Hair dye composition

Abstract

To provide a hair dye composition containing an oxidation dye, where the hair dye composition hardly stains skin but is excellent in a dyeing performance and in emulsion stability.SOLUTION: A hair dye composition contains (A) 1-10 mass% of an ascorbic acid or an erythorbic acid or their salt or ester, and (B) an oxidation dye comprising a sulfate of a compound represented by a general formula (1) in the figure, where R represents a C1-6 linear or branched alkyl group, a C2-6 linear or branched mono- or polyhydroxyalkyl group, or a linear or branched mono- or polyaminoalkyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a hair dye composition for dyeing hair, etc. More specifically, the present invention relates to a hair dye composition containing a dye, which causes little skin staining, has excellent hair dyeing power, and further has excellent emulsion stability. [Background technology]

[0002] As a composition for dyeing hair, there is a hair dye composition using an oxidation dye. Although this hair dye composition has excellent hair dyeing power, it has an aspect of causing skin staining.

[0003] For example, Patent Document 1 discloses that by containing 1 to 20% by weight of an ascorbic acid in an oxidation hair dye, scalp staining is reduced without reducing hair dyeing power.

[0004] Patent Document 2 discloses that a hair dye composition contains an oxidation dye, at least one component selected from ascorbic acids and their salts, polyethylene glycol, a nonionic surfactant, and an oxidation dye, and the total content of the at least one component selected from ascorbic acids and their salts is 7 to 15 mass%, the content of polyethylene glycol is 4 to 20 mass%, and the content of polyethylene glycol that is solid at 25°C is 3 mass% or more, thereby achieving both good hair dyeing power and little skin staining and excellent emulsion stability. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2002-29946 A [Patent Document 2] JP 2013-151464 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a hair dye composition containing an oxidation dye, which causes little skin staining, has excellent hair dyeing power, and further has excellent emulsion stability. [Means for solving the problem]

[0007] As a result of intensive research into the above-mentioned problems, the inventors have found that by using a sulfate of a heterocyclic compound having a specific structure as an oxidation dye in a hair dye composition containing ascorbic acid, erythorbic acid, or a salt or ester thereof, an excellent hair dyeing effect can be obtained while maintaining a high effect of inhibiting background staining, and that the hair dye composition has high emulsion stability, and have thus completed the present invention.

[0008] That is, the present invention relates to an emulsion composition containing an oily component, and is a hair dye composition characterized by containing (A) 1 to 10 mass % of ascorbic acid, erythorbic acid, a salt or an ester thereof, and (B) an oxidation dye consisting of a sulfate salt of a compound represented by the following general formula (1). [ka] (wherein R represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, or a linear or branched mono- or polyaminoalkyl group.) By preparing a hair dye composition as an emulsion composition containing 1 to 10 mass % of (A) ascorbic acid, erythorbic acid, or a salt or ester thereof (hereinafter also referred to as "Component A") and (B) an oil component containing an oxidation dye consisting of a sulfate salt of the compound represented by the above general formula (1), it is possible to obtain an excellent hair dyeing effect while maintaining a high effect of inhibiting soiling of the scalp. In addition, since the composition maintains high emulsion stability without being affected by other components contained therein, it can be made into a hair dye composition of various compositions.

[0009] Furthermore, the hair dye composition of the present invention is characterized in that it contains 1-hydroxyethyl-4,5-diaminopyrazole sulfate as the sulfate of the compound represented by the general formula (1) (B). By containing 1-hydroxyethyl-4,5-diaminopyrazole sulfate, the hair dye composition of the present invention can exhibit the effects of the present invention to a greater extent.

[0010] Furthermore, the hair dye composition of the present invention is characterized in that the mass ratio (B / A) of (A) ascorbic acid, erythorbic acid, a salt thereof, or an ester thereof to (B) the sulfate of the compound represented by general formula (1) is more than 0.1 and less than 1, and the sum of the content of (A) ascorbic acid, erythorbic acid, a salt thereof, or an ester thereof and the content of (B) the sulfate of the compound represented by general formula (1) is less than 7 mass%. By preparing a hair dye composition in which the mass ratio of the component (A) to the sulfate of the compound represented by general formula (1) satisfies the above-mentioned relationship, it is possible to achieve both a higher effect of inhibiting scalp staining and a more excellent hair dyeing effect. Furthermore, by preparing a hair dye composition in which the content of the component (A) to the sulfate of the compound represented by general formula (1) satisfies the above-mentioned relationship, it is possible to obtain higher emulsion stability.

[0011] Furthermore, the hair dye composition of the present invention is characterized in that it further contains (C) an alkanolamine. A hair dye composition containing 1 to 10% by mass of component (A) and the sulfate salt of the compound represented by general formula (1) can further improve the effect of inhibiting scalp staining and the hair dyeing effect by further containing an alkanolamine. Effect of the Invention

[0012] According to the present invention, it is possible to provide a hair dye composition containing an oxidation dye, which causes less skin staining, has excellent hair dyeing power, and further has excellent emulsion stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Next, the present invention will be described including the best mode for carrying out the present invention. The hair dye composition of the present invention is an emulsion composition containing an oily component, (A) 1 to 10% by mass of ascorbic acid, erythorbic acid, salts or esters thereof, and (B) an oxidation dye consisting of a sulfate salt of a compound represented by the following general formula (1): The hair dye composition is characterized by comprising: [ka] (wherein R represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, or a linear or branched mono- or polyaminoalkyl group.)

[0014] Hair dyes are classified into temporary hair dyes, semi-permanent hair dyes, and permanent hair dyes based on the durability of the hair dyeing effect, i.e., fastness. The hair dye composition of the present invention may be used as any of the hair dyes. For example, it may be used as an oxidation hair dye (permanent hair dye) containing an oxidation dye, a color treatment (semi-permanent hair dye) containing a direct dye, etc.

[0015] The hair dye composition of the present invention is an emulsion composition containing an oily component and a surfactant. The emulsion composition may be of any form, such as an oil-in-water type or a water-in-oil type, but is preferably an oil-in-water type emulsion composition.

[0016] The hair dye composition of the present invention may be in any form as long as it is an emulsion composition. For example, it may be in the form of a liquid, cream, gel, mist, etc. Note that it is sufficient to be an emulsion composition during storage, and it may be in the form of a foam or mist during use. When it is in the form of a foam, an aerosol foamer container, a non-aerosol foamer container, etc. may be used.

[0017] The hair dye composition of the present invention can be used as the first agent of a multi-agent oxidative hair dye, preferably a two-agent oxidative hair dye. The two-agent oxidative hair dye is composed of a first agent, which is the hair dye composition of the present invention containing an oil component and an oxidative dye, and a second agent containing an oxidizing agent, and the first agent and the second agent are mixed together when used.

[0018] Each component contained in the hair dye composition of the present invention will be described in detail below. The content of each component is the content of the hair dye composition during storage unless otherwise specified. For example, in the case of a two-component oxidative hair dye, it is the content of the first component containing the oil component and the oxidative dye.

[0019] [Ascorbic acid, erythorbic acid, their salts or esters] (A) Ascorbic acid, erythorbic acid, or a salt or ester thereof is contained in the hair dye composition in an amount of 1 to 10% by mass in order to promote the oxidative polymerization reaction of the oxidation dye by the oxidizing agent during the preparation of the mixture and to suppress background staining. From the viewpoint of the effect of suppressing background staining and hair dyeing power, the content is preferably 2% by mass or more as the lower limit, more preferably 3% by mass or more, and preferably 8% by mass or less as the upper limit, more preferably 6% by mass or less. By making it 1% by mass or more, a sufficient background staining prevention effect can be obtained, and by making it 10% by mass or less, the hair dyeing power is improved and further the emulsion stability of the dye composition is improved, which are preferable.

[0020] In the hair dye composition of the present invention, ascorbic acid, erythorbic acid, salts or esters thereof are used. Specific examples include ascorbic acid, sodium ascorbate, potassium ascorbate, calcium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, diethanolamine ascorbate, erythorbic acid, sodium erythorbate, disodium ascorbyl sulfate, magnesium ascorbyl phosphate, ascorbyl palmitate, ascorbyl stearate, ascorbyl dipalmitate, ascorbyl tetra-2-hexyldecanoate, ascorbyl myristate, lauryl phosphate, and the like. Examples of the ascorbyl phosphate include ascorbyl acetate, ascorbyl propionate, ascorbyl tartrate, ascorbyl citrate, ascorbyl succinate, ascorbyl benzoate, potassium (ascorbyl / tocopheryl) phosphate, ethyl ascorbyl, allantoin ascorbyl, chitosan ascorbate, methylsilanol ascorbate, tetradecylhexyl ascorbyl, aminopropyl ascorbyl phosphate, ascorbic acid polypeptide, ascorbyl glucoside, and ascorbyl methylsilanol pectinate.

[0021] Among these, ascorbic acid, sodium ascorbate, potassium ascorbate, calcium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, diethanolamine ascorbate, erythorbic acid, sodium erythorbate, disodium ascorbyl sulfate, magnesium ascorbyl phosphate, ascorbyl palmitate, ascorbyl stearate, ascorbyl dipalmitate, ascorbyl tetra-2-hexyldecanoate, potassium (ascorbyl / tocopheryl) phosphate, ethyl ascorbyl, allantoin ascorbyl, chitosan ascorbate, methylsilanol ascorbate, tetradecylhexyl ascorbyl, aminopropyl ascorbyl phosphate, ascorbyl polypeptide, ascorbyl glucoside, ascorbyl methylsilanol pectinate are preferred. Ascorbic acid or erythorbic acid are more preferred, and ascorbic acid is the most preferred.

[0022] In the present invention, one or more of these can be used. From the viewpoint of safety, it is preferable that the component (A) is contained in the first agent.

[0023] [Oxidation dyes] Oxidation dyes are dyes that develop color through oxidative polymerization with an oxidizing agent. Oxidation dyes include dye intermediates that develop color through their own oxidation, and couplers that produce various colors when combined with dye intermediates. The hair dye composition of the present invention contains a sulfate of a heterocyclic compound having a specific structure, which is a dye intermediate.

[0024] <Sulfates of heterocyclic compounds> The hair dye composition of the present invention contains a sulfate of a heterocyclic compound represented by the following general formula (1). [ka] (wherein R represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, or a linear or branched mono- or polyaminoalkyl group.)

[0025] As the sulfate of the compound of general formula (1) above (B), 1-hydroxyethyl-4,5-diaminopyrazole sulfate shown in the following formula is preferred. [ka]

[0026] When the oxidation dye consisting of the sulfate of the compound of the above general formula (1) is used in a hair dye composition containing a large amount (1 to 10%) of the component (A), it shows a higher hair dyeing power than the oxidation dye to which other sulfates are added while maintaining the effect of suppressing background staining. In addition, oxidation dye salts generally have low emulsion stability, and therefore the composition acceptable for the hair dye composition, which is an emulsion, tends to be limited, but the hair dye composition containing the oxidation dye consisting of the sulfate of the above compound has high emulsion stability, and other compositions are not limited, and it can be made into a hair dye composition having various compositions.

[0027] The content of the sulfate of the compound of the general formula (1) in the hair dye composition is not particularly limited, but is preferably 0.05 to 5% by mass from the viewpoint of hair dyeing power and emulsion 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 making it 5% by mass or less, it is possible to obtain a hair dye composition that exhibits high hair dyeing power and has even higher emulsion stability, and by making it 0.05% by mass or more, it is possible to obtain sufficient hair dyeing power.

[0028] The mass ratio (B / A) of the sulfate of the compound of the above general formula (1) to the component (A) is not particularly limited, but is, for example, 0.05 to 2. The lower limit is preferably more than 0.1, and more preferably 0.2 or more. The upper limit is preferably less than 1, and more preferably 0.5 or less. When (B / A) is 0.05 or more, the hair dyeing effect can be further enhanced, and when it is 2 or less, the effect of inhibiting scalp staining can be further enhanced.

[0029] The sum of the content of the component (A) and the content of the sulfate of the compound of general formula (1) (B) is not particularly limited, but is, for example, 11% by mass or less, and the upper limit is preferably less than 7% by mass. By making the sum of the contents 11% by mass or less, higher emulsion stability can be obtained. From the viewpoint of further exerting the effects of the present invention, the lower limit is preferably 2% by mass or more, and more preferably 4% by mass or more.

[0030] <Other oxidation dyes> The hair dye composition of the present invention may contain other oxidation dyes. The other oxidation dyes include dye intermediates and couplers. The dye intermediates are dye precursors, mainly o- or p-phenylenediamines or aminophenols, and are usually colorless or weakly colored compounds by themselves. Specific 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-chloro-p-phenylenediamine, 4-amino-m-cresol, 2-amino-4-hydroxyethylaminoanisole, 2,4-diaminophenol, and salts thereof.

[0031] Examples of couplers include mainly m-diamines, aminophenols, and diphenols. Specific examples include resorcinol, catechol, pyrogallol, phloroglucinol, 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, and tannic acid and salts thereof.

[0032] The oxidation dye includes the acid addition salts of the above-mentioned compounds. Examples of the acid addition salts include addition salts of inorganic acids such as hydrochlorides and sulfates, and addition salts of organic acids such as acetates. The content of the acid addition salts of the oxidation dye is not particularly limited, but from the viewpoint of emulsion 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.

[0033] These oxidation dyes can be used alone or in combination according to the desired color tone. The content of the other oxidation dye in the hair dye composition is not particularly limited, but is preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass.

[0034] [Alkaline agent] The alkaline agent has the effect of swelling the hair and promoting the penetration of dyes and oxidizing agents. Examples of the alkaline agent include alkanolamines, ammonia, silicates, carbonates, hydrogencarbonates, metasilicates, phosphates, sulfates, chlorides, organic amines, basic amino acids, hydroxides of alkali metals or alkaline earth metals, etc. Specifically, examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, aminomethylpropanol, isopropylamine, etc.; examples of silicates include sodium silicate and potassium silicate, etc.; examples of carbonates include sodium carbonate, ammonium carbonate, magnesium carbonate, guanidine carbonate, etc.; examples of hydrogencarbonates include sodium hydrogencarbonate and ammonium hydrogencarbonate, etc.; examples of metasilicates include sodium metasilicate and potassium metasilicate, etc.; examples of phosphates include primary ammonium phosphate. Examples of the sulfate include ammonium sulfate, etc., examples of the chloride include ammonium chloride, examples of the organic amine include 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-methyl-1,3-propanediol, and guanidine, examples of the basic amino acid include arginine, lysine, and salts thereof, and examples of the hydroxide of an alkali metal or alkaline earth metal include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide, etc. Among these, it is preferable to contain an alkanolamine, and it is more preferable to contain monoethanolamine.

[0035] The content of the alkaline agent in the hair dye composition is not particularly limited, but is preferably 0.5 to 10% by mass. The lower limit is more preferably 1% by mass or more, and even more preferably 2% by mass or more. The upper limit is more preferably 7% by mass or less, and even more preferably 5% by mass or less.

[0036] The hair dye composition of the present invention particularly preferably contains an alkanolamine (C). The hair dye composition containing 1 to 10% by mass of component (A) and the sulfate salt of the compound of general formula (1) can further improve the effect of inhibiting scalp staining and the hair dyeing effect by further containing an alkanolamine.

[0037] The mass ratio (A / C) of component (A) to alkanolamine (C) is not particularly limited, but is preferably 0.7 to 6. The lower limit is more preferably 0.9 or more, and the upper limit is more preferably less than 5. When (A / C) is 0.7 or more, the effect of inhibiting scalp staining and the effect of dyeing hair can be further enhanced, and when it is 6 or less, the effect of inhibiting scalp staining can be further enhanced and deterioration of the feel due to residual alkali can be suppressed.

[0038] The mass ratio (B / C) of the sulfate of the compound of general formula (1) (B) to the alkanolamine (C) is not particularly limited, but is preferably 0.10 to 10.0. The lower limit is more preferably 0.20 or more, even more preferably 0.25 or more, and particularly preferably 0.30 or more. The upper limit is more preferably 5.0 or less, even more preferably 2.0 or less, and particularly preferably 1.0 or less. When the mass ratio (B / C) is within the above range, the effect of inhibiting background staining and the effect of dyeing hair can be further enhanced.

[0039] [Oily ingredients] The hair dye composition of the present invention contains an oil component. Examples of the oil component include higher alcohols, oils and fats, waxes, hydrocarbons, higher fatty acids, esters, silicone oils, fluorine oils, etc. One or more of these oil components can be selected and used. By containing an oil component, the hair dyeing power can be improved.

[0040] Examples of higher alcohols include cetyl alcohol (cetanol), stearyl alcohol, cetostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, arachyl alcohol, behenyl alcohol, lauryl alcohol, myristyl alcohol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, decyltetradecanol, phytosterol, phytostanol, cholesterol, cholestanol, lanosterol, and ergosterol.

[0041] The fats and oils are triglycerides, i.e. triesters of fatty acids and glycerin. Examples of the fats and oils include olive oil, rosehip oil, camellia oil, shea butter, macadamia nut oil, almond oil, tea seed oil, camellia oil, safflower oil, sunflower oil, soybean oil, cottonseed oil, sesame oil, beef tallow, cacao butter, corn oil, peanut oil, rapeseed oil, rice bran oil, rice germ oil, wheat germ oil, pearl barley oil, grape seed oil, avocado oil, carrot oil, castor oil, linseed oil, coconut oil, mink oil, egg yolk oil, etc.

[0042] Waxes are esters of higher fatty acids and higher alcohols, such as beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, spermaceti, rice bran wax, sugarcane wax, palm wax, montan wax, cotton wax, bayberry wax, ivory wax, kapok wax, and shellac wax.

[0043] Hydrocarbons are compounds consisting of carbon and hydrogen. Examples include liquid paraffin, paraffin, microcrystalline wax, petrolatum, isoparaffins, ozokerite, ceresin, polyethylene, α-olefin oligomer, polybutene, synthetic squalane, squalene, hydrogenated squalane, limonene, and turpentine.

[0044] 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 lanolin fatty acid.

[0045] Esters are compounds obtained by dehydration reaction between 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 acid (C10-30) (cholesteryl / lanosteryl), lauryl lactate, octyldodecyl lactate, lanolin acetate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, lanolin derivatives, etc.

[0046] Silicone oil is a synthetic polymer in which silicon with organic groups and oxygen are alternately linked by chemical bonds. Examples include dimethylpolysiloxane (INCI name: dimethicone), dimethylpolysiloxane with hydroxyl end groups (INCI name: dimethiconol), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, polyether-modified silicone, highly polymerized silicone with an average degree of polymerization of 650 to 10,000, amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, and fluorine-modified silicone.

[0047] Of the above, examples of amino-modified silicones include aminopropylmethylsiloxane-dimethylsiloxane copolymer (INCI name: aminopropyl dimethicone), aminoethylaminopropylsiloxane-dimethylsiloxane copolymer (INCI name: amodimethicone), and aminoethylaminopropylmethylsiloxane-dimethylsiloxane copolymer (INCI name: trimethylsilylamodimethicone).

[0048] The content of the oily component in the hair dye composition is not particularly limited, but is preferably 0.1 to 30% by mass. The lower limit is more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more. The upper limit is more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0049] [Other ingredients] The hair dye composition of the present invention may contain the following components, if necessary, in addition to the above components. Other ingredients include, for example, direct dyes, surfactants, antioxidants such as sodium sulfite anhydride, preservatives such as phenoxyethanol and sodium benzoate, organic solvents such as ethanol, sugars such as sorbitol and maltose, water-soluble polymers such as hydroxyethyl cellulose and carboxyvinyl polymer, cationic water-soluble polymers such as polychlorinated dimethyldimethylene piperidinium solution (polychlorinated dimethyldimethylene pyrrolidinium solution), diallyldimethylammonium chloride and hydroxyethyl cellulose, polyhydric alcohols such as polyethylene glycol and dipropylene glycol, chelating agents such as ethylenediaminehydroxyethyl triacetate trisodium dihydrate and hydroxyethanediphosphonic acid 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, pyrophosphoric acid, gluconic acid, glucuronic acid, pH adjusters, hair growth ingredients, plant extracts, herbal extracts, amino acids and peptides, urea, vitamins other than ascorbic acid (excluding vitamin A), fragrances, and ultraviolet absorbers.

[0050] <Direct dye> The direct dye is a compound having a color, and is not particularly limited as long as it adheres to or penetrates into hair to dye it. Examples of the direct dye include acid dyes, basic dyes, natural dyes, nitro dyes, HC dyes, and disperse dyes. These direct dyes may be used alone or in combination of two or more depending on the desired hair color tone.

[0051] Specific examples of acid dyes include 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, and Black No. 401.

[0052] Specific examples of basic dyes include 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, and Basic Yellow 87.

[0053] Specific examples of natural dyes include gardenia dye, turmeric dye, annatto dye, sodium copper chlorophyllin, paprika dye, lac dye, and henna.

[0054] Specific examples of nitro dyes include 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, picramic acid, picric acid, and salts thereof.

[0055] 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, and HC Yellow No. 15.

[0056] Specific examples of disperse dyes include 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.

[0057] The content of the direct dye 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.

[0058] <Surfactant> The surfactant may be a nonionic surfactant, a cationic surfactant, an anionic surfactant, or an amphoteric surfactant. In the following description, POE stands for polyoxyethylene chain, POP stands for polyoxypropylene chain, and the numbers in parentheses following each indicate the number of moles added. The number in parentheses following alkyl indicates the number of carbon atoms in the fatty acid chain.

[0059] Examples of nonionic surfactants include POE alkyl ethers, POE alkyl phenyl 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, alkyl polyglucosides, etc. Specific examples of POE alkyl ethers include POE lauryl ether, POE cetyl ether, POE stearyl ether, POE behenyl ether, POE lanolin, POE phytosterol, etc. The number of repeating units of POE and POP is, for example, 2 to 100, and any of them can be used as long as they exhibit a surface active effect.

[0060] The content of the nonionic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 40% by mass. The lower limit is more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0061] Examples of cationic surfactants include alkyl quaternary ammonium salts such as monoalkyl-type quaternary ammonium salts, dialkyl-type quaternary ammonium salts, trialkyl-type quaternary ammonium salts, benzalkonium-type quaternary ammonium salts, and monoalkyl ether-type quaternary ammonium salts; amine salts such as alkylamine salts, fatty acid amide amine salts, ester-containing tertiary amine salts, and arcobel-type tertiary amine salts; cyclic quaternary ammonium salts such as alkylpyridinium salts and alkylisoquinolium salts; and benzethonium chloride.

[0062] Preferred are alkyl quaternary ammonium salts, more preferred are monoalkyl-type quaternary ammonium salts and dialkyl-type quaternary ammonium salts, and particularly preferred are monoalkyl-type quaternary ammonium salts.

[0063] Examples of monoalkyl quaternary ammonium salts include lauryl trimethyl ammonium chloride, lauryl trimethyl ammonium bromide, alkyl (16,18) trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium saccharin, stearyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium chloride, stearyl trimethyl ammonium saccharin, alkyl (28) trimethyl ammonium chloride, diPOE (2) oleyl methyl ammonium chloride, diPOE stearyl methyl ammonium chloride, POE (1) POP (25) diethyl methyl ammonium chloride, POP methyl diethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, behenyl trimethyl ammonium methyl sulfate, etc. Particularly preferred are stearyl trimethyl ammonium chloride, alkyl (16,18) trimethyl ammonium chloride, and cetyl trimethyl ammonium chloride.

[0064] Examples of dialkyl-type quaternary ammonium salts include dialkyl(12-15)dimethylammonium chloride, dialkyl(12-18)dimethylammonium chloride, dialkyl(14-18)dimethylammonium chloride, dicocoyl dimethylammonium chloride, dicetyl dimethylammonium chloride, distearyl dimethylammonium chloride, and isostearyl lauryl dimethylammonium chloride.

[0065] The content of the cationic surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 10% by mass. The lower limit is more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. The upper limit is more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0066] 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-sulfonic acid salts, N-acylamino acid surfactants, phosphoric acid mono- or diester surfactants, and sulfosuccinic acid esters. The counter ion of the anionic group of these surfactants may be, for example, any of sodium ion, potassium ion, and triethanolamine.

[0067] 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 taurine, triethanolamine dodecylbenzenesulfonate, sodium tetradecenesulfonate, sodium lauryl phosphate, POE lauryl ether phosphate and salts thereof, N-lauroyl glutamate salts (such as sodium lauroyl glutamate), N-lauroyl methyl-β-alanine salts, N-acyl glycine salts, N-acyl glutamate salts, higher fatty acids such as lauric acid and myristic acid, and salts of these higher fatty acids. One or more of these may be used.

[0068] The content of the anionic surfactant in the hair dye composition is not particularly limited, but is preferably 0.01 to 5% 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 3% by mass or less, and even more preferably 1.5% by mass or less.

[0069] Examples of the amphoteric surfactant include amino acid type amphoteric surfactants and betaine type amphoteric surfactants. Specific examples of the amino acid type amphoteric surfactant include, for example, N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (sodium lauroamphoacetate), 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, sodium undecylhydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, N-coconut oil fatty acid acyl-N'-carboxyethyl-N'-hydroxyethylethylenediamine sodium, N-coconut oil fatty acid acyl-N'-carboxyethoxyethyl-N' glycine type amphoteric surfactants such as N-carboxyethylethylenediamine disodium, N-coconut oil fatty acid acyl-N'-carboxymethoxyethyl-N'-carboxymethylethylenediamine disodium, sodium lauryldiaminoethylglycine, and palm oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium; aminopropionic acid type amphoteric surfactants such as sodium lauryl aminopropionate, sodium lauryl aminodipropionate, and triethanolamine lauryl aminopropionate; and the like. Specific examples of betaine-type amphoteric surfactants include aminoacetic acid betaine-type amphoteric surfactants such as coconut oil alkyl betaine, lauryl dimethylaminoacetic acid betaine, myristyl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, sodium stearyl dimethyl betaine, coconut oil fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, ricinoleic acid amidopropyl betaine, and stearyl dihydroxyethyl betaine; and sulfobetaine-type amphoteric surfactants such as lauryl hydroxysulfobetaine.

[0070] The content of the amphoteric surfactant in the hair dye composition is not particularly limited, but is preferably 0.001 to 5% by mass. The lower limit is more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more. The upper limit is more preferably 3% by mass or less, and even more preferably 2.5% by mass or less.

[0071] 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.

[0072] <Polyhydric alcohol> Examples of polyhydric alcohols include polyethylene glycol and dipropylene glycol. Among these, from the viewpoint of improving the effect of suppressing background staining, polyethylene glycol is preferred, and (D) polyethylene glycol 400 is more preferred. The content of the polyhydric alcohol in the hair dye composition is not particularly limited, but is preferably 0.1 to 20% by mass. The lower limit is more preferably 1% by mass or more, and the upper limit is more preferably 10% by mass or less.

[0073] The pH of the hair dye composition of the present invention is not particularly limited, but is, for example, pH 7 to 11 immediately after mixing. The sulfate of the compound of formula (1), particularly 1-hydroxyethyl-4,5-diaminopyrazole sulfate, has a characteristic of showing red color in the low pH range, which is not seen in other oxidation dyes. From the viewpoint of improving hair dyeing power, the upper limit of pH immediately after mixing is preferably pH 9.5 or less, more preferably pH 9.2 or less, and even more preferably pH 9 or less. Also, from the viewpoint of producing a vivid red color, the lower limit of pH immediately after mixing is preferably pH 7.5 or more, more preferably pH 7.8 or more, and even more preferably pH 8.0 or more.

[0074] The pH of the hair dye composition can be adjusted using an acid such as phosphoric acid or an alkali such as sodium hydroxide. The pH of the hair dye composition of the present invention is a value measured immediately after mixing a 10% solution of a 1:1 mixture of the first and second agents. The measurement can be performed using a pH meter such as pH-METERF-22 manufactured by HORIBA.

[0075] [Composition of the second agent] When the hair dye composition of the present invention is used as the first agent of a two-agent type oxidation hair dye, the second agent may be a general second agent used in the field of oxidation hair dye. The composition of the second agent is not particularly limited, but it is preferable that it contains an oxidizing agent, and the oxidizing agent is preferably hydrogen peroxide. The content of hydrogen peroxide in the second agent is 0.1 to 9% by mass from the viewpoint of the effect of suppressing background staining, and the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 6% by mass or less, and more preferably 3% by mass or less. When it is 9% by mass or less, the effect of suppressing background staining is further improved. In addition, by making the concentration 0.1% by mass or more, a sufficient effect as an oxidizing agent can be obtained. EXAMPLES

[0076] The present invention will be described in detail below with reference to examples, but the technical scope of the present invention is not limited to these examples.

[0077] 1. Evaluation of hair dye compositions [Preparation of hair dye composition] (Hair dye composition containing an oxidation dye) A first agent of a two-agent type oxidation hair dye was prepared as a hair dye composition containing an oxidation dye. The formulation of the first agent is shown in Tables 1 to 3 below. The preparation of the first agent was carried out according to a conventional method. The blending amounts in the tables are in mass%.

[0078] [Preparation of the second agent] A second agent having the following composition (hydrogen peroxide concentration: 2% by mass) was prepared by a conventional method. (Second agent) Cetanol 1.2% by mass POE(30) cetyl ether 0.3% by mass POE(10) cetyl ether 0.3% by mass Stearyltrimethylammonium chloride 1.0% by mass Hydrogen peroxide (35% by mass) 5.7% by mass Hydroxyethanediphosphonic acid 0.1% by mass Hydroxyethanediphosphonic acid tetrasodium 0.2% by mass Phenoxyethanol 0.1% by mass Purified water remainder Total 100% by mass

[0079] [Evaluation method] <Emulsification stability> 30 grams of the hair dye composition (first agent) prepared above was weighed out into a No. 4 standard bottle, the bottle was covered with an inner lid and a lid, and the bottle was left to stand at 50°C and 60°C, and evaluated according to the following criteria. (Emulsion stability criteria) 5: No separation was observed even after storing at 50°C for one month or at 60°C for two weeks. 4: No separation was observed even after storing at 50°C for one month or at 60°C for one week. 3: No separation was observed even after storing at 50°C for one month or at 60°C for three days. 2: No separation was observed even when left at 50°C for one month or at 60°C for one day. 1: No separation was observed at 50°C for one month, but separation was observed after one day at 60°C.

[0080] <Skin stains> The hair dye composition (first agent) according to each example was mixed with the second agent in a 1:1 ratio to prepare an oxidation hair dye, and 1 g of the oxidation hair dye was applied to a circular area of ​​1 cm in diameter on the inside of the arm, left for 10 minutes, and then washed off with warm water. Next, the area was lightly rubbed with soap and fingers for 1 minute, and washed off with warm water.

[0081] After the above-mentioned treatment, 10 panelists visually observed the skin staining (degree of dyeing to the skin). In the visual evaluation, the skin staining was evaluated according to the following evaluation criteria, and the average of the evaluation scores of the 10 panelists was rounded off to the nearest whole number to obtain the evaluation score of each hair dye composition. (Criteria for determining background stains) 5: Very little staining of the scalp. 4: Less dirt on the scalp. 3: Slightly less dirt on the scalp. 2: There is a lot of dirt on the scalp. 1: There is a lot of scalp dirt.

[0082] <Hair dyeing power> (Hair dyeing method using hair dye composition) The hair dye composition (first agent) and the second agent according to each example were mixed at a ratio of 1:1 to prepare an oxidation hair dye. 1 g of this oxidation hair dye was applied to 1 g of hair bundle and left at 30°C for 30 minutes. The hair bundle was then washed with shampoo to wash off the oxidation hair dye. Next, a conditioner was applied to the hair bundle. After rinsing the hair bundle to wash off the conditioner, the moisture of the hair bundle was wiped off with a towel and finally dried with a hair dryer.

[0083] The hair bundles dyed as described above were visually observed by 10 panelists for their dyed condition. In the visual evaluation, the dyeing ability was evaluated according to the following evaluation criteria, and the average of the scores given by the 10 panelists was rounded off to the nearest whole number to obtain the evaluation score for each hair dye composition. (Criteria for judging hair dyeing power) 5: Very high dyeing power. 4: High dyeing power. 3: Slightly strong dyeing power. 2: Low dyeing power. 1: Very poor dyeing power.

[0084] [Table 1]

[0085] Referring to Table 1, in Examples 1 to 3 containing 1 to 10% by mass of (A) ascorbic acid and (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate, it was found that a high scalp stain suppression effect, hair dyeing power, and emulsion stability were achieved at the same time, compared to Comparative Examples 1 to 3 in which the ascorbic acid content was outside the specified range. In Comparative Examples 4 and 5, which did not contain 1-hydroxyethyl-4,5-diaminopyrazole sulfate, it was difficult to achieve a high scalp stain suppression effect, hair dyeing power, and emulsion stability at the same time.

[0086] [Table 2]

[0087] In Table 2, the mass ratio and total content of (A) ascorbic acid and (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate were examined. In examples where the mass ratio (B / A) of (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate to (A) ascorbic acid exceeded 0.1, excellent hair dyeing power was confirmed. In addition, in examples where (B / A) was less than 1, excellent scalp stain suppression effect was confirmed.

[0088] Furthermore, excellent emulsion stability was confirmed in the examples in which the sum of the content of (A) ascorbic acid and the content of (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate was less than 7 mass %.

[0089] [Table 3]

[0090] In Table 3, the presence or absence and content of (C) alkanolamines are examined. Compared with Example 10 which did not contain the (C) alkanolamine monoethanolamine, Examples 1, 7 to 9 which contained monoethanolamine showed a high scalp stain suppression effect and an excellent hair dyeing effect. Also, a higher scalp stain suppression effect was confirmed in Examples in which the mass ratio (A / C) of (A) ascorbic acid to (C) alkanolamine was 0.7 or more, and particularly in Example 1 in which the mass ratio was 0.9 or more and less than 5, it was confirmed that both the scalp stain suppression effect and the hair dyeing effect were achieved. Furthermore, the effect of inhibiting scalp staining and the improvement in hair dyeing effect due to alkanolamine were not observed in the comparative examples not containing (B) 1-hydroxyethyl-4,5-diaminopyrazole sulfate.

[0091] 2. Effects of the composition of the second agent In order to confirm the influence of the composition of the second agent on the effect of inhibiting scalp staining and hair dyeing effect, oxidative hair dyes A and B were prepared using the second agent (second agent-A) used in the above experiment shown in Table 4 and second agent-B, in which the hydrogen peroxide concentration was increased to 5.8%, and experiments were carried out in the same manner as the previous experiment regarding scalp staining and hair dyeing ability. The hair dye composition of Example 1 used in the above experiment was used as the first agent. The results of the experiment are shown in Table 5. The units of the blend amounts in the table are mass %.

[0092] [Table 4]

[0093] [Table 5]

[0094] As shown in Table 5, oxidative hair dye B, which has a high hydrogen peroxide concentration of 6% by mass in the second agent, was found to have a lower effect of inhibiting scalp staining compared to oxidative hair dye A, which has a hydrogen peroxide concentration of 2% by mass. However, no difference was observed in hair dyeing power. [Industrial Applicability]

[0095] The oxidative hair dye composition of the present invention is used for dyeing human head hair, beard, eyebrows, leg hair, and other body hair. It can also be used as a hair dye for pets and other animals. It may be used. The oxidation hair dye composition of the present invention is a hair dye for coloring in beauty salons, barber shops, etc. It can be used as a hair dye for self-coloring.

Claims

1. An emulsion composition containing an oily component, (A) 1 to 6% by mass of one or more components selected from the group consisting of ascorbic acid, sodium ascorbate, potassium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, diethanolamine ascorbate, erythorbic acid, sodium erythorbate, disodium ascorbyl sulfate, magnesium ascorbyl phosphate, ascorbyl acetate, ascorbyl propionate, ascorbyl tartrate, ascorbyl benzoate, ethyl ascorbyl, allantoin ascorbyl, aminopropyl ascorbyl phosphate, and ascorbyl glucoside, and (B) containing an oxidation dye consisting of a sulfate salt of a compound represented by the following general formula (1), A hair dye composition, characterized in that the sum of the content of the component represented by (A) and the content of the sulfate salt of the compound represented by general formula (1) (B) is less than 7 mass%. 【Chemistry 1】 (wherein R represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, or a linear or branched mono- or polyaminoalkyl group.)

2. An emulsion composition containing an oily component, A hair dye composition comprising: (A) 1 to 10% by mass of one or more components selected from the group consisting of ascorbic acid, sodium ascorbate, potassium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, diethanolamine ascorbate, erythorbic acid, sodium erythorbate, disodium ascorbyl sulfate, magnesium ascorbyl phosphate, ascorbyl acetate, ascorbyl propionate, ascorbyl tartrate, ascorbyl benzoate, ethyl ascorbyl, allantoin ascorbyl, aminopropyl ascorbyl phosphate, and ascorbyl glucoside; and (B) an oxidation dye comprising a sulfate salt of a compound represented by the following general formula (1): The hair dye composition is used in combination with a second agent containing an oxidizing agent, or the second agent or both of said second agents contain a cationic surfactant. 【Chemistry 1】 (wherein R represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, or a linear or branched mono- or polyaminoalkyl group.)

3. An emulsion composition containing an oily component, The composition contains (A) 1 to 10 mass % of one or more components selected from the group consisting of ascorbic acid, sodium ascorbate, potassium ascorbate, ammonium ascorbate, monoethanolamine ascorbate, diethanolamine ascorbate, erythorbic acid, sodium erythorbate, disodium ascorbyl sulfate, magnesium ascorbyl phosphate, ascorbyl acetate, ascorbyl propionate, ascorbyl tartrate, ascorbyl benzoate, ethyl ascorbyl, allantoin ascorbyl, aminopropyl ascorbyl phosphate, and ascorbyl glucoside, and (B) an oxidation dye consisting of a sulfate salt of a compound represented by the following general formula (1), A hair dye composition, characterized in that the mass ratio (B / A) of the sulfate salt of the compound represented by general formula (1) (B) to the component represented by (A) is greater than 0.1 and less than 1. 【Chemistry 1】 (wherein R represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched mono- or polyhydroxyalkyl group having 2 to 6 carbon atoms, or a linear or branched mono- or polyaminoalkyl group.)

4. The hair dye composition according to any one of claims 1 to 3, wherein the sulfate of the compound represented by formula (1) (B) is 1-hydroxyethyl-4,5-diaminopyrazole sulfate.

5. The hair dye composition according to any one of claims 1 to 4, characterized in that the mass ratio (B / A) of the sulfate of the compound represented by general formula (1) (B) to the component represented by general formula (A) is more than 0.1 and less than 1, the content of the component represented by general formula (A) is 1 to 6 mass%, and the sum of the contents of the component represented by general formula (A) and the sulfate of the compound represented by general formula (1) (B) is less than 7 mass%.

6. The hair dye composition according to any one of claims 1 to 5, further comprising (C) an alkanolamine.

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