Hair dye composition

Abstract

To provide a hair dye composition which has high chroma and inhibits discoloration caused by washing hair.SOLUTION: The hair dye composition contains (A) a compound represented by general formula (1) or a salt thereof, and (B) a coupler. (In the formula, each R is independently a hydrogen atom, methyl group or ethyl group, and n is an integer from 1 to 3.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a hair dye composition.

Background Art

[0002] As a hair dye, an oxidative hair dye is known. In an oxidative hair dye, a dye intermediate mainly develops color by oxidative polymerization to exhibit a hair dyeing effect. Conventionally, p-phenylenediamine, p-toluylenediamine, p-aminophenol, etc. have been widely used as typical dye intermediates. Among these, hair dye-containing substances using a 4,5-diaminopyrazole derivative as a dye intermediate have been used. For example, Patent Document 1 describes a hair dye-containing substance containing a 4,5-diaminopyrazole derivative, an m-aminophenol derivative, and an m-phenylenediamine derivative. Further, Patent Document 2 describes a hair dye-containing substance containing a 4,5-diaminopyrazole derivative and a cellulose-based compound. Furthermore, Patent Document 3 describes a hair dye-containing substance containing 4,5-diamino-1-hydroxyethylpyrazole, an anionic surfactant, and a specific nonionic surfactant.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, when using the typical dye intermediates mentioned above, the reaction with the coupler they are combined with can produce various forms of oxidized polymers (dye polymers), such as dimers or trimers with different combinations. This can lead to a problem where subtractive color mixing is likely to result in a decrease in saturation. Furthermore, daily hair care (such as washing) can cause oxidized polymers (dye polymers) to leach out of the hair. Since the ease with which these polymers leach out varies depending on their structure, this can sometimes lead to discoloration.

[0005] The object of the present invention is to provide a hair dye composition that has high saturation and suppresses discoloration due to washing. [Means for solving the problem]

[0006] A hair dye composition in one aspect of the present invention contains (A) a compound represented by general formula (1) or a salt thereof and (B) a coupler. [ka] (Here, R is independently a hydrogen atom, a methyl group, or an ethyl group, and n is an integer between 1 and 3.)

[0007] In the hair dye composition of the present invention, it is preferable that the (B) coupler contains one or more selected from the group consisting of 5-amino-o-cresol, 5-(2-hydroxyethylamino)-2-methylphenol, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, m-aminophenol, α-naphthol, 1,5-dihydroxynaphthalene, and resorcinol.

[0008] In the hair dye composition of the present invention, it is preferable that the (B) coupler comprises 5-amino-o-cresol and 2,6-diaminopyridine.

[0009] In the hair dye composition of the present invention, it is preferable that it does not contain p-phenylenediamine, p-toluylenediamine, p-aminophenol, and N,N-bis(2-hydroxyethyl)-p-phenylenediamine, or their salts.

[0010] In the hair dye composition of the present invention, it is preferable that the mass ratio (A) / (B) of (A) a compound represented by general formula (1) or a salt thereof to (B) a coupler is 0.01 or more and 30 or less. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a hair dye composition that has high saturation and suppresses discoloration due to washing. [Brief explanation of the drawing]

[0012] [Figure 1] This is a photograph of an oxidative hair dye composition containing the hair dye composition of Example 2, developed using thin-layer chromatography. [Modes for carrying out the invention]

[0013] The hair dye composition of the present invention will be described below. In the present invention, "dye intermediate" refers to a dye precursor that develops color through oxidative polymerization by an oxidizing agent. In this specification, POE represents a polyoxyethylene chain, POP represents a polyoxypropylene chain, and the number in parentheses following them indicates the number of moles added. The number in parentheses following alkyl indicates the number of carbon atoms in the fatty acid chain.

[0014] Each component contained in the hair dye composition of the present invention is described below. [Hair dye composition] <(A) Compounds represented by general formula (1) or their salts> The hair dye composition of the present invention contains a compound represented by the following general formula (1) or a salt thereof. The compound represented by the following general formula (1) or its salt acts as a dye intermediate. [ka] (Here, each R independently represents a hydrogen atom, a methyl group, or an ethyl group, and n represents 1, 2, or 3.)

[0015] When the compound represented by the general formula (1) is used as a dye intermediate, the oxidation polymer derived from the compound represented by the general formula (1) has a relatively uniform structure, degree of polymerization, etc. Since it is a relatively uniform oxidation polymer, the color development by the oxidation polymer, the ease of remaining on the hair, and the outflow from the hair by shampooing are also relatively uniform. Therefore, it has excellent leveling property and can be uniformly dyed to the target concentration and color tone even when hairs with different degrees of damage are mixed. Also, it is difficult to change color by daily hair care (such as shampooing).

[0016] (A) The salt of the compound represented by the general formula (1) is a reactant with a Bronsted acid. Examples of the Bronsted acid include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid, and organic acids such as acetic acid, benzoic acid, or salicylic acid. The salt of the compound represented by the general formula (1) is preferably a sulfate because of the excellent stability of the compound.

[0017] As the compound of the above (A) general formula (1), (A1) 1-hydroxyethyl-4,5-diaminopyrazole or its salt shown in the following general formula (2) is preferable.

Chemical formula

[0018] As the component (A), at least one of a single kind or two or more kinds of the compound represented by the general formula (1) and a single kind or two or more kinds of the salt of the compound represented by the general formula (1) can be used. To limit the products of oxidative polymerization, it is preferable to use a single compound represented by general formula (1) and its salt, and more preferably to use either a single compound represented by general formula (1) or a salt of a single compound represented by general formula (1).

[0019] The content of the compound of general formula (1) or its salt in the hair dye composition is not particularly limited, but is preferably 0.03 to 5% by mass from the viewpoint of dyeing power and formulation stability. The lower limit is more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. The upper limit is more preferably 4% by mass or less, and even more preferably 3% by mass or less. By setting it to 5% by mass or less, a hair dye composition that exhibits high dyeing power and has high formulation stability can be made, and by setting it to 0.03% by mass or more, sufficient dyeing power can be obtained.

[0020] <(B) Coupler> Couplers have the effect of promoting the oxidative polymerization of dye intermediates or reacting with dye intermediates to produce color. (B) Couplers mainly include m-diamines, aminophenols, or diphenols. Specific examples of couplers include, for example, resorcinol, catechol, pyrogallol, phloroglucin, gallic acid, hydroquinone, 5-amino-o-cresol, m-aminophenol, 5-(2-hydroxyethylamino)-2-methylphenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, toluene-3,4-diamine, α-naphthol, 2,6-diaminopyridine, diphenylamine, 3,3'-iminodiphenyl, 1,5-dihydroxynaphthalene, tannic acid, and their salts. Couplers can be used individually or in combination of two or more.

[0021] (B) It is preferable to use a coupler that contains one or more selected from 5-amino-o-cresol, 5-(2-hydroxyethylamino)-2-methylphenol, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, m-aminophenol, α-naphthol, 1,5-dihydroxynaphthalene, and resorcinol.

[0022] Furthermore, it is more preferable to use a coupler (B) that includes one or more selected from 5-amino-o-cresol, 5-(2-hydroxyethylamino)-2-methylphenol, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, and resorcinol.

[0023] Furthermore, it is even more preferable to use a coupler (B) that includes one or more selected from 5-amino-o-cresol and 2,6-diaminopyridine as the coupler. In addition, it is most preferable to use a coupler containing 5-amino-o-cresol and 2,6-diaminopyridine as the (B) coupler. Using the above coupler further improves color saturation, colorfastness, and uniformity.

[0024] By further limiting the types of products produced with dye intermediates, it is possible to further improve saturation, color change suppression effect, and uniform dyeing properties. Therefore, it is preferable to limit the types of couplers used as (C) couplers.

[0025] (B) It is preferable to use a coupler consisting of one or more selected from 5-amino-o-cresol, 5-(2-hydroxyethylamino)-2-methylphenol, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, m-aminophenol, α-naphthol, 1,5-dihydroxynaphthalene, and resorcinol. Furthermore, it is more preferable to use a coupler consisting of one or more selected from 5-amino-o-cresol, 5-(2-hydroxyethylamino)-2-methylphenol, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, and resorcinol as (B) coupler. Furthermore, it is even more preferable to use a coupler consisting of one or more selected from 5-amino-o-cresol and 2,6-diaminopyridine as (B) the coupler. In addition, it is most preferable to use a coupler consisting of 5-amino-o-cresol and 2,6-diaminopyridine as the (B) coupler.

[0026] The content of component (B) in the hair dye composition is not particularly limited, but a lower limit of 0.001% by mass is preferred, and 0.01% by mass or more is preferred. An upper limit of 3% by mass or less is preferred, and 2% by mass or less is preferred. When the content of component (B) is 0.001% by mass or more, the dyeing power, saturation, and uniformity of the dye improve. Furthermore, when the content of component (B) is 3% by mass or less, the uniformity of the dye improves.

[0027] When 5-amino-o-cresol (5AOC) and 2,6-diaminopyridine (2,6-DAPy) are used together as a coupler, the ratio is not particularly limited. The 5AOC / 2,6-DAPy ratio (mass ratio) is preferably 0.01 or higher, more preferably 0.25 or higher, and even more preferably 2 or higher. Furthermore, the 5AOC / 2,6-DAPy ratio (mass ratio) is preferably 40 or lower, more preferably 17 or lower, even more preferably 13 or lower, and even more preferably 8 or lower. If the 5AOC / 2,6-DAPy ratio (mass ratio) is between 0.01 and 40, fading suppression and uniform dyeing performance will be improved.

[0028] In the hair dye composition, the coupler ratio of component (A) to component (B) (mass ratio) is preferably 0.01 or higher, more preferably 0.1 or higher, and even more preferably 0.5 or higher. Furthermore, the ratio of component (A) to component (B) (mass ratio) is preferably 30 or lower, more preferably 20 or lower, and even more preferably 8 or lower. Within the above range for the ratio of component (A) to component (B) (mass ratio), high saturation, fade suppression effect, and uniform dyeing performance are further improved.

[0029] Furthermore, the total amount (mass ratio) of (5AOC+2,6-DAPy) / component (B) in the hair dye composition is not particularly limited, but is preferably 0.5 or higher, more preferably 0.8 or higher, and even more preferably 0.9 or higher. By keeping the (5AOC+2,6-DAPy) / total amount (mass ratio) of component (B) within the above range, high saturation is obtained, and the discoloration suppression effect, fading suppression effect, and uniform dyeing performance are further improved.

[0030] [Other ingredients] In addition to the above components, the hair dye composition of the present invention may also contain the following components as needed. Other ingredients include, for example, alkaline agents, oily components, direct dyes, surfactants, dye intermediates (excluding compounds represented by general formula (1) and their salts), antioxidants such as anhydrous sodium sulfite, preservatives such as phenoxyethanol and sodium benzoate, organic solvents such as ethanol, sugars such as sorbitol and maltose, water-soluble polymers such as hydroxyethylcellulose and carboxyvinyl polymer, polydimethylmethylene piperidinium chloride solution (polydimethylmethylene pyrrolidinium chloride solution), and cationized water such as diallyldimethylammonium chloride / hydroxyethylcellulose. Examples of ingredients include soluble polymers, polyhydric alcohols such as polyethylene glycol and dipropylene glycol, chelating agents such as ethylenediamine hydroxyethyl triacetate trisodium dihydrate and hydroxyethanediphosphonate tetrasodium solution, inorganic salts such as sodium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, citric acid, tartaric acid, lactic acid, malic acid, succinic acid, fumaric acid, maleic acid, pyrophosphate, gluconic acid, glucuronic acid, pH adjusters, hair growth ingredients, plant extracts, herbal extracts, amino acids and peptides, urea, vitamins (excluding vitamin A), fragrances, and UV absorbers.

[0031] <Alkaline agent> Alkaline agents have the effect of swelling hair and promoting the penetration of dyes and oxidizing agents. Examples of alkaline agents include alkanolamines, ammonia, silicates, carbonates, bicarbonates, metasilicates, phosphates, sulfates, chlorides, organic amines, basic amino acids, alkali metals, or alkaline earth metal hydroxides. Specifically, examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, and isopropylamine; examples of silicates include sodium silicate and potassium silicate; examples of carbonates include sodium carbonate, ammonium carbonate, magnesium carbonate, and guanidine carbonate; examples of bicarbonates include sodium bicarbonate and ammonium bicarbonate; examples of metasilicates include sodium metasilicate and potassium metasilicate; and examples of phosphates include ammonium phosphate. Examples include ammonium, disodium phosphate, disodium monohydrogen phosphate, trisodium phosphate, etc. Examples of sulfates include ammonium sulfate, examples of chlorides include ammonium chloride, examples of organic amines include 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol, guanidine, examples of basic amino acids include arginine, lysine and their salts, etc. Examples of alkali metal or alkaline earth metal hydroxides include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide, etc. Among these, it is preferable to contain alkanolamines, and more preferable to contain monoethanolamines.

[0032] The content of the alkaline agent in the hair dye composition is not particularly limited, but is preferably 0.5 to 10% by mass. More preferably, the lower limit is 1% by mass or more, and even more preferably 2% by mass or more. More preferably, the upper limit is 7% by mass or less, and even more preferably 5% by mass or less.

[0033] <Oily components> The hair dye composition of the present invention contains oily components. Examples of oily components include higher alcohols, fats and oils, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, and fluorinated oils. One or more of these oily components can be selected and used. The inclusion of oily components improves the hair dyeing power.

[0034] Examples of higher alcohols include cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachidyl alcohol, behenyl alcohol, lauryl alcohol, myristyl alcohol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, decyltetradecanol, phytosterol, phytostanol, cholesterol, cholestanol, lanosterol, and ergosterol.

[0035] Fats and oils are triglycerides, that is, triesters of fatty acids and glycerol. Examples include olive oil, rosehip oil, camellia oil, shea butter, macadamia nut oil, almond oil, tea seed oil, sasanqua oil, safflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, beef tallow, cocoa butter, corn oil, peanut oil, rapeseed oil, rice bran oil, rice germ oil, wheat germ oil, Job's tears oil, grape seed oil, avocado oil, carrot oil, castor oil, linseed oil, coconut oil, mink oil, and egg yolk oil.

[0036] Waxes are esters of higher fatty acids and higher alcohols. Examples include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, whale wax, rice bran wax, sugarcane wax, palm wax, montan wax, cotton wax, bayberry wax, privet wax, kapok wax, and shellac wax.

[0037] Hydrocarbons are compounds composed of carbon and hydrogen. Examples include liquid paraffin, paraffin, microcrystalline wax, petrolatum, isoparaffins, ozokerite, ceresin, polyethylene, α-olefin oligomers, polybutene, synthetic squalane, squalene, hydrogenated squalane, limonene, and turpentine oil.

[0038] Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, hydroxystearic acid, 12-hydroxystearic acid, oleic acid, undecylenic acid, linoleic acid, ricinoleic acid, and lanolinic acid.

[0039] Esters are compounds obtained by the dehydration reaction of fatty acids and alcohols. Examples include diisopropyl adipate, 2-hexyldecyl adipate, isopropyl myristate, myristyl myristate, cetyl octanoate, cetyl isooctanoate, isononyl isononanoate, diisopropyl sebacate, isopropyl palmitate, 2-ethylhexyl palmitate, cetyl ethylhexanoate, butyl stearate, isocetyl isostearate, hexyl laurate, decyl oleate, fatty acids (C10-30) (cholesteryl / lanosteryl), lauryl lactate, octyldodecyl lactate, lanolin acetate, dipentaerythritol fatty acid esters, N-alkyl glycol monoisostearate, and lanolin derivatives.

[0040] Silicone oils are synthetic polymers in which silicon atoms with organic groups and oxygen atoms are alternately linked by chemical bonds. Examples include dimethylpolysiloxane (INCI name: dimethicone), dimethylpolysiloxane with hydroxyl-terminated groups (INCI name: dimethiconol), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicones, highly polymerized silicones with an average degree of polymerization of 650 to 10000, amino-modified silicones, betaine-modified silicones, alkyl-modified silicones, alkoxy-modified silicones, mercapto-modified silicones, carboxy-modified silicones, and fluorine-modified silicones.

[0041] Among the above, examples of amino-modified silicones include aminopropylmethylsiloxane-dimethylsiloxane copolymer (INCI name: aminopropyldimethicone), aminoethylaminopropylsiloxane-dimethylsiloxane copolymer (INCI name: amodimethicone), and aminoethylaminopropylmethylsiloxane-dimethylsiloxane copolymer (INCI name: trimethylsilylamodimethicone).

[0042] The content of oily components in the hair dye composition is not particularly limited, but is preferably 0.1 to 30% by mass. More preferably, the lower limit is 0.02% by mass or more, and even more preferably 0.5% by mass or more. More preferably, the upper limit is 20% by mass or less, and even more preferably 10% by mass or less.

[0043] <Direct dye> Direct dyes are compounds that have color, and are not particularly limited as long as they adhere to or penetrate the hair to color it. Examples include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes, and disperse dyes. Furthermore, these direct dyes may be blended individually or in combination of two or more, depending on the desired hair color.

[0044] Specific examples of acid dyes include, for example, Red No. 2, Red No. 3, Red No. 102, Red No. 104 (1), Red No. 105 (1), Red No. 106, Red No. 227, Red No. 230 (1), Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 203, Orange No. 205, Orange No. 207, Orange No. 402, Green No. 3, Green No. 204, Green No. 401, Purple No. 401, Blue No. 1, Blue No. 2, Blue No. 202, Brown No. 201, Black No. 401, and so on.

[0045] Specific examples of basic dyes include, for example, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 26, Basic Blue 41, Basic Blue 47, Basic Blue 75, Basic Blue 99, Basic Blue 124, Basic Brown 4, Basic Brown 16, Basic Brown 17, Basic Green 1, Basic Green 4, Basic Orange 1, Basic Orange 2, Basic Orange 31, Basic Red 1, Basic Red 2, Basic Red 22, Basic Red 46, Basic Red 51, Basic Red 76, Basic Red 118, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 11:1, Basic Violet 14, Basic Violet 16, Basic Yellow 11, Basic Yellow 28, Basic Yellow 57, Basic Yellow 87, and so on.

[0046] Examples of natural dyes include gardenia pigment, turmeric pigment, annatto pigment, copper chlorophyllin sodium, paprika pigment, lac pigment, and henna.

[0047] Specific examples of nitro dyes include, for example, 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, picric acid, and their salts.

[0048] Specific examples of HC dyes include HC Blue No.2, HC Blue No.5, HC Blue No.6, HC Blue No.9, HC Blue No.10, HC Blue No.11, HC Blue No.12, HC Blue No.13, HC Blue No.16, HC Orange No.1, HC Orange No.2, HC Orange No.3, HC Red No.1, HC Red No.3, HC Red No.7, HC Red No.10, HC Red. No.11, HC Red No.13, HC Red No.14, HC Violet No.1, HC Violet No.2, HC Yellow No.2, HC Yellow No.4, HC Yellow No.5, HC Yellow No.6, HC Yellow No.9, HC Yellow No.10, HC Yellow No.11, HC Yellow No.12, HC Yellow No.13, HC Yellow No.14, HC Yellow No.15, etc.

[0049] Specific examples of disperse dyes include, for example, Disperse Black 9, Disperse Blue 1, Disperse Blue 3, Disperse Blue 7, Disperse Brown 4, Disperse Orange 3, Disperse Red 11, Disperse Red 15, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, and Disperse Violet 15.

[0050] The content of direct dyes in the hair dye composition is not particularly limited, but is preferably 0.001% by mass or more and 20.0% by mass or less. The lower limit is more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. On the other hand, the upper limit is more preferably 15.0% by mass or less, even more preferably 10.0% by mass or less, and particularly preferably 5.0% by mass or less.

[0051] <Surfactants> Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0052] Examples of nonionic surfactants include POE alkyl ethers, POE alkylphenyl ethers, POE·POP alkyl ethers, POE sorbitan fatty acid esters, POE mono fatty acid esters, POE glycerin fatty acid esters, polyglycerin fatty acid esters, monoglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and alkyl polyglucosides. Specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether, POE lanolin, and POE phytosterol. The number of repeating units for POE and POP can range from 2 to 100, and any combination that exhibits surfactant activity can be used.

[0053] The content of nonionic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 40% by mass. More preferably, the lower limit is 0.01% by mass or more, and even more preferably 0.05% by mass or more. More preferably, the upper limit is 30% by mass or less, and even more preferably 20% by mass or less.

[0054] Examples of cationic surfactants include alkyl quaternary ammonium salts such as monoalkyl quaternary ammonium salts, dialkyl quaternary ammonium salts, trialkyl quaternary ammonium salts, benzalkonium quaternary ammonium salts, and monoalkyl ether quaternary ammonium salts; amine salts such as alkylamine salts, fatty acid amidoamine salts, ester-containing tertiary amine salts, and Arcover tertiary amine salts; cyclic quaternary ammonium salts such as alkylpyridinium salts and alkylisoquinolium salts; and benzethonium chloride.

[0055] Preferably, the salts are alkyl quaternary ammonium salts, more preferably monoalkyl quaternary ammonium salts and dialkyl quaternary ammonium salts, and particularly preferably monoalkyl quaternary ammonium salts.

[0056] Examples of monoalkyl quaternary ammonium salts include lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, alkyl(16,18)trimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium saccharin, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, behenyltrimethylammonium chloride, stearyltrimethylammonium saccharin, alkyl(28)trimethylammonium chloride, diPOE(2)oleylmethylammonium chloride, diPOEstearylmethylammonium chloride, POE(1)POP(25)diethylmethylammonium chloride, POPmethyldiethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, and behenyltrimethylammonium methyl sulfate. Particularly preferred are stearyltrimethylammonium chloride, alkyl(16,18)trimethylammonium chloride, and cetyltrimethylammonium chloride.

[0057] Examples of dialkyl-type quaternary ammonium salts include dialkyl(12-15)dimethylammonium chloride, dialkyl(12-18)dimethylammonium chloride, dialkyl(14-18)dimethylammonium chloride, dicocoyldimethylammonium chloride, dicetyldimethylammonium chloride, distearyldimethylammonium chloride, and isostearyllauryldimethylammonium chloride.

[0058] The content of cationic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 10% by mass. More preferably, the lower limit is 0.01% by mass or more, and even more preferably 0.05% by mass or more. More preferably, the upper limit is 5% by mass or less, and even more preferably 3% by mass or less.

[0059] Examples of anionic surfactants include alkyl ether sulfates, POE alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono or diester type surfactants, and sulfosuccinate esters. The counterions of the anionic groups of these surfactants may be, for example, sodium ions, potassium ions, and triethanolamine.

[0060] More specifically, examples include sodium lauryl sulfate, sodium myristyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sodium POE lauryl ether sulfate, triethanolamine POE lauryl ether sulfate, ammonium POE lauryl ether sulfate, sodium POE stearyl ether sulfate, sodium stearoyl methyl taurate, triethanolamine dodecylbenzenesulfonate, sodium tetradecenesulfonate, sodium lauryl phosphate, POE lauryl etheric acid and its salts, N-lauroyl glutamates (such as sodium lauroyl glutamate), N-lauroyl methyl-β-alanine salt, N-acylglycine salt, N-acyl glutamate, the higher fatty acids lauric acid, myristic acid, and salts of these higher fatty acids, and one or more of these can be used.

[0061] The content of anionic surfactant in the hair dye composition is not particularly limited, but is preferably 0.01 to 5% by mass. More preferably, the lower limit is 0.05% by mass or more, and even more preferably 0.1% by mass or more. More preferably, the upper limit is 3% by mass or less, and even more preferably 1.5% by mass or less.

[0062] Examples of amphoteric surfactants include amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants. Specific examples of amino acid-type amphoteric surfactants include, for example, sodium N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, sodium undecylhydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, sodium N-coconut oil fatty acid acyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine, and sodium N-coconut oil fatty acid acyl-N'-carboxyethoxyethyl-N Examples include glycine-type amphoteric surfactants such as '-carboxyethylethylenediamine disodium, N-coconut oil fatty acid acyl-N'-carboxymethoxyethyl-N'-carboxymethylethylenediamine disodium, lauryldiaminoethylglycine sodium, palm oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium; aminopropionic acid-type amphoteric surfactants such as laurylaminopropionate sodium, laurylaminodipropionate sodium, and laurylaminopropionate triethanolamine; and others. Specific examples of betaine-type amphoteric surfactants include, for example, aminoacetic acid betaine-type amphoteric surfactants such as coconut oil alkyl betaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, stearyldimethylbetaine sodium, coconut oil fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, ricinoleic acid amidopropyl betaine, and stearyldihydroxyethyl betaine; and sulfobetaine-type amphoteric surfactants such as laurylhydroxysulfobetaine.

[0063] The content of amphoteric surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 5% by mass. More preferably, the lower limit is 0.005% by mass or more, and even more preferably 0.01% by mass or more. More preferably, the upper limit is 3% by mass or less, and even more preferably 2.5% by mass or less.

[0064] The total content of all surfactants in the hair dye composition is not particularly limited, but is preferably 0.01 to 50% by mass. The lower limit is more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. The upper limit is more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0065] <Dye intermediate> The hair dye composition of the present invention may contain other dye intermediates to the extent that they do not impair the effects of the present invention. Other dye intermediates are mainly dye precursors which are or- or p-phenylenediamines or aminophenols, and are usually colorless or weakly colored compounds. Specifically, examples include p-phenylenediamine, toluene-2,5-diamine (p-toluylenediamine), N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, p-aminophenol, o-aminophenol, p-methylaminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2-hydroxyethyl-p-phenylenediamine, o-chlor-p-phenylenediamine, 4-amino-m-cresol, 2-amino-4-hydroxyethylaminoanisole, 2,4-diaminophenol, and their salts.

[0066] The dye intermediates include acid addition salts of the compounds mentioned above. Examples of acid addition salts include addition salts of inorganic acids such as hydrochloride and sulfate, and addition salts of organic acids such as acetate. The content of acid addition salts in the dye intermediates is not particularly limited, but from the viewpoint of formulation stability, it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0067] These dye intermediates can be used individually or in combination of two or more, depending on the desired color tone.

[0068] However, since it is preferable to further limit the types of products produced by oxidative polymerization for the effects of the present invention, it is preferable, more preferable, to be substantially free of p-phenylenediamine, p-toluylenediamine, p-aminophenol, and N,N-bis(2-hydroxyethyl)-p-phenylenediamine and their salts, and even more preferable to be free of dye intermediates other than the compound represented by general formula (1) and its salts. Substantially free means 0.1% by mass or less.

[0069] Furthermore, the ratio of component (A) to the total amount of dye intermediates (by mass) in the hair dye composition is not particularly limited, but is preferably 0.5 or higher, more preferably 0.8 or higher, and even more preferably 0.9 or higher. By keeping the ratio of component (A) to the total amount of dye intermediates (by mass) within the above range, high saturation can be obtained, and the discoloration suppression effect, fading suppression effect, and uniform dyeing performance are further improved.

[0070] The pH of a hair dye composition can be adjusted using acidic compounds such as phosphoric acid or alkaline compounds such as sodium hydroxide.

[0071] The hair dye composition of the present invention may take any form, such as a sol, gel, mousse, cream, emulsion (W / O type or O / W type), liquid, powder, granules, or tablet. When used as an oxidative hair dye composition as described later, the hair dye composition of the present invention is suitably used for hair with varying degrees of damage that has undergone repeated chemical treatments such as oxidative hair dyes and perming agents. For example, when dyeing hair that has both new black hair growth and bleached (previously dyed) hair, it is necessary to minimize the difference in brightness and hue between the new black hair growth and the bleached (previously dyed) hair. When vivid color development is achieved in the dyeing process of black hair, the hue (brightness) becomes more noticeable, thus reducing the difference in brightness and hue between the new black hair growth and the bleached (previously dyed) hair. The hair dye composition of the present invention can vividly color new black hair growth, and is therefore particularly suitable for dyeing hair that has both new black hair growth and bleached (previously dyed) hair.

[0072] [Oxidative hair dye composition] The oxidative hair dye composition of the present invention is a multi-component mixture comprising at least the hair dye composition of the present invention and a composition containing an oxidizing agent which will be described later as a second agent. Therefore, the oxidative hair dye composition of the present invention includes, for example, a multi-component hair dye composition comprising a first agent and a second agent when the hair dye composition is the first agent. The oxidative hair dye composition of the present invention can be used for any purpose, such as new growth, previously dyed hair, or damaged hair. The oxidative hair dye composition of the present invention is excellent in uniform dyeing, as it easily produces color due to relatively uniform polymerization, and can dye hair to the desired intensity and tone even when hair with different degrees of damage is mixed together. For example, bleaching removes color, but it also damages the hair. This hair damage often varies from section to section. The oxidative hair dye composition of the present invention has excellent uniformity, allowing for better color development and a more beautiful dyeing result after bleaching.

[0073] While not limiting, the following are possible reasons why the present invention exhibits excellent uniformity in dyeing. The degree of hair damage affects its hydrophilic / hydrophobic properties (the more damaged the hair, the more hydrophilic it becomes). On the other hand, polymers can have different polarities depending on their structure, and the amount that adheres to the hair may vary depending on whether the hair is hydrophilic or hydrophobic. For this reason, there may be polymer species that adhere excessively to hair that has become hydrophilic due to damage. The generation of many polymer species means that polymers of various polarities can be produced, and since the effect of each polymer on the fixation varies depending on the degree of hair damage, it is thought that damaged hair is more likely to not be dyed to the intended color. Therefore, by dyeing with a uniform polymer (using a limited number of polymer types), differences in dyeing properties among polymers are less likely to occur, and as a result, high uniformity of dyeing can be achieved. Because this invention uses a limited number of polymer types, it is considered easier to achieve the desired color, although it is somewhat affected by the degree of damage.

[0074] The mixing ratio of the hair dye composition of the present invention and the composition containing the oxidizing agent in the oxidative hair dye composition of the present invention varies depending on the concentration of the dye intermediate in the hair dye composition and the concentration of the oxidizing agent in the composition containing the oxidizing agent. Generally, the hair dye composition / composition containing the oxidizing agent (mass ratio) is preferably 1 / 3 or more, more preferably 1 / 2.8 or more, even more preferably 1 / 2.5, preferably 5 / 1 or less, more preferably 3 / 1 or less, and even more preferably 2 / 1 or less.

[0075] [Compositions containing oxidizing agents] The oxidizing agent is used as the second component in the oxidative hair dye composition. The components contained in the oxidizing agent are as follows: <Oxidizing agent> Oxidizing agents have the effect of oxidizing oxidative dyes to produce color, or of breaking down melanin inside the hair. Specifically, examples include hydrogen peroxide, urea peroxide, melamine peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, ammonium persulfate, potassium persulfate and sodium persulfate, and other persulfates, sodium peroxide, potassium peroxide, magnesium peroxide, barium peroxide, calcium peroxide, strontium peroxide, hydrogen peroxide adducts of sulfates, hydrogen peroxide adducts of phosphates, hydrogen peroxide adducts of pyrophosphates, peracetic acid and its salts, formic acid and its salts, permanganate, bromate, etc. Among these, hydrogen peroxide is preferred. In addition, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate may be included as oxidizing aids.

[0076] The content of the oxidizing agent in the composition containing the oxidizing agent of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more. Furthermore, the content of the oxidizing agent in the composition containing the oxidizing agent of the present invention is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Reducing the amount of oxidizing agents can further reduce damage to the hair.

[0077] When hydrogen peroxide is included as an oxidizing agent, it is preferable to include ethylene glycol phenyl ether (phenoxyethanol), hydroxyethane diphosphonic acid, or a salt thereof as a stabilizer to improve its stability.

[0078] <Other ingredients> Compositions containing an oxidizing agent may contain any other components. Examples include oily components, surfactants, preservatives such as sodium benzoate, organic solvents such as ethanol, sugars such as sorbitol and maltose, water-soluble polymers such as hydroxyethylcellulose and carboxyvinyl polymer, cationized water-soluble polymers such as polydimethylmethylene piperidinium chloride solution and diallyldimethylammonium chloride / hydroxyethylcellulose, polyhydric alcohols such as polyethylene glycol and dipropylene glycol, chelating agents such as ethylenediamine hydroxyethyl triacetate trisodium dihydrate and hydroxyethanediphosphonate tetrasodium solution, inorganic salts such as sodium chloride, pH adjusters such as ammonium bicarbonate, direct dyes, hair growth components, plant extracts, herbal extracts, amino acids / peptides, urea, vitamins, fragrances, and UV absorbers.

[0079] <Oily components> Examples of oily components include higher alcohols, fats and oils, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, and fluorinated oils. One or more of these oily components can be used. Specifically, oily components and the like exemplified in the section on hair dye compositions can be used.

[0080] <Surfactants> Examples of surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. One or more of these can be used. Specifically, surfactants and the like exemplified in the section on hair dye compositions can be used. [Examples]

[0081] The present invention will be specifically described below with reference to examples, but the scope of the invention is not limited by these examples. Unless otherwise specified, the values ​​in the column for each component in the table are in parts by mass.

[0082] The evaluation method used in this invention is as follows. [1] Evaluation by thin-layer chromatography (TLC) (1) Method for preparing the sample The hair dye composition prepared in the example and the second agent (composition containing an oxidizing agent) having the composition shown in Table 1 were mixed in a 1:1 (mass ratio), stirred for 2 minutes until homogeneous, and then left at 40°C for 60 minutes to allow the reaction and color development to occur, and the resulting sample was obtained. (2) Evaluation method using TLC One μL of each sample was collected using a capillary tube and spotted onto a thin-layer plate with silica gel as the stationary phase. Next, the thin-layer plate with the spotted sample was placed in a developing layer where the gas phase and liquid phase were in equilibrium, containing a mobile phase (developing solvent) of methanol and 28% aqueous ammonia mixed in a 1 / 10 (volume ratio). Development was then carried out at room temperature. The number of colored spots after development was used to identify and evaluate the number of reaction products (number of polymer species). (Evaluation Criteria) ○: The number of colored spots is 3 or less. ×: The number of colored spots is 4 or more.

[0083] Second component (composition containing an oxidizing agent) [Table 1]

[0084] [2] Evaluation by hair dyeing "Discoloration suppression," "fading," "saturation," and "uniformity" were evaluated using the methods described below. (1) Preparation of hair dyeing performance evaluation samples Each oxidative hair dye composition was evaluated using untreated white hair bundles (10 cm, manufactured by Beaulux) as a model for new hair growth. These untreated white hair bundles will also be referred to below as "undamaged white hair." Damaged hair was also used in the evaluation of "uniform dyeing." Damaged hair was prepared by using untreated hair bundles and subjecting them to the chemical treatment described in the preparation of damaged hair below. Damaged hair was prepared for both undamaged white hair and untreated black hair bundles (10 cm, manufactured by Beaulux). These untreated black hair bundles will also be referred to as "undamaged black hair" below. (Preparation of damaged hair) Damaged hair was prepared by using Promaster LT (manufactured by Hoyu Co., Ltd.) and dyeing hair bundles twice at 30°C for 30 minutes each time.

[0085] (2) Hair dyeing method a. Preparation of oxidative hair dye compositions A first hair dye composition, which was prepared in each example, and a second hair dye composition having the composition described in Table 1 were mixed in a 1:1 (mass ratio) to prepare an oxidative hair dye composition. I. Hair dyeing treatment Using a brush, an oxidative hair dye composition in an amount three times the weight of the hair bundle was applied to the hair bundle (bath ratio 1:3), and it was left at 30°C for 30 minutes. After the waiting period, the hair bundle was rinsed with water, then washed with shampoo to remove the oxidative hair dye composition. Next, conditioner was applied to the hair bundle. After rinsing the hair bundle to remove the conditioner, the hair bundle was towel-dried, and finally dried with a hairdryer.

[0086] (3) Evaluation method A. Evaluation method for discoloration suppression Undamaged white hair, dyed using an oxidative hair dye composition, was immersed in a 1% sodium lauryl sulfate aqueous solution heated to 50°C for 15 minutes. Afterward, the 1% sodium lauryl sulfate aqueous solution was rinsed off with water, followed by a treatment and rinse. The hair strands were then towel-dried, and finally, dried with a hairdryer. Ten panelists visually evaluated the degree of color change between hair strands that had undergone the aforementioned color-fading treatment and hair strands that had not undergone the treatment, under a standard light source. Each panelist scored the results on a four-point scale: "4 points: No change in color tone before and after processing," "3 points: Slight change in color tone before and after processing," "2 points: Change in color tone before and after processing," and "1 point: Significant change in color tone before and after processing." The average score was calculated based on each panelist's results. (evaluation) 5: Average score is 3.5 or higher 4: Average score is 3.0 or higher but less than 3.5 3: Average score is between 2.5 and 3.0 2: Average score is 2.0 or higher but less than 2.5 1: Average score is less than 2.0

[0087] I. Evaluation method for color fading suppression The same method as described in "A. Evaluation Method for Discoloration Suppression" was applied to undamaged white hair, and 10 panelists visually evaluated the degree of change in dyeing intensity between the hair bundles that had undergone the aforementioned fading treatment and the hair bundles that had not undergone the aforementioned fading treatment, under a standard light source. Each panelist scored the results on a four-point scale: "4 points: No or almost no change in concentration before and after treatment," "3 points: Slight change in concentration before and after treatment," "2 points: Change in concentration before and after treatment," and "1 point: Significant change in concentration before and after treatment." The average score was calculated based on each panelist's results. (evaluation) 5: Average score is 3.5 or higher 4: Average score is 3.0 or higher but less than 3.5 3: Average score is between 2.5 and 3.0 2: Average score is between 2.0 and 2.5 1: Average score is less than 2.0

[0088] (c) Method for evaluating saturation Using an oxidative hair dye composition, undamaged white hair was dyed, and the saturation of the resulting hair bundles was visually evaluated by 10 panelists under a standard light source. Each panelist scored the items on a four-point scale: "4 points: Very vividly colored," "3 points: Vividly colored," "2 points: Slightly dull," and "1 point: Quite dull." The average of each panelist's score was then calculated. (evaluation) 5: Average score is 3.5 or higher 4: Average score is 3.0 or higher but less than 3.5 3: Average score is between 2.5 and 3.0 2: Average score is between 2.0 and 2.5 1: Average score is less than 2.0

[0089] E. Method for evaluating uniformity of staining Using an oxidative hair dye composition, undamaged and damaged white and black hair were dyed separately. For each type of white and black hair, the intensity of dyeing, hue, and saturation of hair bundles between dyed undamaged hair and dyed damaged hair were compared and evaluated visually by 10 panelists under standard lighting. Each panelist scored the white and black hair samples on a four-point scale: "4 points: nearly identical dyeing results, with undamaged and damaged hair blending well," "3 points: slight difference in dyeing results, but undamaged and damaged hair blending relatively well," "2 points: difference in dyeing results, with slightly poor blending of undamaged and damaged hair," and "1 point: significant difference in dyeing results, with poor blending of undamaged and damaged hair." The average scores for each panelist's scores were then calculated for both white and black hair samples. (evaluation) 5: Average score is 3.5 or higher 4: Average score is 3.0 or higher but less than 3.5 3: Average score is between 2.5 and 3.0 2: Average score is between 2.0 and 2.5 1: Average score is less than 2.0

[0090] [Example 1] 1 part by mass of 1-hydroxyethyl-4,5-diaminopyrazole sulfate, 0.3 parts by mass of 5-amino-o-cresol, 0.3 parts by mass of 2,6-diaminopyridine, and the other components and amounts listed in Table 2 were added to a total of 100 parts by mass to prepare a hair dye composition. The manufactured hair dye compositions were evaluated according to the method described above. The results are shown in Table 3.

[0091] [Table 2]

[0092] [Example 2] 0.5 parts by mass of 1-hydroxyethyl-4,5-diaminopyrazole sulfate, 0.3 parts by mass of 5-amino-o-cresol, 0.1 parts by mass of 2,6-diaminopyridine, and the other components and amounts listed in Table 2 were added to a total of 100 parts by mass to prepare a hair dye composition. The manufactured hair dye compositions were evaluated according to the method described above. The results are shown in Table 3.

[0093] Figure 1 shows the thin-layer chromatography image after development. In the thin-layer chromatography of the sample 1, there were two colored spots after development, and the origin 2 (the position of the sample before development) was colorless. In the thin-layer chromatography after development (Figure 1), there is one pink spot 3 near the origin and one orange spot 4 far away in the direction of development.

[0094] [Examples 3-21] Each of the hair dye compositions in Examples 3 to 21 was prepared in the same manner as in Example 1, except that the amounts of 1-hydroxyethyl-4,5-diaminopyrazole sulfate, 5-amino-o-cresol, and 2,6-diaminopyridine added were replaced with the amounts listed in Tables 3 to 6. Each hair dye composition manufactured was evaluated according to the evaluation method described above. The results are shown in Tables 3 to 6.

[0095] [Table 3] The meanings of the abbreviations used in Tables 3-7 are as follows: 1HE:1-Hydroxyethyl-4,5-diaminopyrazole sulfate 5AOC: 5-amino-o-cresol 2,6-DAPy: 2,6-diaminopyridine

[0096] In all of Examples 1 to 7, the number of polymer species was "〇" (3 or less), indicating a good result. Furthermore, all of Examples 1 to 7 demonstrated excellent effectiveness in suppressing discoloration. On the other hand, saturation improved further at A / B = 0.04 or higher, and even further at 0.8 or higher. Regarding fade resistance and uniform dyeing properties, improvements were further observed at values ​​of 0.1 or higher, and even further at values ​​of 0.8 or higher. While not a limiting factor, one possible reason is that the discoloration-inhibiting effect is less affected by the amount of polymer produced, whereas the fading-inhibiting effect, saturation, and uniformity may depend on the amount of polymer produced. Furthermore, the evaluations for the uniform dyeing (white hair) and uniform dyeing (black hair) categories became similar. Therefore, it is considered that the uniformity of hair dyeing using the hair dye composition of the present invention is hardly affected by melanin.

[0097] [Table 4]

[0098] In all of Examples 8 to 12, the number of polymer species was "〇" (3 or less), indicating a good result. Furthermore, in all of Examples 8 to 12, excellent effects were observed in suppressing discoloration. On the other hand, saturation improved further at A / B = 20 or less, and even further at 8 or less. Furthermore, uniformity improved further at A / B = 23 or less, and even further at 8 or less.

[0099] [Table 5]

[0100] The mass ratio of 1-hydroxyethyl-4,5-diaminopyrazole sulfate (1HE) and 5-amino-o-cresol (5AOC) was kept constant, while the proportion of 2,6-diaminopyridine (2,6-DAPy) was varied. The uniformity of the staining in Examples 15 and 16 was rated as "3," but the difference between this and a rating of "4" was minimal. In all of Examples 13 to 17, the number of polymer species was "〇" (3 or less), indicating a good result. When the A / 2,6-DAPy (mass ratio) is 0.35 or higher, uniform dyeing is further improved, and in particular, when the A / 2,6-DAPy (mass ratio) is around 5 to 10, both fading suppression and uniform dyeing are thought to be even better. Furthermore, it is thought that uniform dyeing is further improved when the 5AOC / 2,6-DAPy ratio (mass ratio) is 0.35 or higher, and that fading suppression and uniform dyeing are further improved when the 5AOC / 2,6-DAPy ratio (mass ratio) is around 3 to 6.

[0101] [Table 6]

[0102] The mass ratio of 1-hydroxyethyl-4,5-diaminopyrazole sulfate (1HE) and 2,6-diaminopyridine (2,6-DAPy) was kept constant, while the proportion of 5-amino-o-cresol (5AOC) was varied. The uniformity of the staining in Example 19 was rated as "3," but the difference between this and a rating of "4" was very small. In all of Examples 18-21, the number of polymer species was "〇" (3 or less), indicating a good result. When the A / 5AOC (mass ratio) is 0.3 or higher, uniform dyeing is further improved, and in particular, when the A / 5AOC (mass ratio) is around 1.6 to 2.5, both fading suppression and uniform dyeing are thought to be even more improved. Furthermore, it is thought that uniform dyeing is further improved when the 5AOC / 2,6-DAPy ratio (mass ratio) is 0.3 or higher, and that fading suppression and uniform dyeing are further improved when the 5AOC / 2,6-DAPy ratio (mass ratio) is around 2 to 3.

[0103] [Example 22] 0.5 parts by mass of 1-hydroxyethyl-4,5-diaminopyrazole sulfate, 0.3 parts by mass of 5-amino-o-cresol, 0.1 parts by mass of 2,6-diaminopyridine, and 0.1 parts by mass of p-phenylenediamine, along with the other components and amounts listed in Table 2, were added to a total of 100 parts by mass to prepare a hair dye composition. The manufactured hair dye compositions were evaluated according to the method described above. The results are shown in Table 7.

[0104] [Table 7] The meanings of the abbreviations used in the table are as follows: pPD: p-phenylenediamine

[0105] In both cases, when 1-hydroxyethyl-4,5-diaminopyrazole sulfate (1HE) was used alone as a dye intermediate, and when p-phenylenediamine (pPD) was used in combination with it, the number of polymer species was "〇" (3 or less), which was favorable. However, when 1-hydroxyethyl-4,5-diaminopyrazole sulfate (1HE) is used alone as a dye intermediate, it exhibits superior resistance to discoloration, fading, saturation, and uniform dyeing compared to when p-phenylenediamine (pPD) is also used in combination. In particular, saturation and uniform dyeing improved significantly from "3" to "5" when 1-hydroxyethyl-4,5-diaminopyrazole sulfate (1HE) is used alone as a dye intermediate, compared to when p-phenylenediamine (pPD) is also used in combination.

[0106] [Examples 23-28] The hair dye compositions for Examples 23 to 28 were prepared in the same manner as in Example 1, except that the amounts of 1-hydroxyethyl-4,5-diaminopyrazole sulfate, 5-amino-o-cresol, and 2,6-diaminopyridine added in Example 1 were replaced with the amounts listed in Table 8, and toluene-2,5-diamine was added in Example 25. The manufactured hair dye compositions were evaluated according to the method described above. The results are shown in Table 8.

[0107] [Comparative Examples 1 and 2] The hair dye compositions of Comparative Examples 1 and 2 were prepared in the same manner as in Example 2, except that 1-hydroxyethyl-4,5-diaminopyrazole sulfate described in Example 2 was replaced with p-phenylenediamine or toluene-2,5-diamine. Each hair dye composition manufactured was evaluated according to the evaluation method described above. The results are shown in Table 8.

[0108] [Table 8] The meanings of the abbreviations used in the table are as follows: pPD: p-phenylenediamine pTD: Toluene-2,5-diamine Resorcinol mAP: Meta-aminophenol

[0109] The results from Examples 23 and 24 showed that, under constant conditions of A / B (mass ratio), the effects of the present invention can be fully demonstrated even when the 5AOC / 2,6-DAPy ratio (mass ratio) is changed. Furthermore, the results from Example 25 showed that the higher the 1HE / total amount of dye intermediates, the higher the saturation obtained, and the better the suppression of discoloration, fading, and uniform dyeing. Furthermore, it was confirmed that the effects of the present invention can be obtained even with the hair dye compositions of Examples 26 to 28, which include couplers other than 5-amino-o-cresol (5AOC) and 2,6-diaminopyridine (2,6-DAPy). Furthermore, in Comparative Examples 1 and 2, which do not contain 1-hydroxyethyl-4,5-diaminopyrazole sulfate, the number of polymer species was "×" (4 or more), indicating that a large number of polymer species were observed, and it was confirmed that the effects of the present invention could not be obtained. [Industrial applicability]

[0110] The hair dye composition of the present invention can be used as a first agent and in combination with a composition containing an oxidizing agent as a second agent to form an oxidative hair dye composition. One or more agents other than the first and second agents can be optionally used in combination with this oxidative hair dye composition. The oxidative hair dye composition containing the hair dye composition of the present invention dyes hair uniformly even when used on hair with varying degrees of damage, and is therefore suitable for use on hair that has undergone chemical treatment and has different degrees of damage. In particular, even hair that has undergone repeated chemical treatments and whose degree of damage varies greatly from section to section can be uniformly dyed by the oxidative hair dye composition containing the hair dye composition of the present invention. Furthermore, the oxidative hair dye composition containing the hair dye composition of the present invention can uniformly dye hair even when used on hair with varying degrees of damage, and the causes of varying degrees of hair damage are not limited to chemical treatments. For this reason, the oxidative hair dye composition containing the hair dye composition of the present invention can uniformly dye hair with varying degrees of damage, such as that caused by everyday use of irons or ultraviolet rays. Compounds represented by general formula (1) or their salts, particularly oxidized polymers of 1-hydroxyethyl-4,5-diaminopyrazole or its salts, have vivid warm tones. For this reason, the hair dye composition of the present invention can be suitably used as one component in an oxidative hair dye composition for dyeing hair with fashion colors. [Explanation of Symbols]

[0111] 1. Thin-layer chromatography, 2. Origin, 3. Pink color spot, and 4. Orange color spot.

Claims

1. A hair dye composition comprising (A) a compound represented by general formula (1) or a salt thereof and (B) a coupler, The aforementioned component (B) comprises at least (B-1)5-amino-o-cresol, At least one of the following conditions is met: the mass ratio (A) / (B) of component (A) to component (B) is 0.83 or greater, and the mass ratio (A) / (B-1) of component (A) to component (B-1) is 1.67 or greater and 5 or less. If the hair dye composition contains a dye intermediate other than component (A), the hair dye composition contains a total of three or four types of component (A), component (B), and dye intermediates, and if it does not contain the dye intermediate, the hair dye composition contains a total of two to four types of component (A) and component (B). 【Chemistry 1】 (Here, R is independently a hydrogen atom, a methyl group, or an ethyl group, and n is an integer from 1 to 3.)

2. A hair dye composition comprising (A) a compound represented by general formula (1) or a salt thereof and (B) a coupler, The aforementioned component (B) is 5-amino-o-cresol and 2,6-diaminopyridine, A hair dye composition wherein, if the hair dye composition contains a dye intermediate other than component (A), there are a total of four types of components (A), component (B), and the dye intermediate in the hair dye composition, and if the hair dye composition does not contain the dye intermediate, there are a total of three types of components (A) and component (B) in the hair dye composition. 【Chemistry 2】 (Here, R is independently a hydrogen atom, a methyl group, or an ethyl group, and n is an integer from 1 to 3.)

3. The hair dye composition according to claim 1, wherein the (B) component further comprises (B-2)2,6-diaminopyridine.

4. A hair dye composition according to any one of claims 1 to 3, which does not contain p-phenylenediamine, p-toluylenediamine, p-aminophenol, and N,N-bis(2-hydroxyethyl)-p-phenylenediamine or salts thereof.

5. The hair dye composition according to claim 2, wherein the mass ratio (A) / (B) of component (A) to component (B) is 0.01 or more and 30 or less.

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