeter with a CIE colorimetric system (L*, a*, b*). For further calculation purposes, this was referred to as 'new staining' (1).

[0098] [Wash fastness test] [] Each hair stripe was then placed in a shaking bath containing 1.5% sodium lauryl ether sulfate solution and kept at 40°C and 100 rpm for 30 minutes. The hair stripes were then rinsed with water and dried. Colorimetric measurements were performed again to obtain (L*, a*, b*) values. For further calculation purposes, this is referred to as "washed" (2).

[0099] [] [ΔE* , a,b , ] [calculate] [] To assess the color difference between washed hair (2) and newly dyed hair (1), the L*, a* and b* values ​​of each sample were obtained.

[0100] Then, ΔE* is calculated using the following equation: []

[0101] The following examples are within the scope of this invention. [Example] [4] [] [weight] [%] [] HC Blue 18 0.1 HC Red 18 0.05 HC Yellow 16 0.08 Triethanolamine 0.8 2-Aminomethylpropanol 2.5 Cetearyl alcohol ether-30 3.0 Sodium lauryl sulfate 1.5 Cetearyl alcohol 4.0 Benzyl alcohol 1.0 1.5% acrylate copolymer Adjust the pH to 9.5 using NaOH / HCl. Add water to a level of 100.0

Claims

1. A method for dyeing keratin fibers, comprising the following steps: i) mixing an aqueous dyeing composition A comprising: a) HC Red 18, HC Blue 18, HC Yellow 16, Disperse Black 9, Acid Red 14, Acid Yellow 1, and / or salts thereof, and / or mixtures thereof; b) one or more alkalizing agents having at least one basic functional group, the pKa value of the conjugate acid of the basic functional group being in the range of 6.0 to 8.0, determined by acid-base titration of a 0.1 M solution of the alkalizing agent in water at 20°C under atmospheric conditions, with a pH in the range of 1 to 6 and, if applicable, comprising one or more oxidizing agents, to produce a ready-to-use composition with a pH in the range of 7 to 12; ii) applying the ready-to-use composition to keratin fibers and leaving it for a period of time ranging from 1 minute to 60 minutes; iii) rinsing the keratin fibers and, if applicable, washing the keratin fibers with shampoo. Wherein, one or more of the compounds in group b) are triethanolamine and / or its salts.

2. The method of claim 1, wherein one or more of the compounds according to group a) are selected from HC Blue 18, HC Red 18, HC Yellow 16, Disperse Black 9, and / or their salts, and / or mixtures thereof.

3. The method of claim 1, wherein the total concentration of the compounds according to group a) is in the range of 0.001% by weight to 10% by weight, calculated based on the total weight of composition A.

4. The method of claim 1, wherein the total concentration of the compounds according to group a) is in the range of 0.1% by weight to 1% by weight, calculated based on the total weight of composition A.

5. The method of any one of claims 1 to 4, wherein one or more of the compounds according to group b) are selected from triethanolamine and / or its inorganic salts.

6. The method of any one of claims 1 to 4, wherein one or more of the compounds according to group b) are selected from triethanolamine and / or its hydrochloride, sulfate, bisulfate, or nitrate.

7. The method of any one of claims 1 to 4, wherein the total concentration of the compound according to group b) is in the range of 0.1% by weight to 40% by weight, calculated based on the total weight of composition A.

8. The method of any one of claims 1 to 4, wherein the total concentration of the compound according to group b) is in the range of 1% by weight to 15% by weight, calculated based on the total weight of composition A.

9. The method of any one of claims 1 to 4, wherein the weight ratio of the compound according to group b) to the compound according to group a) in composition A is in the range of 0.1 to 200.

10. The method of any one of claims 1 to 4, wherein the weight ratio of the compound according to group b) to the compound according to group a) in composition A is in the range of 10 to 75.

11. The method of any one of claims 1 to 4, wherein the pH of composition A is in the range of 7 to 12.

12. The method of any one of claims 1 to 4, wherein the pH of composition A is in the range of 8.5 to 10.

5.

13. The method of any one of claims 1 to 4, wherein the total concentration of water, calculated based on the total weight of composition A, is 50% by weight or higher.

14. The method of any one of claims 1 to 4, wherein composition A comprises one or more alkalizing agents different from the compound according to group b), selected from ammonia and / or its salts, organic alkyl and / or alkanolamines, and / or their salts, and / or mixtures thereof, the organic alkyl and / or alkanolamine having at least one basic functional group, the pKa of the conjugate acid of the basic functional group being greater than 8.0, and determined by acid-base titration of a 0.1 M solution of the alkalizing agent in water at 20°C under atmospheric conditions.

15. The method of any one of claims 1 to 4, wherein it comprises one or more direct dyes different from the direct dyes of group a).

16. The method of any one of claims 1 to 4, wherein it comprises one or more oxidizing dyes.

17. The method of any one of claims 1 to 4, wherein the oxidant in composition C is hydrogen peroxide.

18. The method of claim 17, wherein composition C contains hydrogen peroxide in a total concentration ranging from 0.1% to 20% by weight, calculated based on the total weight of composition C.

19. The method of claim 17, wherein composition C contains hydrogen peroxide in a total concentration ranging from 0.5% to 12% by weight, calculated based on the total weight of composition C.

20. The method of any one of claims 1 to 4, wherein the pH of composition C is in the range of 2 to 4.

5.

21. The method of any one of claims 1 to 4, wherein composition A comprises one or more thickening polymers selected from polymers that result in an aqueous solution and / or an aqueous dispersion with a pH between 8 and 10, and has a viscosity of at least 5,000 mPa•s in water at 25°C at a polymer concentration of 1% by weight of the total weight of composition A, the viscosity being determined by measuring for 1 minute at 25°C with a Brookfield viscometer using a suitable rotor, such as at 10 rpm.

22. A component kit comprising an aqueous dyeing composition A as defined in any one of claims 1 to 21, a composition B comprising Acid Yellow 1 and / or its salt, and a composition C as defined in any one of claims 1 to 21.