Hair dye composition and hair dyeing method

Abstract

To provide a hair dyeing composition that avoids contamination of the hands and skin, prevents damage to the hair and scalp, and exhibits high dyeing power, as well as a hair dyeing method using the hair dyeing composition.SOLUTION: A hair dyeing composition includes a dye precursor such as 4-methoxy-1-naphthol. A hair dyeing method includes the step of oxidizing a dye precursor in the hair dyeing composition with atmospheric oxygen to form the dye.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hair dye composition and a hair dyeing method. [Background technology]

[0002] A conventionally known method for dyeing hair in stages involves adding a small amount of dye to a shampoo, conditioner, or treatment, and gradually transferring the dye to the hair during the shampooing, conditioning, or treatment process. Another conventional hair dyeing method involves using a compound (dye precursor) that is converted into a dye by air oxidation, and oxidizing the compound with air during hair care treatment to form a dye, thereby coloring the hair in stages.

[0003] The method of gradually applying the dye to the hair has the disadvantage of inevitably staining the hands and skin during hair care, whereas the method of gradually coloring the hair by forming a pigment through air oxidation takes a little longer to dye the hair but has the advantage of reducing staining of the hands and skin.

[0004] Known methods for gradually coloring hair by air oxidation include a method using 1,2,4-trihydroxybenzene (Patent Document 1), a method using 5,6-dihydroxyindole (Patent Document 2), and a method using 1,8-dihydroxynaphthalene (Patent Document 3). However, all of these methods require a long time or multiple hair dyeing treatments to achieve the desired degree of coloring. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 63-064401 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-160669 [Patent Document 3] Special Publication No. 2013-512861 Summary of the Invention [Problem to be solved by the invention]

[0006] The problem to be solved by the present invention is to provide a hair dye composition and a hair dyeing method that do not stain hands and skin, do not damage hair and scalp, and have high hair dyeing power. [Means for solving the problem]

[0007] The present inventors have conducted extensive research in light of the above-mentioned problems and have found that certain compounds are rapidly oxidized by oxygen in the air to form pigments with high hair-dyeing power. The present invention has been completed based on these findings.

[0008] The present invention relates to a compound represented by the following general formula (1): and ( 3 and a dye precursor represented by the following general formula (1): and (3) In this case, R1 is Sulfobutoxy group or 2-hydroxy-3-trimethylammoniopropoxy group and R2 and R3 represent Each represents a hydrogen atom or a hydroxyl group, and in the following general formula (3), R 1 represents a methoxy group or a 3-trimethylammoniopropoxy group, and R 2 and R 3 represents a hydrogen atom The present invention relates to a hair dye composition characterized by the following formula:

[0009] [ka]

[0011] [ka]

[0013] The hair dye composition preferably comprises: Transition metal complex catalyst or oxidase It further contains The hair dye composition is more preferably 1-Hydroxybenzotriazole, N-hydroxyphthalimide, N-hydroxysuccinimide, violuric acid, syringaldazine, syringaldehyde, guaiacol, 2,6-dimethoxyphenol, nicotinamide adenine dinucleotide, flavin, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) It further contains

[0014] Furthermore, the present invention relates to a hair dyeing method comprising the step of oxidizing the dye precursor in the hair dye composition with oxygen in the air to form a dye. [Effects of the Invention]

[0015] The hair dye composition of the present invention provides a hair dye composition that does not stain hands or skin, does not damage hair or scalp, and has high hair dyeing power. The hair dyeing method of the present invention provides a hair dyeing method that does not stain hands or skin, does not damage hair or scalp, and achieves high hair dyeing power in a short period of time. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will now be described in further detail. Unless otherwise specified, the symbol "to" in a numerical range indicates a range from above to below, and both ends of the range are included. Furthermore, when a numerical range is indicated, the upper and lower limits can be combined as appropriate, and the resulting numerical range is also considered to be disclosed.

[0017] <Dye precursor> The hair dye composition of the present invention contains at least one dye precursor selected from the group consisting of dye precursors represented by the following general formulas (1) to (4): One or more dye precursors are used to adjust the color tone.

[0018] [ka]

[0019] [ka]

[0020] [ka]

[0021] [ka]

[0022] In the above general formulas (1) to (4), R1 represents an alkyl group, an alkoxy group, or an acyloxy group, and R2 and R3 each represent a hydrogen atom, a hydroxyl group, or an alkoxy group. In the above general formula (1) or (2), R1 and R2 may be linked to each other to form a ring structure.

[0023] The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent. Examples of the alkyl group include methyl, ethyl, hydroxyethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, and hexyl.

[0024] The alkoxy group is preferably an alkoxy group having from 1 to 12 carbon atoms, more preferably from 1 to 10 carbon atoms, and even more preferably from 1 to 8 carbon atoms. The alkoxy group may have a substituent. Examples of the alkoxy group include methoxy, ethoxy, isopropyloxy, benzyloxy, hydroxyethoxy, 2-hydroxypropoxy, sulfoethoxy, sulfopropoxy, sulfobutoxy, sulfopropylthioethoxy (these sulfo groups may be salts of Na, K, ammonium, etc.), (2-trimethylammonio)ethoxy, (3-trimethylammonio)propoxy, (2-hydroxy-3-trimethylammonio)propoxy, (2-hydroxy-3-dimethylhydroxyethylammonio)propoxy (counter anions of these quaternary ammonium groups include chloride ion, sulfate ion, toluenesulfonate ion, 1,5-naphthalenedisulfonate ion, etc.).

[0025] The acyloxy group is preferably an acyloxy group having from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms, and even more preferably from 1 to 10 carbon atoms. The acyloxy group may have a substituent. Examples of the acyloxy group include acetyloxy, propionyloxy, butyryloxy, benzoyloxy, pivaloyloxy, 3-sulfobenzoyloxy, 2-sulfobenzoyloxy, and 3-trimethylammoniobenzoyloxy (counter anion is a chloride ion).

[0026] Each of the alkyl group, the alkoxy group, and the acyloxy group may have a substituent T other than the above-mentioned substituents. The substituent T is not particularly limited, but is preferably a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group (aromatic heterocyclic group), or an aliphatic heterocyclic group.

[0027] The cycloalkyl group preferably has a carbon number of 3 to 8, more preferably 3 to 6. Examples of the cycloalkyl group include cyclopentyl and cyclohexyl.

[0028] The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 6 carbon atoms. Examples of the alkenyl group include vinyl, allyl, and butenyl.

[0029] The alkynyl group preferably has 2 to 8 carbon atoms, and more preferably has 2 to 6 carbon atoms. Examples of the alkynyl group include ethynyl and butynyl.

[0030] The aryl group is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include phenyl and tolyl.

[0031] When the aromatic heterocycle is a fused ring, it includes not only groups consisting of a monocyclic aromatic heterocycle but also groups consisting of a fused heterocycle in which another ring, such as an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a heterocycle, is fused to the monocyclic aromatic heterocycle. The number of ring-constituting heteroatoms constituting the aromatic heterocycle may be one or more, and the heteroatom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. Furthermore, the number of ring members in the aromatic heterocycle is preferably 5 to 6. The number of carbon atoms in the aromatic heterocycle is preferably 5 to 12, more preferably 5 to 10, and even more preferably 5 to 8. The number of carbon atoms in the aromatic heterocycle is preferably 5 to 12, more preferably 5 to 10, and even more preferably 5 to 8. Examples of 5-membered aromatic heterocycles and fused heterocycles containing 5-membered aromatic heterocycles include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a triazole ring, a furan ring, a thiophene ring, a benzimidazole ring, a benzoxazole ring, and a benzothiazole ring. Furthermore, examples of the 6-membered aromatic heterocycle and the fused heterocycle containing a 6-membered aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a quinoline ring, and a quinazoline ring.

[0032] The substituent T also includes the following groups. an aryloxy group (preferably an aryloxy group having from 6 to 12 carbon atoms, for example, phenoxy, 1-naphthyloxy, 4-methylphenoxy, 4-methoxyphenoxy, etc.); heterocyclic oxy group (a group in which an —O— group is bonded to the above heterocyclic group), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having from 2 to 12 carbon atoms, for example, ethoxycarbonyl, butoxycarbonyl, etc.); an aryloxycarbonyl group (preferably an aryloxycarbonyl group having from 6 to 12 carbon atoms, for example, phenoxycarbonyl, 1-naphthyloxycarbonyl, 4-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.); amino groups (unsubstituted or substituted amino groups having from 0 to 10 carbon atoms, for example, amino (-NH), N,N-dimethylamino, N,N-diethylamino, N-ethylamino, anilino, etc.); a sulfamoyl group (preferably a sulfamoyl group having from 0 to 12 carbon atoms, for example, N,N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.); acyl groups (including alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, arylcarbonyl groups, and heterocyclic carbonyl groups, preferably acyl groups having 1 to 12 carbon atoms, for example, acetyl, propionyl, butyryl, octanoyl, hexadecanoyl, acryloyl, methacryloyl, crotonoyl, benzoyl, naphthoyl, nicotinoyl, etc.); an aryloyloxy group (preferably an aryloyloxy group having from 7 to 13 carbon atoms, for example, benzoyloxy, etc.); a carbamoyl group (preferably a carbamoyl group having from 1 to 12 carbon atoms, for example, N,N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.); acylamino groups (preferably acylamino groups having 1 to 12 carbon atoms, for example, acetylamino, benzoylamino, etc.); an alkylthio group (preferably an alkylthio group having from 1 to 12 carbon atoms, for example, methylthio, ethylthio, isopropylthio, benzylthio, etc.); an arylthio group (preferably an arylthio group having from 6 to 12 carbon atoms, for example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.); heterocyclic thio group (a group in which the above heterocyclic group is bonded to an -S- group), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 12 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, etc.); an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 12 carbon atoms, for example, benzenesulfonyl, etc.); A phosphoryl group (preferably a phosphate group having 0 to 12 carbon atoms, for example, —OP(═O)(R P )2)、 A phosphonyl group (preferably a phosphonyl group having 0 to 12 carbon atoms, for example, —P(═O)(R P )2)、 A phosphinyl group (preferably a phosphinyl group having 0 to 12 carbon atoms, for example, -P(R P ) 2), sulfo group (sulfonic acid group), carboxy group, hydroxy group, sulfanyl group, cyano group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). R P is a hydrogen atom or a substituent (preferably a group selected from the above-mentioned substituents). Each of the groups listed as the substituents may further have a substituent T.

[0033] The content of the dye precursor is not limited to a particular range, but is preferably in the range of 0.01 to 3% by mass, more preferably 0.03 to 2% by mass, of the hair dye composition of the present invention.

[0034] The dye precursor can be synthesized from a corresponding 1-naphthol derivative, 2-naphthol derivative, 1,2-naphthoquinone derivative, or 1,4-naphthoquinone derivative, etc. Specifically, methods that can be applied include a method involving functional group conversion of a 1-naphthol derivative having a substituent at the 4-position, a method involving alkylation or acylation of the hydroxy group of 1,4-dihydroxynaphthalene, and a method involving reductive alkylation of a 1,4-naphthoquinone derivative.

[0035] <Oxidation catalyst> In the present invention, the dye precursor may be oxidized with oxygen in the air to form the dye, and in this case, an oxidation catalyst that promotes the oxidation reaction is preferably used.

[0036] Known catalysts can be used as the oxidation catalyst. Examples include transition metal complex catalysts and oxidases. Examples of useful transition metal complex catalysts include complexes of base metals such as Fe, Co, Ni, Mn, and Cu, and complexes of noble metals such as Pt, Rh, Ru, and Pd. Co, Mn, and Cu are particularly preferred. In these transition metal complexes, ligands coordinated to the metal include 1,3-diketone derivatives (acetylacetone, benzoylacetone, etc.), diaminobipyridyl derivatives (6,6'-bisbenzoylamino-2,2'-bipyridyl, etc.), salen derivatives (bissalicylideneethylenediamine, etc.), porphyrin derivatives, cyclam derivatives, hydroxycarboxylic acids (lactic acid, gluconic acid, etc.), nitrogen-containing heterocyclic carboxylic acids (2-pyrrolidone-5-carboxylic acid, etc.), amino acids (glycine, histidine, etc.), and peptides (glycylglycine, etc.). Examples of the oxidase include laccase, catalase, cytochrome oxidase, and xanthine oxidase.

[0037] The content of the oxidation catalyst is not limited to a particular range, but is preferably in the range of 0 to 500% by mass, more preferably 0.05 to 100% by mass, of the dye precursor.

[0038] The oxidation catalyst may be selected as desired based on the oxidizable properties of the dye precursor. To enhance the hair dyeing properties of the hair dye composition of the present invention, an oxidation catalyst with high oxidation activity is preferred. On the other hand, when the hair dye composition of the present invention is a one-pack hair dye composition, an oxidation catalyst with appropriate activity is selected because it is necessary to suppress oxidation reactions during the process of producing the hair dye composition and the process of filling the composition into a container.

[0039] <Mediator> In the present invention, a mediator (electron transfer agent) can be used to promote the oxidation reaction of the dye precursor by the oxidation catalyst and oxygen. Examples of mediators include 1-hydroxybenzotriazole, N-hydroxyphthalimide, N-hydroxysuccinimide, violuric acid, syringaldazine, syringaldehyde, guaiacol, 2,6-dimethoxyphenol, NADH, flavin, and ABTS.

[0040] The content of the mediator is not limited to a particular range, but is preferably in the range of 0 to 100% by mass, more preferably 0.05 to 10% by mass, of the dye precursor.

[0041] The dye precursor, the oxidation catalyst, and the mediator may be water-soluble or slightly soluble in water. Compounds having multiple hydroxyl groups, sulfo groups, or quaternary ammonium groups are generally water-soluble, while others are highly soluble in polar organic solvents such as lower alcohols. The solvent for the hair dye composition can be selected depending on the solubility of the compounds.

[0042] In general, in the absence of the oxidation catalyst, the dye precursor solution is stable even in the presence of air and can be stored for a long period of time if the pH is 6 or less. On the other hand, at a pH of 8 or higher, air oxidation (autoxidation) gradually occurs, and particularly at a pH higher than 9, the oxidation reaction is more likely to occur. Therefore, it is desirable to store the dye precursor solution in the presence of air at a neutral to weakly acidic pH.

[0043] The activity of the oxidation catalyst is also sensitive to pH, with some catalysts exhibiting high activity at low pH and others at high pH. Therefore, the optimum pH is selected in consideration of the properties of the dye precursor and the oxidation catalyst and the desired oxidation rate.

[0044] When the hair dye composition of the present invention is a one-component type, the dye precursor, oxidation catalyst, and mediator are all mixed in advance. On the other hand, when the hair dye composition of the present invention is a two-component type, the dye precursor and the mediator are mixed in advance, and the oxidation catalyst is separated separately, and these are mixed and used during hair dyeing. The dye precursor may also be separated from a mixture of the mediator and the oxidation catalyst, and these are mixed during hair dyeing.

[0045] When the hair dye composition of the present invention is a one-part type, the hair dye composition is prepared in an airtight environment at a pH of 8 or less, and is filled and stored in an airless container that can completely block air or an aerosol-type container into which a propellant gas is pressurized.

[0046] The form of the hair dye composition of the present invention is not limited. That is, the hair dye composition of the present invention may be in the form of a cream, gel, or liquid dissolved in a solvent. Because the hair dye composition of the present invention does not stain hands or skin and does not damage hair or scalp, it is recommended for use in shampoos, hair conditioners, hair treatments, and other hair dyes that are frequently used daily. It can also be used as a hair dye that can provide high hair dyeing properties with a single treatment. These forms include liquid, cream, gel, and foam, but a mousse form dispensed from an aerosol can is preferred because it increases the surface area in contact with air, accelerates the oxidation reaction, and enhances hair dyeing properties.

[0047] When the present invention is applied to shampoo, specifically a mousse-like shampoo dispensed from an aerosol can, the propellant may be liquefied petroleum gas, dimethyl ether, carbon dioxide, nitrogen gas, etc. The ratio of the propellant to the hair dye composition of the present invention is preferably in the range of 1:20 to 1:1, more preferably 1:20 to 1:10, on a mass basis.

[0048] The hair dye composition of the present invention may further contain other dye precursors that undergo air oxidation to produce colored substances. Specific preferred examples of the other dye precursors include gallic acid, ethyl gallate, propyl gallate, tannic acid, taratannin, catechins, 3,4-dihydroxyphenylalanine (L-DOPA), brazilin, hematoxylin, 1,8-dihydroxynaphthalene, 2-methyl-1-naphthol, 1,2,4-trihydroxybenzene, and 2,6-dimethoxyphenol. One or more of these compounds may be used.

[0049] When the hair dye composition of the present invention is used as a shampoo, the content of the other dye precursors is preferably in the range of 0.01 to 1.0% by mass, more preferably 0.05 to 0.5% by mass, based on the shampoo solution.

[0050] When the hair dye composition of the present invention is used as a shampoo, a gradual dyeing shampoo can be prepared by dissolving the dye precursor in water or an organic solvent in advance, and then adding an appropriate amount of surfactant under an air-tight condition.

[0051] Examples of the organic solvent include ethanol, propanol, isopropanol, propylene glycol, butylene glycol, isoprene glycol, pentylene glycol, benzyl alcohol, benzyloxyethanol, ethyl benzoate, hydroxyethyl benzoate, carbitol, ethoxydiglycol, etc. One or more of these organic solvents may be used.

[0052] The organic solvent is preferably an organic solvent that has high solubility for the dye precursor and good hair dyeing properties, such as propylene glycol, butylene glycol, isoprene glycol, benzyl alcohol, benzyloxyethanol, and ethoxydiglycol.

[0053] The content of the organic solvent is not limited to a particular range, but is preferably in the range of 10 to 1000% by mass, more preferably 20 to 200% by mass, of the dye precursor.

[0054] The hair dye composition of the present invention may contain a surfactant, such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.

[0055] Examples of the anionic surfactant include sodium olefin sulfonate, sodium laureth sulfate, sodium lauryl sulfate, sodium stearoyl methyl taurate, sodium cocoyl glutamate, sodium lauroyl methyl alanine, and sodium stearoyl glutamate.

[0056] Examples of the cationic surfactant include behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, and stearamidopropyldimethylamine.

[0057] Examples of the nonionic surfactant include alkyl glucosides, fatty acid alkanolamides, polyvinylpyrrolidones, polyethylene oxides, polyethylene oxide monoalkyl ethers, polyethylene oxide diethers, polyethylene oxide monophenyl ethers, polypropylene oxides, polypropylene oxide monoalkyl ethers, polypropylene oxide dialkyl ethers, polyethylene oxide fatty acid esters, glycerin fatty acid esters, glycerin monoethers, and sorbitan fatty acid esters.

[0058] Examples of the amphoteric surfactant include cocamidopropyl betaine, cocamidopropyl hydroxysultaine, and lauramidopropyl betaine. One or more of these surfactants may be used.

[0059] Preferred surfactants in the present invention are anionic surfactants, nonionic surfactants, and amphoteric surfactants, each having an appropriate level of detergency, and are selected depending on the charge characteristics of the dye precursor and the dye to be used in combination.

[0060] The content of the surfactant is not limited to a particular range, but is preferably in the range of 10 to 1000% by mass, more preferably 20 to 800% by mass, of the dye precursor.

[0061] The hair dye composition of the present invention may contain a dye in addition to the dye precursor. Examples of such dyes include acid dyes, basic dyes, and HC dyes. More preferred dyes include Yellow No. 406, Yellow No. 407, Orange No. 205, Red No. 227, Purple No. 401, Black No. 401, Basic Yellow 40, Basic Yellow 57, Basic Yellow 87, Basic Orange 1, Basic Orange 31, Basic Red 51, Basic Red 76, Basic Blue 99, and Basic Blue 124. Plant-derived dyes such as lawsone, juglone, brazilein, and hematein can also be used in combination.

[0062] The hair dye composition of the present invention may contain various cationic polymers for the purpose of improving hair quality after shampooing. Specific examples of the cationic polymer include hydroxypropyltrimonium derivatives of natural polysaccharides such as starch, cellulose, guar gum, tara gum, chitosan, and hyaluronic acid, and polyquaterniums in which quaternary ammonio groups have been introduced into synthetic polysaccharides. Preferred examples of the polyquaterniums include Polyquaternium 6, Polyquaternium 7, Polyquaternium 10, Polyquaternium 11, Polyquaternium 22, and Polyquaternium 53. The content of the cationic polymer in the hair dye composition of the present invention is preferably in the range of 0.02 to 1.5% by mass.

[0063] The hair dye composition of the present invention may contain a stabilizer to inhibit oxidation of the dye precursor. Specific examples of the stabilizer include ascorbic acid, erythorbic acid, sodium bisulfite, and sodium sulfite. The content of the stabilizer in the hair dye composition of the present invention is preferably in the range of 0.005 to 0.5% by mass.

[0064] The hair dye composition of the present invention may contain various additives, such as humectants, thickeners, oily components, higher alcohols, animal and plant extracts, amino acids, preservatives, UV absorbers, sequestering agents, pH adjusters, skin conditioning agents, anti-inflammatory agents, pigments, and fragrances.

[0065] Examples of the humectant include glycerin, diglycerin, propylene glycol, 1,3-butanediol, isoprene glycol, pentanediol, dipropylene glycol, polyethylene glycol, sorbitol, glucose, maltitol, xylose, dihydroxyacetone, and erythrulose.

[0066] Examples of the thickener include pectin, carrageenan, galactomannan, xanthan gum, guar gum, tara gum, gum arabic, methylcellulose, hydroxyethylcellulose, and gelatin.

[0067] Examples of the oily component include ethylhexyl palmitate, isopropyl myristate, mineral oil, dimethicone, and amodimethicone.

[0068] Examples of the higher alcohols include behenyl alcohol, stearyl alcohol, cetyl alcohol, cetearyl alcohol, and myristyl alcohol.

[0069] Examples of the animal and plant extracts include placenta extract, marine placenta extract, hydrolyzed collagen, hydrolyzed keratin, hydrolyzed silk, hydrolyzed elastin, yeast extract, aloe extract, comfrey extract, peony extract, perilla extract, swertia japonica extract, witch hazel water, sedge extract, hop extract, sage extract, horse chestnut extract, peach leaf extract, saxifrage extract, melissa extract, mugwort extract, rosemary extract, fermented rice bran extract, pine extract, prune extract, trehalose, sodium hyaluronate, fermented soybean extract, hydroxyethyl chitosan, water-soluble collagen, Gynostemma pentaphyllum extract, fennel extract, Pueraria lobata extract, kiwi extract, cucumber extract, gardenia extract, chlorella extract, rehmannia root extract, burdock root extract, loofah extract, peony extract, coltsfoot extract, poria cocos extract, grape leaf extract, coix seed extract, mugwort extract, and apple extract. , umbilical cord extract, hydrolyzed yeast extract, mucopolysaccharide, honey, hydrolyzed silk, aloe vera extract, peach leaf extract, St. John's wort extract, artemisia capillaris extract, raspberry extract, grapefruit extract, orchid extract, astragalus extract, and atelocollagen.

[0070] Examples of the amino acids include glycine, alanine, γ-aminobutyric acid, L-aspartic acid, L-arginine, L-isoleucine, L-glutamine, L-glutamic acid, L-threonine, L-tyrosine, L-tryptophan, L-valine, L-histidine hydrochloride, L-hydroxyproline, L-proline, L-leucine, L-methionine, and lysine hydrochloride.

[0071] Examples of the preservative include methylparaben, ethylparaben, propylparaben, butylparaben, isobutylparaben, phenoxyethanol, bisabolol, hinokitiol, benzoic acid, sodium benzoate, salicylic acid, sodium salicylate, sorbic acid, potassium sorbate, undecylenic acid, pionin, l-menthol, and d-camphor.

[0072] Examples of the ultraviolet absorber include para-aminobenzoic acid, ethyl para-aminobenzoate, glyceryl para-aminobenzoate, 2-ethylhexyl para-dimethylaminobenzoate, oxybenzone, dihydroxybenzophenone, dihydroxydimethoxybenzophenone, sodium dihydroxydimethoxybenzophenone sulfonate, sodium hydroxymethoxybenzophenone sulfonate, and octyl salicylate.

[0073] Examples of the sequestering agent include edetic acid, edetate salts, trisodium ethylenediaminehydroxyethyltriacetate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, ethylenediaminetetrakis(2-hydroxyisopropyl)dioleate, hydroxyethanedisulfonate, and phytic acid.

[0074] Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, and salts thereof, potassium carbonate, sodium bicarbonate, ammonium bicarbonate, potassium hydroxide, sodium hydroxide, monoethanolamine, triethanolamine, and 2-amino-2-methylpropanediol.

[0075] Examples of the skin conditioning agent include carboxyvinyl polymer, polyvinylpyrrolidone, cationized cellulose, cationized guar gum, sodium hyaluronate, sodium polyacrylate, hydrogenated polyisobutene, hydrolyzed elastin, hydrolyzed keratin, hydrolyzed collagen, hydrolyzed ethyl collagen, hydrolyzed hexadecyl collagen, water-soluble collagen, xylitol, guanosine, guanine, glucuronic acid, sodium chondroitin sulfate, intercellular lipids, acidic mucopolysaccharides, water-soluble elastin, sphingolipids, sericin, soybean lysophospholipid lysolecithin, soybean phospholipid, comb extract, egg yolk phospholipid, hydrolyzed conchiolin, hydrolyzed eggshell membrane hydrolyzate, animal placenta extract, and royal jelly extract.

[0076] Examples of the anti-inflammatory agent include dipotassium glycyrrhizinate, allantoin, diphenhydramine hydrochloride, sodium guaiazulenesulfonate, benzyl nicotinate, lysozyme chloride, and aminocaproic acid.

[0077] The hair dye composition of the present invention can be used for various purposes. When the hair dye composition of the present invention is used as a shampoo, repeated shampooing of the hair can provide a high hair dyeing effect. The number of shampooing sessions is not limited to a specific range, but is preferably once a day for at least one week, more preferably for at least one month. It is even more preferable to use the hair dye composition of the present invention on a daily basis as a regular shampoo. When using the hair dye composition of the present invention as a shampoo, the amount used per session can be adjusted appropriately depending on the hair volume, and the longer the shampooing time, the better, but it is usually in the range of 1 to 10 minutes. After shampooing, the hair can be simply rinsed with hot water, or a conditioner and / or treatment can be applied subsequently.

[0078] When the hair dye composition of the present invention is used as a color treatment, repeated treatment of the hair can provide a high hair dyeing effect. The number of treatments is not limited to a specific range, but it is preferable to perform the treatment three consecutive days in the first week, and then perform the treatment once a week from the following week. When using the hair dye composition of the present invention as a color treatment, the amount used per treatment is adjusted appropriately according to the hair volume, and the longer the treatment time, the better, but it is usually in the range of 3 to 15 minutes. After the treatment, the hair can be rinsed thoroughly with hot water. Alternatively, shampooing may be performed subsequently.

[0079] When the hair dye composition of the present invention is used as a hair dye that can be sufficiently dyed with a single treatment, the hair is first washed with hot water to swell the hair, and then a sufficient amount of the hair dye composition of the present invention is applied to the hair using a comb or brush and left to stand for typically 5 to 30 minutes. During this time, wrapping the hair in a thin polymer film improves the dyeing properties. After that, the hair is thoroughly rinsed with hot water, followed by shampooing and treatment. [Example]

[0080] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0081] (Synthesis Example 1) Synthesis of Compound 1 in which R1=methoxy group, R2=R3=H in the general formula (1) To a mixture of 20 g of 1,4-naphthoquinone, 250 ml of methanol, and 90 ml of concentrated hydrochloric acid, 100 g of stannous chloride dihydrate was added in small portions and stirred at 40°C for 3 hours. After cooling to room temperature, 500 ml of water was added and stirred for 2 hours. The precipitated 4-methoxy-1-naphthol (compound 1, where R1 = methoxy group, R2 = R3 = H in the general formula (1)) was collected by filtration (yield: 17.7 g). The purified product was obtained by recrystallization from a mixed solvent of n-hexane and ethyl acetate (volume ratio 1 / 1).

[0082] (Synthesis Example 2) Synthesis of Compound 2 in which R1=hydroxyethoxy group, R2=R3=H in the general formula (1) To a mixture of 20 g of 1,4-naphthoquinone, 300 ml of ethylene glycol, and 100 ml of concentrated hydrochloric acid, 100 g of stannous chloride dihydrate was added in small portions and stirred at 70°C for 3 hours. After cooling to room temperature, 500 ml of water was added and the mixture was extracted twice with 500 ml of ethyl acetate. The resulting extract was washed with brine and dried over anhydrous magnesium sulfate, after which the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 10.5 g of compound 2 (a compound represented by the general formula (1) above, in which R1 = hydroxyethoxy group, R2 = R3 = H).

[0083] (Synthesis Example 3) Synthesis of Compound 3 in which R1=sulfobutoxy group, R2=R3=H in the general formula (1) Under a nitrogen stream, 16 g of 1,4-naphthohydroquinone was added to a solution of 30 ml of ethanol and 5.2 g of sodium hydroxide in 200 ml of water. Then, under a nitrogen stream, 13.6 g of butane sultone was added dropwise at room temperature. After stirring at 80°C for 3 hours, the mixture was cooled to room temperature and neutralized with dilute hydrochloric acid. 200 ml of ethyl acetate was added and the mixture was shaken to separate the ethyl acetate-soluble fraction. Excess potassium chloride was added to the aqueous layer to salt out, and the precipitated crystals were filtered out as the potassium salt (compound 3, where R1 = sulfobutoxy group, R2 = R3 = H in the general formula (1) above) (yield: 13.9 g). The crude product was recrystallized from an aqueous potassium chloride solution to obtain a purified product.

[0084] (Synthesis Example 4) Synthesis of Compound 4, wherein R1=2-hydroxy-3-trimethylammoniopropoxy group, R2=R3=H in the general formula (1) To a mixture of 10 g of 1,4-naphthohydroquinone, 12 g of an 80% by weight aqueous solution of glycidyltrimethylammonium chloride, and 100 ml of ethanol, 125 ml of 1N aqueous sodium hydroxide solution was added under a nitrogen stream. After stirring at 40°C for 4 hours under a nitrogen stream, the mixture was cooled to room temperature and neutralized with dilute hydrochloric acid. 200 ml of ethyl acetate was added to the reaction mixture and the mixture was shaken to separate the ethyl acetate-soluble components. 100 ml of saturated brine was added to the aqueous layer, and the mixture was extracted twice with 100 ml of acetonitrile. The solvent was removed from the extract under reduced pressure, and 200 ml of methanol was added to the residue and heated, and the insoluble components were filtered off. The solvent was removed from the filtrate under reduced pressure to obtain the target product as a chloride (compound 4, represented by the general formula (1) above, where R1 = 2-hydroxy-3-trimethylammoniopropoxy, R2 = R3 = H) (yield: 8.2 g).

[0085] (Synthesis Example 5) Synthesis of Compound 5 in which R1=methoxy group, R2=H, and R3=hydroxyl group in the general formula (1) 2.0 g of juglone and 9.0 g of stannous chloride dihydrate were added to 60 ml of a 2 M solution of hydrogen chloride in methanol and stirred at 65°C for 2 hours. After cooling to room temperature, the reaction mixture was poured into 500 ml of cold water and extracted twice with 200 ml of ethyl acetate. After washing twice with saturated brine, the mixture was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from ethyl acetate / hexane, and pale gray crystals of compound 5, represented by the general formula (1) above, in which R1 = methoxy, R2 = H, and R3 = hydroxyl, were collected by filtration (yield: 1.5 g).

[0086] (Synthesis Example 6) Synthesis of Compound 6 in which R1=ethoxy group, R2=H, and R3=OH in the general formula (1) To a mixture of 5 g of juglone, 50 ml of ethanol, and 10 ml of concentrated hydrochloric acid, 20 g of stannous chloride dihydrate was added in small portions and stirred at 40°C for 3 hours. After cooling to room temperature, 300 ml of water was added to the reaction mixture, and the mixture was extracted twice with 150 ml of ethyl acetate. The extract was washed with brine and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography to obtain 2.9 g of the target compound 6 (general formula (1) above, R1 = ethoxy group, R2 = H, R3 = OH).

[0087] (Synthesis Example 7) Synthesis of Compound 7 in which R1=sulfobutoxy group, R2=R3=H in the general formula (2) 3.0 g of the compound of Synthesis Example 3 was dissolved in 100 ml of water and stirred in the atmosphere at 40°C for 48 hours. After cooling to room temperature, 50 ml of water was distilled off under reduced pressure. After standing overnight, the precipitated white crystals of the target dipotassium salt (Compound 7, where R1 = sulfobutoxy group, R2 = R3 = H in the general formula (2)) were collected by filtration (yield: 2.1 g).

[0088] (Synthesis Example 8) Synthesis of Compound 8 in which R1=methoxy group, R2=R3=H in the general formula (3) 1.68 g of 2-methoxy-1-naphthaldehyde was dissolved in 10 mL of methylene chloride. Next, 10 mL of 30% aqueous hydrogen peroxide, 1 mL of trifluoroacetic acid, and 0.1 g of selenium dioxide were added and vigorously stirred at room temperature. After stirring for 4 hours, the reaction mixture was poured into ice water, and 100 mL of saturated saline and 100 mL of ethyl acetate were added to separate the organic layer. The organic layer was washed with aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography (hexane / ethyl acetate = 4:1) to yield white crystals (formyl form of compound 8). This was added to 20 mL of 5% aqueous sodium hydroxide under nitrogen and stirred at room temperature for 1 hour. The mixture was neutralized with dilute hydrochloric acid, extracted with ethyl acetate, washed with water, and dried. The solvent was evaporated under reduced pressure to yield compound 8 (0.75 g), a colorless liquid with general formula (3), in which R1 = methoxy and R2 = R3 = H.

[0089] (Synthesis Example 9) Synthesis of Compound 9, wherein R1=3-trimethylammoniopropoxy group, R2=R3=H in the general formula (3) 3.44 g of 2-hydroxy-1-naphthaldehyde, 6.26 g of 3-bromopropyltrimethylammonium bromide, and 3.32 g of anhydrous potassium carbonate were added to 100 ml of acetonitrile and stirred for 5 hours under heat. After cooling, the solvent was evaporated under reduced pressure. The residue was dissolved in methanol, and the soluble fraction was purified by silica gel chromatography (eluent: methanol / methylene chloride (1:3)) to obtain 3.70 g of crystalline bromide of 2-(3-trimethylammoniopropoxy)-1-naphthaldehyde. 2.5 g of the above compound was added to 15 mL of 30% aqueous hydrogen peroxide, followed by 2 mL of trifluoroacetic acid and 0.1 g of selenium dioxide, and the mixture was stirred at 40°C for 3 hours. After cooling, the reaction mixture was added to 30 mL of ice water, and 7.21 g of 1,5-naphthalenedisulfonic acid tetrahydrate was added. The mixture was stirred at room temperature for 2 hours, yielding 1.45 g of pale pink crystals of compound 9, in which the hydroxyl group was formylated (the anion was 1,5-naphthalenedisulfonate). This was added to 20 mL of 5% aqueous sodium hydroxide solution under nitrogen and stirred at room temperature for 1 hour. Subsequently, 7.21 g of 1,5-naphthalenedisulfonic acid tetrahydrate was added to the reaction mixture for neutralization, yielding pale pink crystals of compound 9 (yield: 0.98 g).

[0090] (Synthesis Example 10) Synthesis of Compound 10 in which R1=methoxy group, R2=R3=H in the general formula (4) 0.50 g of compound 8 was dissolved in 10 ml of ethanol and stirred at room temperature for 24 hours. The solvent was evaporated under reduced pressure, and 10 ml of n-hexane was added to the residue and stirred at room temperature to obtain pale pink crystals of compound 10 (yield 0.28 g).

[0091] Example 1 In a glove box filled with nitrogen, 200 mg of Compound 1 and 50 mg of cobalt(II) salen complex were heated and dissolved in a mixture of 200 mg of ethanol and 200 mg of benzyloxyethanol, and the solution was mixed with 9.35 g of a surfactant stock solution having the composition shown below to prepare Shampoo 1.

[0092] Cocamidopropyl betaine 3.50% by mass Sodium lauroylmethylalanine 0.10% by mass Olefin (C14-C16) Sodium Sulfonate 0.05% by mass Decyl glucoside 1.60% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Sodium hydrogen sulfite 0.02% by mass Lactic acid 0.20% by mass Purified water was added to make the total amount 100% by mass.

[0093] An appropriate amount of the shampoo 1 was applied to 1 g of a 100% human gray hair bundle (manufactured by Beaulax) moistened with warm water, and the shampoo was left for 5 minutes while creating sufficient lather. The hair bundle was then rinsed with warm water and dried with a hair dryer. The gray hair bundle was dyed a light blue-green color. After repeating the shampooing procedure five times, the hair bundle was dyed a dark blue-green color.

[0094] Example 2 In a glove box filled with nitrogen, 200 mg of Compound 2 and 100 mg of manganese(II) acetylacetonate complex were heated and dissolved in a mixture of 200 mg of ethanol and 200 mg of benzyloxyethanol, and the solution was mixed with 9.3 g of a surfactant stock solution having the composition shown below to prepare Shampoo 2.

[0095] Cocamidopropyl betaine 3.00% by mass Sodium lauroylmethylalanine 0.10% by mass Olefin (C14-C16) Sodium Sulfonate 0.05% by mass Decyl glucoside 3.60% by mass Lauramidopropyl betaine 1.50% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Ascorbic acid 0.05% by mass Lactic acid 0.20% by mass Purified water was added to make the total amount 100% by mass.

[0096] When shampooing was carried out in the same manner as in Example 1, the white hair strands were dyed pale blue.

[0097] Example 3 Instead of Compound 1 in Example 1, 250 mg of Compound 3 was dissolved in 2 ml of water, and the solution was mixed with 7.75 g of a surfactant stock solution having the composition shown below to prepare Shampoo 3.

[0098] Lauramidopropyl betaine 3.50% by mass Sodium lauroylmethylalanine 0.10% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.20% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Copper gluconate 0.30% by mass Ascorbic acid 0.05% by mass Lactic acid 0.30% by mass Purified water was added to make the total amount 100% by mass.

[0099] When shampooed in the same manner as in Example 1, the white hair strands were dyed a pale blue-green color.

[0100] Example 4 Instead of the compound 1 in Example 1, 250 mg of the compound 4 was mixed with 9.75 g of a surfactant stock solution having the composition shown below to prepare shampoo 4.

[0101] Lauramidopropyl betaine 2.50% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.50% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.30% by mass Copper 2-pyrrolidone-5-carboxylate 0.30% by mass Ascorbic acid 0.05% by mass Lactic acid 0.10% by mass Purified water was added to make the total amount 100% by mass.

[0102] When shampooed in the same manner as in Example 1, the white hair strands were dyed a relatively deep green-blue color.

[0103] Example 5 In Example 4, 100 mg of laccase derived from Coriolus versicolor was added instead of copper 2-pyrrolidone-5-carboxylate, and mixed with 9.65 g of a surfactant stock solution having the composition shown below to prepare Shampoo 5.

[0104] Lauramidopropyl betaine 3.50% by mass Sodium lauroylmethylalanine 0.10% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.20% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Ascorbic acid 0.05% by mass Lactic acid 0.20% by mass Purified water was added to make the total amount 100% by mass.

[0105] When shampooed in the same manner as in Example 1, the gray hair strands were dyed a deep blue-green color.

[0106] Example 6 Shampoo 6 was prepared by mixing 200 mg of Compound 8, instead of Compound 1 in Example 1, with 9.8 g of a surfactant stock solution having the composition shown below.

[0107] Lauramidopropyl betaine 3.50% by mass Sodium lauroylmethylalanine 0.05% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.20% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Copper 2-pyrrolidone-5-carboxylate 0.30% by mass Ascorbic acid 0.05% by mass Lactic acid 0.20% by mass Purified water was added to make the total amount 100% by mass.

[0108] When shampooed in the same manner as in Example 1, the white hair strands were dyed pale pink.

[0109] Example 7 Instead of compound 1 in Example 1, 250 mg of compound 9 was mixed with 9.75 g of a surfactant stock solution having the composition shown below to prepare shampoo 7.

[0110] Lauramidopropyl betaine 3.50% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.20% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Copper 2-pyrrolidone-5-carboxylate 0.30% by mass Ascorbic acid 0.05% by mass Lactic acid 0.10% by mass Purified water was added to make the total amount 100% by mass.

[0111] When shampooed in the same manner as in Example 1, the white hair strands were dyed dark reddish purple.

[0112] Example 8 Instead of compound 1 in Example 1, 200 mg of compound 4 was mixed with 9.8 g of a surfactant stock solution having the composition shown below to prepare shampoo 8.

[0113] Lauramidopropyl betaine 3.50% by mass Sodium lauroylmethylalanine 0.10% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.20% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Copper 2-pyrrolidone-5-carboxylate 0.30% by mass Basic Orange 31 0.01% by mass Ascorbic acid 0.05% by mass Lactic acid 0.10% by mass Purified water was added to make the total amount 100% by mass.

[0114] When shampooed in the same manner as in Example 1, the white hair strands were dyed brown.

[0115] Example 9 Instead of compound 1 in Example 1, 100 mg of compound 4 was mixed with 9.8 g of a surfactant stock solution having the composition shown below to prepare shampoo 9.

[0116] Lauramidopropyl betaine 3.50% by mass Sodium lauroylmethylalanine 0.10% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.20% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Copper 2-pyrrolidone-5-carboxylate 0.30% by mass Basic Orange 31 0.01% by mass Basic Blue 124 0.02% by mass Ascorbic acid 0.05% by mass Lactic acid 0.10% by mass Purified water was added to make the total amount 100% by mass.

[0117] When shampooed in the same manner as in Example 1, the white hair strands were dyed black.

[0118] Example 10 In Example 4, 30 mg of N-hydroxysuccinimide was further added as a mediator, and mixed with 9.72 g of a surfactant stock solution having the composition shown below to prepare Shampoo 10.

[0119] Lauramidopropyl betaine 3.50% by mass Sodium lauroylmethylalanine 0.05% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.20% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Copper gluconate 0.30% by mass Ascorbic acid 0.05% by mass Lactic acid 0.10% by mass Purified water was added to make the total amount 100% by mass.

[0120] When shampooed in the same manner as in Example 1, the gray hair strands were dyed a relatively dark blue-green color.

[0121] Example 11 Shampoo 11 was prepared by mixing 9.7 g of a surfactant stock solution having the composition shown below with a mixture of 200 mg of compound 4 and 100 mg of hematoxylin in place of compound 1 in Example 1.

[0122] Lauramidopropyl betaine 3.50% by mass Sodium lauroylmethylalanine 0.10% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.20% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 0.80% by mass Cobalt(II) salen complex 0.30% by mass Ascorbic acid 0.05% by mass Lactic acid 0.10% by mass Purified water was added to make the total amount 100% by mass.

[0123] When shampooed in the same manner as in Example 1, the white hair strands were dyed a light dark brown.

[0124] Example 12 In a nitrogen-filled glove box, 300 mg of compound 4 was dissolved in 2.0 g of water by heating, and the solution was mixed with 19.7 g of a surfactant concentrate solution having the composition shown below to prepare a shampoo solution. The shampoo solution was filled into a 50 ml aerosol can, and then 2.0 g of liquefied petroleum gas was injected to prepare an aerosol shampoo 12.

[0125] Lauramidopropyl betaine 3.50% by mass Decyl glucoside 1.20% by mass Cocamidopropyl betaine 1.00% by mass Lauric acid polyglyceride-10 1.00% by mass Polyquaternium 10 1.00% by mass Copper 2-pyrrolidone-5-carboxylate 0.30% by mass Ascorbic acid 0.05% by mass Lactic acid 0.10% by mass Purified water was added to make the total amount 100% by mass.

[0126] A mousse-like shampoo was dispensed from the aerosol can, and a sufficient amount was applied evenly to a 1g bundle of 100% human gray hair (manufactured by Beaulax) moistened with warm water, and left for 5 minutes. The bundle was then rinsed thoroughly with warm water and dried with a hair dryer. The gray hair bundle was dyed a light blue-green color. Repeating the same procedure five times resulted in the hair bundle being dyed a dark blue-green color.

[0127] (Comparative Example 1) Comparative shampoo 1 was prepared using 200 mg of 1,2,4-trihydroxybenzene instead of Compound 1 and the cobalt(II) salen complex in Example 1, and shampooing was carried out once, five times, and ten times in the same manner as in Example 1. The gray hair tresses were gradually dyed brown, but the dyeability was significantly lower than in Example 1.

[0128] (Comparative Example 2) Comparative Shampoo 2 was prepared using 200 mg of 1,8-dihydroxynaphthalene instead of Compound 1 and the cobalt(II) salen complex in Example 1, and the shampooing procedure was carried out in the same manner as in Example 1. The shampooing time was extended to 15 minutes, but the gray hair strands were hardly dyed.

[0129] Example 13 Application to color treatment Phase A was prepared by mixing the compounds in the proportions shown below at 80°C until they were homogenized. Cetearyl alcohol 5.00g Behenyl alcohol 0.50g Sorbitan palmitate 0.50g Polysorbate 20 0.20g PPG-52 Butyl 0.50g

[0130] Phase B was prepared by mixing the compounds in the proportions shown below at 80°C until they were homogenized. 79.4g water Propylene glycol 2.00g Hydroxypropyl methylcellulose 0.20g Aluminum chlorohydrate 0.10g Ascorbic acid 0.05g Sodium hydroxide 0.07g Compound 4 0.50 g

[0131] Phase C was prepared by mixing the compounds in the proportions shown below at 80°C until they were homogenized. Ethylhexylglycerin 0.20g Phenoxyethanol 0.50g Water 10.00g Copper 2-pyrrolidone-5-carboxylate 0.50g

[0132] Preparation of color treatment solution Under a nitrogen atmosphere, while stirring with a homomixer, Phase A was gradually added to Phase B at 80° C. The resulting mixture was then stirred at 80° C. and 4000 rpm for 10 minutes and cooled to 60° C. Thereafter, Phase C was added to the mixture while stirring, and the mixture was poured into an airless bottle while still warm to prepare Color Treatment 1.

[0133] An appropriate amount of the Color Treatment 1 was evenly applied to 1 g of 100% human gray hair bundle manufactured by Bealux and left at room temperature for 10 minutes. The hair bundle was then rinsed with hot water until the wash liquid was no longer colored, and then dried with a hair dryer. The gray hair bundle was dyed blue-green. After repeating the Color Treatment procedure five times, the gray hair bundle was dyed a deep dark blue-green.

[0134] Example 14 Color Treatment 2 was prepared in the same manner as in Example 13, except that 0.01 g of Basic Orange 31 was added to Phase B.

[0135] An appropriate amount of Color Treatment 2 was evenly applied to 1 g of 100% human gray hair bundle manufactured by Bealux and left at room temperature for 10 minutes. The hair bundle was then rinsed with hot water until the wash liquid was no longer colored, and then dried with a hair dryer. The gray hair bundle was dyed brown. After repeating the above procedure five times, the gray hair bundle was dyed a deep dark brown.

[0136] Example 15 Application to hair dyes 300 mg of the dye precursor compound 5 was dissolved in a mixture of 10 ml of water, 10 ml of ethanol, and 0.1 ml of aqueous ammonia, and 1 g of a 100% human gray hair bundle (manufactured by Beaulux) was immersed in the solution. After leaving the solution at room temperature for 30 minutes, the hair bundle was rinsed with hot water, shampooed, and dried with a hair dryer. The gray hair bundle was dyed a deep dark green.

[0137] Example 16 300 mg of the dye precursor compound 5 was dissolved in a mixture of 10 ml of water, 10 ml of ethanol, and 50 mg of ethanolamine, and 1 g of a 100% human gray hair bundle (manufactured by Beaulax) was immersed in the solution. After leaving the solution at room temperature for 30 minutes, the hair bundle was rinsed with hot water, shampooed, and dried with a hair dryer. The gray hair bundle was dyed a deep dark blue-green color.

[0138] Example 17 200 mg of the dye precursor compound 5 and 100 mg of the dye precursor compound 8 were dissolved in a mixture of 10 ml of water, 5 ml of ethanol, 5 ml of propylene glycol, 50 mg of Ceteth 40, and 50 mg of potassium bicarbonate. A solution of 100 mg of copper gluconate dissolved in 5 ml of water was then added. 1 g of a 100% human gray hair bundle (Beaulux) was immersed in the solution and shaken at room temperature for 15 minutes. The hair bundle was rinsed with hot water, shampooed, and dried with a hair dryer. The gray hair bundle was dyed black.

Claims

1. The dye precursor contains at least one selected from the group consisting of dye precursors represented by the following general formulas (1) and (3), and in the following general formula (1), R １ represents a sulfobutoxy group or a 2-hydroxy-3-trimethylammoniopropoxy group, R ２ and R ３ each represents a hydrogen atom or a hydroxyl group, and in the following general formula (3), R 1 represents a methoxy group or a 3-trimethylammoniopropoxy group, and R 2 and R 3 represent hydrogen atoms. 【Chemical 1】 【Chemistry 2】

2. A hair dye composition as described in claim 1, further containing a transition metal complex catalyst or an oxidase.

3. The hair dye composition according to claim 2, further containing 1-hydroxybenzotriazole, N-hydroxyphthalimide, N-hydroxysuccinimide, violuric acid, syringaldazine, syringaldehyde, guaiacol, 2,6-dimethoxyphenol, nicotinamide adenine dinucleotide, flavin, and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid).

4. A hair dyeing method comprising the step of oxidizing the dye precursor in the hair dye composition according to any one of claims 1 to 3 with oxygen in the air to form a dye.

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